US3597172A - Alloys having an aluminum-diffused surface layer - Google Patents

Alloys having an aluminum-diffused surface layer Download PDF

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Publication number
US3597172A
US3597172A US701317A US3597172DA US3597172A US 3597172 A US3597172 A US 3597172A US 701317 A US701317 A US 701317A US 3597172D A US3597172D A US 3597172DA US 3597172 A US3597172 A US 3597172A
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United States
Prior art keywords
aluminum
alloys
nickel
diffused
layer
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US701317A
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Karl Bungardt
Gottfried Becker
Gunter Lehnert
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Deutsche Edelstahlwerke AG
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Deutsche Edelstahlwerke AG
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23PMETAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • B23P15/04Making specific metal objects by operations not covered by a single other subclass or a group in this subclass turbine or like blades from several pieces
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C10/00Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/923Physical dimension
    • Y10S428/924Composite
    • Y10S428/926Thickness of individual layer specified
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736Al-base component
    • Y10T428/1275Next to Group VIII or IB metal-base component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12931Co-, Fe-, or Ni-base components, alternative to each other
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12937Co- or Ni-base component next to Fe-base component

Definitions

  • This invention relates to an improvement in the resistance to oxidation and corrosion of parts made of certain alloys, namely high temperature steels and nickel-based or cobalt-based alloys, having aluminum diffused into their surfaces.
  • the diffusion of aluminum into the surface of parts is a known method of improving the oxidation and corrosion resistance thereof.
  • the conventional procedure consists in packing the objects into a powder mixture substantially consisting of metallic aluminum and aluminum oxide as an inert component. By raising the temperature to between 1000 and 1100 C. the metallic aluminum can be made to diffuse into the surfaces of the parts and to form a diffusion layer which protects the parts against oxidation and corrosion during their subsequent use.
  • the invention relates to a further improvement of the known process of aluminum diffusion, in that high temperature steels, nickel-based alloys and cobalt-based alloys parts are provided with a nickel coating before they are submitted to the process of aluminum diffusion.
  • the accompanying drawing is a graphical illustration of the advantages obtainable by the process of the invention in comparison with untreated parts or with parts that have been submitted only to the aluminum diffusion treatment.
  • the ordinate of the said graph represents the loss in weight per unit of surface area by heating in still air at 1200 C., and the abscissa represents time.
  • the comparative tests were performed using a nickel based alloy containing 20% chromium, 2.4% titanium and 1.4% aluminum.
  • Aluminum was diffused into the surface by heating samples at 1100 C. for a period of 5 hours in a powder mixture containing 5% aluminum and 95% aluminum oxide.
  • the sample that was treated according to the invention was first degreased and pickled and before being subjected to the aluminum diffusion treatment it was electrolytically provided with a a coat- "ice ing of nickel by a minute treatment in a hydrochloric acid nickel chloride bath at 35 C. using a current density of 25 a./dm.
  • the thickness of the nickel coating is from 3 to 20 1, particularly from 5 to 10 1.
  • the thickness of the aluminum diffusion layer is preferably from 20 to 100M, Particularly from to 70.

Abstract

IT IS KNOWN TO PROTECT THE SURFACE OF ALLOYS WITH A LAYER OF DIFFUSED ALUMINUM. IT HAS NOW BEEN FOUND THAT THE OXIDATIVE RESISTANCE OF CERTAIN ALLOYS, NAMELY HIGH TEMPERATURE STEELS, NICKEL BASED AND COBALT BASED ALLOYS, IS IMPROVED IF THE ALUMINUM LAYER IS DIFFUSED ONTO A SUBSTRATE OF NICKEL.

Description

Aug.3, 1971 BUNGARDT ETAL 3,597,172
ALLOYS HAVING AN ALUMINUM-DIFFUSED SURFACE LAYER Filed Jan. 29, 1968 III Ivy/m1 United States Patent 3,597,172 ALLOYS HAVING AN ALUMINUM-DIFFUSED SURFACE LAYER Karl Bungardt, Krefeld, Gottfried Becker, Dusseldorf, and Giinter Lehnert, Krefeld, Germany, assignors to Deutsche Edelstahlwerke Aktiengesellschaft, Krefeld, Germany Filed Jan. 29, 1968, Ser. No. 701,317 Claims priority, application Germany, Jan. 31, 1967, D 52,148 Int. Cl. 1332b 15/00 U.S. Cl. 29194 4 Claims ABSTRACT OF THE DISCLOSURE It is known to protect the surface of alloys with a layer of diffused aluminum. It has now been found that the oxidative resistance of certain alloys, namely high temperature steels, nickel based and cobalt based alloys, is improved it the aluminum layer is diffused onto a substrate of nickel.
This invention relates to an improvement in the resistance to oxidation and corrosion of parts made of certain alloys, namely high temperature steels and nickel-based or cobalt-based alloys, having aluminum diffused into their surfaces.
The diffusion of aluminum into the surface of parts is a known method of improving the oxidation and corrosion resistance thereof. The conventional procedure consists in packing the objects into a powder mixture substantially consisting of metallic aluminum and aluminum oxide as an inert component. By raising the temperature to between 1000 and 1100 C. the metallic aluminum can be made to diffuse into the surfaces of the parts and to form a diffusion layer which protects the parts against oxidation and corrosion during their subsequent use.
Parts consisting for example of an alloy containing about 70% nickel, 20% chromium, remainder accompanying elements such for example as titanium, cobalt, silicon, manganese or iron, superficially oxidise when heated in air to about 1200 C., the oxide layer continuously forming and flaking off without a significant incu bation period. However parts made of the same alloy but provided with an aluminum layer diffused into their surfaces resist oxidative attack under the same conditions for 150 to 200 hours.
The invention relates to a further improvement of the known process of aluminum diffusion, in that high temperature steels, nickel-based alloys and cobalt-based alloys parts are provided with a nickel coating before they are submitted to the process of aluminum diffusion.
The accompanying drawing is a graphical illustration of the advantages obtainable by the process of the invention in comparison with untreated parts or with parts that have been submitted only to the aluminum diffusion treatment. The ordinate of the said graph represents the loss in weight per unit of surface area by heating in still air at 1200 C., and the abscissa represents time.
The comparative tests were performed using a nickel based alloy containing 20% chromium, 2.4% titanium and 1.4% aluminum. Aluminum was diffused into the surface by heating samples at 1100 C. for a period of 5 hours in a powder mixture containing 5% aluminum and 95% aluminum oxide. The sample that was treated according to the invention was first degreased and pickled and before being subjected to the aluminum diffusion treatment it was electrolytically provided with a a coat- "ice ing of nickel by a minute treatment in a hydrochloric acid nickel chloride bath at 35 C. using a current density of 25 a./dm.
It will be seen from the graph that the life of the 5 sample which had been provided with a nickel undercoating (shown in curve C) was substantially longer than that of the sample that had been provided with an aluminum diffusion layer in conventional manner (shown in curve B), which was itself substantially better than an 10 untreated sample, shown in curve A. This result was surprising in view of the fact that the nickel alloy of the parts submitted to the comparative tests as such already contained a major proportion of nickel, and it was not therefore to be expected that the resistance to oxidation 15 and scaling would be very substantially improved by the provision of an underlayer of nickel.
An improvement in the life of parts provided with an undercoating of nickel compared with parts that have been merely aluminised by diffusion was also found to occur with an alloy containing 43% cobalt, 20% chr0- mium, 20% nickel, 4% each of tungsten, molybdenum and niobium, 0.4% carbon, remainder iron, silicon and manganese.
The advantages which the above tests confirm can also be achieved by applying the nickel coating and the aluminised layer by methods other than those herein described.
It is preferred that the thickness of the nickel coating is from 3 to 20 1, particularly from 5 to 10 1., and the thickness of the aluminum diffusion layer is preferably from 20 to 100M, Particularly from to 70 The invention may be applied with advantage to the production of blading for turbines which is exposed at high temperatures to the oxidative and corrosive effect of combustion gases.
What is claimed is:
1. A part made of an alloy selected from the group consisting of a high temperature steel, a nickel based alloy and a cobalt based alloy, said part having a nickel coating; and said part having aluminum diffused into the surface thereof from exteriorly of said nickel coating, said part being thereby provided with improved oxidation and corrosion resistance.
2. The part of claim 1 wherein the part is a turbine blade.
3. The part of claim 1 wherein the nickel coating has a thickness of from 3 to 20,11. and the aluminum has a thickness of from 20 to 100,14.
4. The part of claim 1 wherein the nickel coating has a thickness of from 5 to 10 and the aluminum has a thickness of from 40 to 70 References Cited UNITED STATES PATENTS 2,611,163 9/1952 Schaefer et al 164-75 2,687,565 8/1954 Schaefer et al. 29196.2X 3,000,755 9/1961 Hanink et al 29196.2X 3,044,156 7/ 1962 Whitfield et al. 29l94- 3,129,069 4/1964 Hanink et a1. 29l94X 3,141,744 7/1964 Couch et al. 29194 3,450,512 6/1969 Maxwell 29l94X 3,477,831 11/1969 Talboom et a1 29l94X L. DEWAYNE RUTLEDGE, Primary Examiner E. L. WEISE, Assistant Examiner U.S. Cl. X.R.
US701317A 1967-01-31 1968-01-29 Alloys having an aluminum-diffused surface layer Expired - Lifetime US3597172A (en)

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US (1) US3597172A (en)
BE (1) BE709691A (en)
CH (1) CH498205A (en)
DE (1) DE1621224B1 (en)
FR (1) FR1553233A (en)
GB (1) GB1166591A (en)
NL (1) NL6800878A (en)
SE (1) SE327321B (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859061A (en) * 1973-04-23 1975-01-07 Chromalloy American Corp Corrosion resistant coating system for ferrous metal articles having brazed joints
US3884729A (en) * 1972-11-03 1975-05-20 British Steel Corp Method of providing an aluminum coating on a steel substrate
US3897222A (en) * 1971-06-02 1975-07-29 Standard Pressed Steel Co Protective coating for ferrous metals
US3898052A (en) * 1973-04-23 1975-08-05 Chromalloy American Corp Corrosion resistant coating system for ferrous metal articles having brazed joints
US4071659A (en) * 1975-11-13 1978-01-31 Texas Instruments Incorporated Solar absorption surface panel
US4087589A (en) * 1975-10-14 1978-05-02 General Electric Company Coated article
US4190493A (en) * 1975-02-26 1980-02-26 Sulzer Brothers Limited Coated structural component for a high temperature nuclear reactor
US4241147A (en) * 1978-10-23 1980-12-23 Alloy Surfaces Company, Inc. Diffusion aluminized age-hardenable stainless steel
JPS56273A (en) * 1979-06-14 1981-01-06 Mitsubishi Heavy Ind Ltd Diffusion-penetration method of alloy
US4260654A (en) * 1974-02-27 1981-04-07 Alloy Surfaces Company, Inc. Smooth coating
US5236788A (en) * 1990-02-02 1993-08-17 Mtu Motoren- Und Turbinen-Union Muenchen Gmbh Iron-base alloy structural component having a corrosion-inhibiting coating
US5270081A (en) * 1990-02-02 1993-12-14 Mtu Motoren-Und Turbinen-Union Muenchen Gmbh Iron-base alloy structural component having a corrosion-inhibiting coating, and method of producing the coating

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647517A (en) * 1970-06-22 1972-03-07 Chromalloy American Corp Impact resistant coatings for cobalt-base superalloys and the like
GB1397066A (en) * 1971-06-19 1975-06-11 Rolls Royce High temperature corrosion resistant alloys

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897222A (en) * 1971-06-02 1975-07-29 Standard Pressed Steel Co Protective coating for ferrous metals
US3884729A (en) * 1972-11-03 1975-05-20 British Steel Corp Method of providing an aluminum coating on a steel substrate
US3859061A (en) * 1973-04-23 1975-01-07 Chromalloy American Corp Corrosion resistant coating system for ferrous metal articles having brazed joints
US3898052A (en) * 1973-04-23 1975-08-05 Chromalloy American Corp Corrosion resistant coating system for ferrous metal articles having brazed joints
US4260654A (en) * 1974-02-27 1981-04-07 Alloy Surfaces Company, Inc. Smooth coating
US4190493A (en) * 1975-02-26 1980-02-26 Sulzer Brothers Limited Coated structural component for a high temperature nuclear reactor
US4087589A (en) * 1975-10-14 1978-05-02 General Electric Company Coated article
US4071659A (en) * 1975-11-13 1978-01-31 Texas Instruments Incorporated Solar absorption surface panel
US4241147A (en) * 1978-10-23 1980-12-23 Alloy Surfaces Company, Inc. Diffusion aluminized age-hardenable stainless steel
JPS56273A (en) * 1979-06-14 1981-01-06 Mitsubishi Heavy Ind Ltd Diffusion-penetration method of alloy
JPS5710182B2 (en) * 1979-06-14 1982-02-25
US5236788A (en) * 1990-02-02 1993-08-17 Mtu Motoren- Und Turbinen-Union Muenchen Gmbh Iron-base alloy structural component having a corrosion-inhibiting coating
US5270081A (en) * 1990-02-02 1993-12-14 Mtu Motoren-Und Turbinen-Union Muenchen Gmbh Iron-base alloy structural component having a corrosion-inhibiting coating, and method of producing the coating

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Publication number Publication date
FR1553233A (en) 1969-01-10
DE1621224B1 (en) 1971-02-04
GB1166591A (en) 1969-10-08
BE709691A (en) 1968-05-30
CH498205A (en) 1970-10-31
NL6800878A (en) 1968-08-01
SE327321B (en) 1970-08-17

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