WO2022208861A1 - 耐熱合金部材およびその製造方法ならびに高温装置およびその製造方法 - Google Patents

耐熱合金部材およびその製造方法ならびに高温装置およびその製造方法 Download PDF

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WO2022208861A1
WO2022208861A1 PCT/JP2021/014268 JP2021014268W WO2022208861A1 WO 2022208861 A1 WO2022208861 A1 WO 2022208861A1 JP 2021014268 W JP2021014268 W JP 2021014268W WO 2022208861 A1 WO2022208861 A1 WO 2022208861A1
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Prior art keywords
alloy
heat
layer
resistant alloy
resistant
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English (en)
French (fr)
Japanese (ja)
Inventor
敏夫 成田
泰道 加藤
拓郎 成田
元博 大塚
真由美 荒
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Dbc System R&d Co Ltd
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Dbc System R&d Co Ltd
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Priority to JP2023510128A priority patent/JP7369499B2/ja
Publication of WO2022208861A1 publication Critical patent/WO2022208861A1/ja
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/48—Aluminising
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants

Definitions

  • the present invention relates to a heat-resistant alloy member, a method for manufacturing the same, a high-temperature device, and a method for manufacturing the same, and in particular, incinerators, boilers, gas turbines, and jet engines used in an environment where heating and cooling are repeated in a high-temperature oxidizing atmosphere. , exhaust gas system members, and the like.
  • Thermal Barrier Coating is applied to heat-resistant alloy substrates used in various combustion equipment, turbines, jet engines, and the like.
  • a thermally grown oxide (TGO) mainly composed of Al 2 O 3 is formed at the interface between the top layer and the bond layer to suppress oxidation of the heat resistant alloy base material.
  • the top layer and the bond layer are sometimes called a thermal barrier layer (TBC).
  • the element of the substrate diffuses to the bond layer side and the Al of the bond layer diffuses to the substrate side during use, so the Al concentration in the bond layer decreases, forming a non-protective TGO.
  • the top layer (YSZ) is peeled off at an early stage due to growth, and a solution to this problem is desired.
  • Japanese Patent No. 5905336 Japanese Patent No. 5905354
  • Japanese Patent No. 5905355 Japanese Patent No. 3857689 Japanese Patent No. 3857690 Japanese Patent No. 3910588 Japanese Patent No. 4753720
  • the diffusion barrier layer prevents elements of the base material from diffusing to the bond layer side and Al of the bond layer from diffusing to the base material side during use.
  • the blade base material contains 4.9% or more of Al by weight. Since it is made of a Ni-based single crystal superalloy containing 0.2% or less, protective Al 2 O 3 is formed on the surface of the blade base material during high-temperature oxidation, and oxidation resistance can be ensured.
  • the problem to be solved by the present invention is that even when a heat-resistant alloy base material containing no Al or having a low Al concentration is used, it can be used in an environment in which a heating and cooling cycle is added in a high-temperature oxidizing atmosphere.
  • a heat-resistant alloy member that can maintain the high-temperature properties of a heat-resistant alloy substrate for a long period of time, and is sufficient to provide a top layer in a minimum necessary area, a method for manufacturing the same, and such a heat-resistant alloy member. It is to provide a high temperature device including and a method of manufacturing the same.
  • the present invention a heat-resistant alloy base material; a Re-based, W-based, or Cr-based multi-purpose alloy layer provided in a region including at least a region where heat insulation is to be performed on the surface of the heat-resistant alloy base; a bond layer made of an Al-containing alloy provided on the multi-purpose alloy layer in a region including at least the region where the heat insulation is to be performed; a top layer made of heat-shielding ceramics provided only in the region where the heat-shielding is to be performed on the bond layer; It is a heat-resistant alloy member having
  • the Re-based, W-based or Cr-based multi-purpose layer has, in addition to the diffusion barrier ability, oxidation resistance, improvement of the mechanical properties of the heat-resistant alloy substrate, and improvement of the top layer. It means an alloy layer that has multi-functionality such as improvement of peeling resistance and can be used for many purposes.
  • the Re-based, W-based, or Cr-based multi-purpose alloy layers contain Re, W, and Cr, respectively.
  • the multi-purpose alloy layer is Re-based or W-based
  • the multi-purpose alloy layer, the bond layer and the top layer are provided only in the heat shielding region of the surface of the heat-resistant alloy substrate.
  • the Re-based or W-based multi-purpose alloy layer, bond layer and top layer are provided only in the heat-shielding region of the surface of the heat-resistant alloy substrate, and are provided in areas other than the heat-shielding region.
  • An Al-containing alloy film is provided so as to cover the surface of the heat-resistant alloy base material of the part.
  • a protective Al 2 O 3 film is formed by oxidizing the Al-containing alloy film during oxidation at high temperature, and the high-temperature oxidation resistance of the heat-resistant alloy substrate can be ensured.
  • the Al-containing alloy film is generally a Ni-based alloy having an Al concentration of 50 atomic % (at %) or less and 30 atomic % or more, and preferably has an Al concentration of 40 atomic % or less.
  • the Al-containing alloy coating is typically made of ⁇ -NiAl, but is not limited to this.
  • the multi-purpose alloy layer may be formed by laminating two different layers selected from a Re-based multi-purpose alloy layer and a W-based multi-purpose alloy layer.
  • a Cr-based multi-purpose alloy layer and an Al-containing alloy coating on the multi-purpose alloy layer are provided so as to cover the entire surface of the heat-resistant alloy substrate, and the bond layer and the top layer are formed on the Al-containing alloy coating. It is provided only in areas where heat insulation is to be performed.
  • the multi-purpose alloy layer, the bond layer and the top layer are provided only in the heat-insulating region of the surface of the heat-resistant alloy substrate so as to cover the surface of the heat-resistant alloy substrate other than the heat-insulating region.
  • a multi-purpose alloy layer and an Al-containing alloy coating on the multi-purpose alloy layer are provided.
  • a Cr-based multi-purpose alloy layer and an Al-containing alloy film that also serves as a bond layer are provided on the multi-purpose alloy layer so as to cover the entire surface of the heat-resistant alloy substrate, and the top layer is on the Al-containing alloy film. It is provided only in areas where heat insulation is to be performed.
  • the heat-resistant alloy base material is selected as necessary, and may or may not be particularly limited. Unless otherwise specified, the heat-resistant alloy base material is made of conventionally known alloys such as Fe-based alloys, Co-based alloys, and Ni-based alloys having a Cr content of 20 atomic % or less.
  • the heat-resistant alloy substrate is preferably composed of one or more metals containing at least Cr selected from the group consisting of Cr, Mo, Nb and W. It consists of a Ni-based alloy containing more than 24.5 atomic %.
  • the Ni-based alloy contains 18.7 atomic % or more of Cr, and a total of 5.7 atomic % of one or more metals selected from the group consisting of Mo, Nb and W.
  • the total content of Fe and Nb is 13.1 atomic % or less.
  • the heat-resistant alloy substrate may be made of a Ni-based single crystal superalloy.
  • the shape of the heat-resistant alloy base material is not particularly limited, and is selected according to the application.
  • the heat shielding ceramics constituting the top layer are, for example, oxide ceramics containing zirconium, yttrium and oxygen (typically YSZ), oxide ceramics containing aluminum, yttrium and oxygen, aluminum, lanthanum and oxygen at least selected from the group consisting of oxide ceramics containing and, oxide ceramics containing aluminum, samarium and oxygen, oxide ceramics containing cerium and oxygen, and oxide ceramics containing thorium and oxygen consist of one kind.
  • oxide ceramics containing zirconium, yttrium and oxygen typically YSZ
  • oxide ceramics containing aluminum, yttrium and oxygen, aluminum, lanthanum and oxygen at least selected from the group consisting of oxide ceramics containing and, oxide ceramics containing aluminum, samarium and oxygen, oxide ceramics containing cerium and oxygen, and oxide ceramics containing thorium and oxygen consist of one kind.
  • the heat-resistant alloy member is not particularly limited, but specific examples include gas turbine members, jet engine members, exhaust system members, and the like.
  • this invention forming a Re-, W-, or Cr-based multi-purpose alloy layer on a surface of a heat-resistant alloy base material, including at least a region where heat insulation is to be performed; forming a bond layer made of an Al-containing alloy on a region including at least the region where the heat shield is to be performed on the multi-purpose alloy layer; a step of forming a top layer made of heat-shielding ceramics only on the region where the heat-shielding is to be performed on the bond layer; A method for manufacturing a heat-resistant alloy member having
  • a multi-purpose alloy layer is formed only on the heat-insulating region of the surface of the heat-resistant alloy substrate, and then a bond layer and a top layer are sequentially formed on the multi-purpose alloy layer.
  • thermal spraying, electron beam evaporation, or the like can be used to form the bond layer and the top layer.
  • a multi-purpose alloy layer is formed only on the area of the surface of the heat-resistant alloy base material that should be heat-insulated, and the surface of the heat-resistant alloy base material other than the area that should be heat-insulated is covered by performing Al diffusion treatment. After forming an Al-containing alloy film on the multi-purpose alloy layer, a bond layer and a top layer are sequentially formed on the multi-purpose alloy layer.
  • the heat-resistant alloy base material is made of a Ni-based alloy containing more than 24.5 atomic percent in total of one or more metals containing at least Cr selected from the group consisting of Cr, Mo, Nb and W.
  • oxidation is performed at a high temperature to form a Cr-based layer between the heat-resistant alloy base material and the Al-containing alloy coating due to the reaction between the heat-resistant alloy base material and the Al-containing alloy coating.
  • the heat-resistant alloy base material is made of a Ni-based alloy containing more than 24.5 atomic percent in total of one or more metals containing at least Cr selected from the group consisting of Cr, Mo, Nb and W,
  • An Al-containing alloy film is formed on the entire surface of the heat-resistant alloy substrate by applying Al diffusion treatment, and after sequentially forming a bond layer and a top layer only in the region where heat shielding is to be performed, heat treatment is performed at a high temperature.
  • a Cr-based multi-purpose alloy layer is formed between the heat-resistant alloy substrate and the Al-containing alloy film by reaction between the heat-resistant alloy substrate and the Al-containing alloy film.
  • the heat-resistant alloy base material is made of a Ni-based alloy containing more than 24.5 atomic percent in total of one or more metals containing at least Cr selected from the group consisting of Cr, Mo, Nb and W.
  • this invention a heat-resistant alloy base material; a Re-based, W-based, or Cr-based multi-purpose alloy layer provided in a region including at least a region where heat insulation is to be performed on the surface of the heat-resistant alloy base; a bond layer made of an Al-containing alloy provided on the multi-purpose alloy layer in a region including at least the region where the heat insulation is to be performed; and a top layer made of heat-shielding ceramics provided only on the region where the heat-shielding is to be performed on the bond layer.
  • the high-temperature device may be of various types that partially or wholly contain the above-mentioned heat-resistant alloy member, and specifically includes, for example, a gas turbine, a jet engine, an exhaust gas device, and the like.
  • this invention forming a Re-, W-, or Cr-based multi-purpose alloy layer on a surface of a heat-resistant alloy base material, including at least a region where heat insulation is to be performed; forming a bond layer made of an Al-containing alloy on a region including at least the region where the heat shield is to be performed on the multi-purpose alloy layer; and forming a top layer made of heat-shielding ceramics only on the heat-insulating region on the bond layer, and manufacturing a heat-resistant alloy member.
  • the diffusion barrier In addition to the function and peeling resistance of the top layer of the heat shield layer, excellent high-temperature oxidation resistance can be obtained, and furthermore, the mechanical strength of the heat-resistant alloy substrate can be improved.
  • the high-temperature properties can be maintained for a long period of time, and it is sufficient to provide the top layer in the minimum required area.
  • FIG. 1 is a cross-sectional view showing a heat-resistant alloy member according to a first embodiment of the invention
  • FIG. FIG. 4 is a cross-sectional view showing a heat-resistant alloy member according to a second embodiment of the invention
  • FIG. 5 is a cross-sectional view showing a heat-resistant alloy member according to a third embodiment of the invention
  • FIG. 4 is a cross-sectional view showing a heat-resistant alloy member according to a fourth embodiment of the invention
  • FIG. 5 is a cross-sectional view showing a heat-resistant alloy member according to a fifth embodiment of the present invention
  • FIG. 6 is a cross-sectional view showing a heat-resistant alloy member according to a sixth embodiment of the invention
  • FIG. 11 is a cross-sectional view showing a heat-resistant alloy member according to a seventh embodiment of the present invention
  • FIG. 2 is a perspective view showing a test piece used for high temperature cycle oxidation test
  • FIG. 2 is a cross-sectional view showing a test piece used for creep testing
  • 1 is a cross-sectional view showing the structure of a test piece of Example 1.
  • FIG. 4 is a drawing-substituting photograph showing the cross-sectional structure of the test piece of Example 1.
  • FIG. FIG. 4 is a cross-sectional view showing the structure of a test piece of Example 2; 4 is a drawing-substituting photograph showing the cross-sectional structure of the test piece of Example 2.
  • FIG. 10 is a cross-sectional view showing the structure of a test piece of Example 3; 10 is a drawing-substituting photograph showing the cross-sectional structure of the test piece of Example 3.
  • FIG. FIG. 10 is a cross-sectional view showing the structure of a test piece of Example 4;
  • FIG. 10 is a cross-sectional view showing the structure of a test piece of Example 5;
  • FIG. 10 is a cross-sectional view showing the structure of a test piece of Example 6;
  • 10 is a drawing-substituting photograph showing the cross-sectional structure of the test piece of Example 6.
  • FIG. FIG. 11 is a cross-sectional view showing the structure of a test piece of Example 7;
  • FIG. 10 is a cross-sectional view showing the structure of a test piece of Example 8;
  • FIG. 4 is a cross-sectional view showing the structure of a test piece of a comparative example;
  • FIG. 4 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of a comparative example;
  • FIG. 4 is a schematic diagram showing the dependence of the amount of oxidation on the number of cycles of test pieces of Examples 1 to 8 and a comparative example subjected to heating and cooling cycle oxidation.
  • FIG. 5 is a schematic diagram showing the cycle number dependence of the Al concentration of the bond layers of the test pieces of Examples 1 to 8 and Comparative Example.
  • FIG. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al is diffused into an ALLOY X base material;
  • FIG. Fig. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 601 base material;
  • 2 is a drawing-substituting photograph showing a cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 20 base material.
  • FIG. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 825 base material;
  • FIG. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 800HT base material; 2 is a drawing-substitute photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 625 base material.
  • FIG. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 718 base material;
  • FIG. 2 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY B2 base material.
  • FIG. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 22 base material
  • FIG. Fig. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY C276 base material
  • Fig. 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 22 base material after four-cycle oxidation
  • Fig. 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 625 base material after four-cycle oxidation.
  • Fig. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was performed on an ALLOY 22 base material
  • FIG. Fig. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece after Al diffusion was
  • FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY C276 base material after four-cycle oxidation; 2 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY X base material after four-cycle oxidation.
  • Fig. 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 718 base material after four-cycle oxidation.
  • Fig. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece of an ALLOY 825 base material after four-cycle oxidation.
  • FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 20 base material after four-cycle oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 601 substrate after four-cycle oxidation.
  • Fig. 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 800HT substrate after four-cycle oxidation.
  • FIG. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece of an ALLOY B2 base material after four-cycle oxidation;
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 22 base material after 100 cycles of oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 625 substrate after 100 cycles of oxidation.
  • Fig. 10 is a drawing-substituting photograph showing the cross-sectional structure of a test piece of an ALLOY C276 base material after 100 cycles of oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY X base material after 100 cycles of oxidation.
  • 10 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 718 base material after 100 cycles of oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 825 base material after 100 cycles of oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 20 substrate after 100 cycles of oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 601 substrate after 100 cycles of oxidation.
  • FIG. 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY 800HT substrate after 100 cycles of oxidation.
  • 1 is a drawing-substituting photograph showing a cross-sectional structure of a test piece of an ALLOY B2 base material after 100 cycles of oxidation.
  • FIG. 4 is a schematic diagram showing the results of investigation of creep behavior of test pieces of ALLOY X base material on which various multi-purpose alloy layers are formed.
  • FIG. 3 is a schematic diagram showing a creep curve (strain) of a test piece of an ALLOY X substrate on which a Re-based multi-purpose alloy layer is formed;
  • FIG. 3 is a schematic diagram showing a creep curve (strain rate) of a test piece of an ALLOY X substrate on which a Re-based multi-purpose alloy layer is formed.
  • 1 is a drawing-substituting photograph showing the result of observation of the surface of a test piece of an ALLOY X substrate on which a Re-based multi-purpose alloy layer is formed.
  • FIG. 34B is a drawing-substituting photograph showing an enlarged part of FIG. 34A.
  • 34B is a drawing-substituting photograph showing the result of observation of the cross-sectional structure of the test piece shown in FIG. 34A.
  • FIG. 34C is a photograph substituting for a drawing and showing an enlarged portion of the Re-based multi-purpose alloy layer/ ⁇ -NiAl coating in the cross-sectional structure shown in FIG. 34C.
  • FIG. 35B is a schematic diagram showing the concentration distribution of each element in the direction indicated by the dotted line in FIG. 35A;
  • FIG. 4 is a schematic diagram showing the creep behavior of a test piece of SUS310 substrate on which a Re-based multi-purpose alloy layer is formed.
  • FIG. 10 is a drawing-substituting photograph showing the result of observing the cross-sectional structure of a test piece of a SUS310 base material after a creep test.
  • 37B is a drawing-substituting photograph showing an enlarged part of the cross-sectional structure shown in FIG. 37A.
  • 1 is a drawing-substituting photograph showing the result of observing a cross-sectional structure after a creep test of a test piece of a SUS310 substrate on which a Re-based multipurpose alloy layer having a thickness of 10 ⁇ m is formed.
  • 37C is a photograph substituting for a drawing and showing an enlarged part of the cross-sectional structure shown in FIG. 37C.
  • FIG. 1 is a drawing-substituting photograph showing the result of observing a cross-sectional structure after a creep test of a test piece of a SUS310 substrate on which a Re-based multipurpose alloy layer having a thickness of 20 ⁇ m is formed.
  • 37E is a photograph substituting for a drawing and showing an enlarged part of the cross-sectional structure shown in FIG. 37E.
  • FIG. 1 shows a heat-resistant alloy member according to a first embodiment.
  • a Re-based multi-purpose alloy layer 201, a bond layer 300 and a top layer 400 are sequentially laminated only in a specific region of the surface of a heat-resistant alloy substrate 100 where heat insulation is to be performed. , and the surface of the heat-resistant alloy base material 100 is exposed in other regions.
  • the Re-based multi-purpose alloy layer 201 is made of an alloy layer containing Re, and typically the upper portion is made of a Ni--Cr alloy layer 201a.
  • the alloy layer containing Re the one described in Patent Document 4 or the like is used.
  • the top layer 400 is made of heat insulating ceramics such as YSZ.
  • a TGO-Al 2 O 3 layer is formed between the bond layer 300 and the top layer 400 before or after the start of use.
  • the thickness of this TGO-Al 2 O 3 layer is, for example, about several ⁇ m.
  • the heat-resistant alloy base material 100 is selected as necessary, for example, selected from among those already listed.
  • the amount is 20 atomic % or more, and more than 24.5 atomic % in total of one or more metals containing at least Cr selected from the group consisting of Cr, Mo, Nb and W
  • metals containing at least Cr selected from the group consisting of Cr, Mo, Nb and W
  • Ni-based alloys containing a large amount those made of Ni-based single crystal superalloys, and the like.
  • the thickness of the bond layer 300 is, for example, 50 ⁇ m or more and 150 ⁇ m or less.
  • the thickness of the top layer 400 is, for example, 200 ⁇ m or more and 500 ⁇ m or less.
  • the heat-resistant alloy base material 100 is made of a Ni-based alloy, an Fe-based alloy, a Co-based alloy, or the like.
  • the surface of the heat-resistant alloy base material 100 is masked by covering it with an insulating tape or forming an insulating coating film on the area other than the specific area where the heat is to be shielded, and then only the specific area is plated. to form a Re-containing layer.
  • the Re-based multi-purpose alloy layer 201 is formed by the reaction between the heat-resistant alloy substrate 100 and the Re-containing layer.
  • a Ni—Cr layer 201 a is formed on the Re-based multi-purpose alloy layer 201 .
  • a bond layer 300 and a top layer 400 are sequentially formed on the Re-based multi-purpose alloy layer 201 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. For example, after the bond layer 300 is formed, it is oxidized in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • the bond layer 300 and the top layer 400 are formed through the Re-based multi-purpose alloy layer 201 only in the specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed. is provided, when this heat-resistant alloy member is used in an environment where heating and cooling are repeated in a high-temperature oxidizing atmosphere, the Re-based multi-purpose alloy layer 201 transfers Al of the bond layer 300 to the heat-resistant alloy substrate 100.
  • the Al concentration of the bond layer 300 can be maintained sufficiently high, for example, 13 atomic % or more, and the bond layer 300
  • the TGO-Al 2 O 3 layer can be maintained between the top layer 400 and the top layer 400 for a long period of time, thereby obtaining excellent high temperature corrosion resistance, and the TGO-Al 2 O 3 layer Delamination of the top layer 400 can be effectively prevented by suppressing the formation of non-protective oxides other than the heat-resistant alloy substrate 100, thereby obtaining excellent delamination resistance.
  • This heat-resistant alloy member sufficiently satisfies the characteristics required for high-temperature members such as gas turbines, jet engines, exhaust system members, etc., whose operating temperatures tend to rise in recent years with the aim of increasing output. be.
  • FIG. 2 shows a heat-resistant alloy member according to a second embodiment.
  • a Re-based multi-purpose alloy layer 201, a bond layer 300, and a top layer 400 are sequentially laminated only on a specific region of the surface of a heat-resistant alloy substrate 100 where heat insulation is to be performed.
  • the Re-based multi-purpose alloy layer 201 is the same as in the first embodiment.
  • a portion of the surface of the heat-resistant alloy substrate 100 other than the specific region where heat shielding is to be performed is covered with an Al-containing alloy film 150 .
  • the Al-containing alloy coating 150 is typically made of ⁇ -NiAl or Fe-Al.
  • the heat-resistant alloy base material 100, bond layer 300 and top layer 400 are the same as in the first embodiment.
  • the heat-resistant alloy base material 100 is made of a Ni-based alloy, an Fe-based alloy, a Co-based alloy, or the like.
  • the Re-based multi-purpose alloy layer 201 is formed on a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed, in the same manner as in the first embodiment.
  • an Al-containing alloy film 150 is formed on the surface of the heat-resistant alloy base material 100 at a portion other than the Re-based multi-purpose alloy layer 201 by performing an Al diffusion treatment.
  • the Al diffusion treatment is performed by embedding the heat-resistant alloy base material 100 in, for example, (Al+NH 4 Cl+Al 2 O 3 ) and heating in an Ar atmosphere at a temperature of 700 to 800° C.
  • the heat resistant alloy base material 100 is embedded in (FeAl+NH 4 Cl+Al 2 O 3 ) or (Al+Ni+NH 4 Cl+Al 2 O 3 ) and heated at a temperature of 900 to 1100° C. for 1 to 10 hours in an Ar+3 vol% H 2 atmosphere.
  • a bond layer 300 and a top layer 400 are sequentially formed on the Re-based multi-purpose alloy layer 201 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. For example, after the bond layer 300 is formed, it is oxidized in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • the same advantages as those of the first embodiment can be obtained, and the surface of the heat-resistant alloy substrate 100 other than the Re-based multi-purpose alloy layer 201 is coated with an Al-containing alloy film.
  • a protective Al 2 O 3 film is formed and protected during high-temperature oxidation, so it is possible to obtain the advantage that excellent high-temperature oxidation resistance can be secured.
  • FIG. 3 shows a heat-resistant alloy member according to a third embodiment.
  • a W-based multi-purpose alloy layer 202, a bond layer 300, and a top layer 400 are sequentially laminated only on a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed.
  • the W-based multi-purpose alloy layer 202 is made of an alloy layer containing W, and typically the upper portion is made of a Ni(Cr, Si) layer 202a.
  • a portion of the surface of the heat-resistant alloy substrate 100 other than the specific region where heat shielding is to be performed is covered with an Al-containing alloy film 150 .
  • the Al-containing alloy coating 150 is typically made of ⁇ -NiAl or Fe-Al.
  • the heat-resistant alloy base material 100, bond layer 300 and top layer 400 are the same as in the first embodiment.
  • the heat-resistant alloy base material 100 is made of a Ni-based alloy, an Fe-based alloy, a Co-based alloy, or the like.
  • a W-containing layer is formed by applying a slurry to a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed. Specifically, for example, (25 to 50% by weight) W powder, (15 to 25% by weight) Cr powder, (15 to 30% by weight) Mo powder, and the balance Ni-based self-fluxing alloy (nominal composition (% by weight) ;Ni-15Cr-3Si-2B-5Fe) are dissolved in a slurry liquid. Next, heat treatment is performed at a temperature of, for example, 1100° C. or higher and 1200° C.
  • the W-based multi-purpose alloy layer 202 is formed by the reaction between the heat-resistant alloy substrate 100 and the W-containing layer.
  • a Ni(Cr, Si) layer 202 a is formed on the W-based multi-purpose alloy layer 202 .
  • an Al-containing alloy film 150 is formed on the surface of the heat-resistant alloy base material 100 at portions other than the W-based multi-purpose alloy layer 202 by performing Al diffusion treatment.
  • the Al diffusion treatment is performed by burying the heat-resistant alloy base material 100 in, for example, (Al+NH 4 Cl+Al 2 O 3 ) and heating in an Ar atmosphere at a temperature of 700-800° C. for 1-1.5 hours. Alternatively, it is buried in (FeAl+NH 4 Cl+Al 2 O 3 ) or (Al+Ni+NH 4 Cl+Al 2 O 3 ) and heated at a temperature of 900 to 1100° C. for 1 to 10 hours in an atmosphere of Ar+3 vol % H 2 . Next, a bond layer 300 and a top layer 400 are sequentially formed on the W-based multi-purpose alloy layer 202 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. For example, after the bond layer 300 is formed, it is oxidized in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • the same advantages as in the first embodiment can be obtained, and the surface of the heat-resistant alloy substrate 100 other than the W-based multi-purpose alloy layer 202 is coated with an Al-containing alloy film.
  • a protective Al 2 O 3 film is formed and protected during high-temperature oxidation, so it is possible to obtain the advantage that excellent high-temperature oxidation resistance can be secured.
  • FIG. 4 shows a heat-resistant alloy member according to a fourth embodiment.
  • a Re-based multi-purpose alloy layer 201, a bond layer 300, and a top layer 400 are sequentially laminated only in a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed.
  • the heat-resistant alloy base material 100 is preferably a Ni-based Ni-based material containing at least one or more Cr-containing metals selected from the group consisting of Cr, Mo, Nb and W in a total amount of more than 24.5 atomic %. Made of alloy.
  • a portion of the surface of the heat-resistant alloy substrate 100 other than the specific region where heat shielding is to be performed is covered with a Cr-based multi-purpose alloy layer 203 and an Al-containing alloy film 150 thereon.
  • the Cr-based multi-purpose alloy layer 203 is composed of an alloy layer containing ⁇ -Cr, and typically contains one or more elements selected from the group consisting of the constituent elements of the heat-resistant alloy base material 100, such as Mo, Nb and W. Contains metal.
  • the Al-containing alloy coating 150 is typically made of ⁇ -NiAl. Bond layer 300 and top layer 400 are the same as in the first embodiment. If necessary, a Cr-based multi-purpose alloy layer may be provided between the Re-based multi-purpose alloy layer 201 and the bond layer 300 .
  • a Re-based multi-purpose alloy layer 201 is formed on a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed, in the same manner as in the first embodiment.
  • an Al-containing alloy film 150 is formed on the surface of the heat-resistant alloy base material 100 at a portion other than the Re-based multi-purpose alloy layer 201 by performing an Al diffusion treatment.
  • a Cr-based multi-purpose alloy layer 203 is formed between the heat-resistant alloy substrate 100 and the Al-containing alloy film 150 .
  • a bond layer 300 and a top layer 400 are sequentially formed on the Re-based multi-purpose alloy layer 201 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. For example, after the bond layer 300 is formed, it is oxidized in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • FIG. 5 shows a heat-resistant alloy member according to a fifth embodiment.
  • a W-based multi-purpose alloy layer 202, a bond layer 300, and a top layer 400 are sequentially laminated only in a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed.
  • the heat-resistant alloy base material 100 is preferably a Ni-based Ni-based material containing at least one or more Cr-containing metals selected from the group consisting of Cr, Mo, Nb and W in a total amount of more than 24.5 atomic %. Made of alloy.
  • the surface of the heat-resistant alloy base material 100 is covered with a Cr-based multi-purpose alloy layer 203 and an Al-containing alloy film 150 thereon, except for a specific area where heat insulation is to be performed.
  • the Cr-based multi-purpose alloy layer 203 is the same as in the fourth embodiment.
  • the Al-containing alloy coating 150 is typically made of ⁇ -NiAl. Bond layer 300 and top layer 400 are the same as in the first embodiment. If necessary, a Cr-based multi-purpose alloy layer may be provided between the W-based multi-purpose alloy layer 202 and the bond layer 300 .
  • a W-based multi-purpose alloy layer 202 is formed on a specific region of the surface of the heat-resistant alloy substrate 100 where heat insulation is to be performed, in the same manner as in the second embodiment.
  • the Cr-based multi-purpose alloy layer 203 and the Al-containing alloy film 150 are formed on the surface of the heat-resistant alloy base material 100 at portions other than the W-based multi-purpose alloy layer 202 by performing Al diffusion treatment.
  • a bond layer 300 and a top layer 400 are sequentially formed on the W-based multi-purpose alloy layer 202 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. For example, after the bond layer 300 is formed, it is oxidized in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • FIG. 6 shows a heat-resistant alloy member according to a sixth embodiment.
  • a Cr-based multi-purpose alloy layer 203 and an Al-containing alloy film 150 are provided over the entire surface of a heat-resistant alloy base material 100 .
  • the heat-resistant alloy base material 100 is preferably a Ni-based Ni-based material containing at least one or more Cr-containing metals selected from the group consisting of Cr, Mo, Nb and W in a total amount of more than 24.5 atomic %.
  • the Al-containing alloy coating 150 is typically made of ⁇ -NiAl.
  • the Cr-based multi-purpose alloy layer 203 is the same as in the fourth embodiment.
  • a bond layer 300 and a top layer 400 are sequentially laminated on the Al-containing alloy film 150 only in a specific region of the heat-resistant alloy substrate 100 where heat insulation is to be performed.
  • the Al-containing alloy film 150 in the specific region where this heat shield should be performed constitutes a part of the bond layer 300 .
  • the top layer 400 is similar to that of the first embodiment.
  • the Cr-based multi-purpose alloy layer 203 and the Al-containing alloy film 150 are formed on the entire surface of the heat-resistant alloy base material 100 by performing Al diffusion treatment.
  • a bond layer 300 and a top layer 400 are sequentially formed on the Al-containing alloy film 150 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. For example, after the bond layer 300 is formed, it is oxidized in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • FIG. 7 shows a heat-resistant alloy member according to a seventh embodiment.
  • a Cr-based multi-purpose alloy layer 203 and an Al-containing alloy film 150 are provided over the entire surface of a heat-resistant alloy base material 100 .
  • the heat-resistant alloy base material 100 is preferably a Ni-based Ni-based material containing at least one or more Cr-containing metals selected from the group consisting of Cr, Mo, Nb and W in a total amount of more than 24.5 atomic %.
  • the Al-containing alloy coating 150 is typically made of ⁇ -NiAl.
  • the Cr-based multi-purpose alloy layer 203 is the same as in the sixth embodiment.
  • a top layer 400 is laminated on the Al-containing alloy film 150 only in a specific region of the heat-resistant alloy substrate 100 where heat shielding is to be performed.
  • the Al-containing alloy film 150 in the specific region to be heat shielded also serves as the bond layer 300 .
  • the top layer 400 is similar to that of the first embodiment.
  • the Cr-based multi-purpose alloy layer 203 and the Al-containing alloy film 150 are formed on the entire surface of the heat-resistant alloy base material 100 by performing Al diffusion treatment.
  • a top layer 400 is formed on the Al-containing alloy film 150 by thermal spraying, electron beam deposition, or the like.
  • the TGO-Al 2 O 3 layer between the Al-containing alloy film 150 that also serves as the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere.
  • oxidation treatment is performed in a low oxygen partial pressure atmosphere.
  • the intended heat-resistant alloy member is manufactured.
  • heat-resistant alloy base material 100 As the heat-resistant alloy base material 100, the following (1) and (2) were used.
  • Base material made of Ni-based heat-resistant alloy shown in Table 1 (excerpt from the catalog of Osaka Stainless Co., Ltd.)
  • ALLOY 201 corresponds to Ni (for industrial use).
  • Other alloys can be said to be Ni-based alloys.
  • SUS310 base material (composition (% by weight) is Cr: 25, Ni: 20, Fe: balance)
  • the bond layer 300 of the thermal barrier coating film was made of NiCrAlY (nominal composition (wt %); Ni-25Cr-10Al-0.5Y).
  • the NiCrAlY layer was formed by an HVOF (High Velocity Oxy-Fuel) thermal spraying process (high speed flame spraying method).
  • the thickness of the NiCrAlY layer was set to 100 ⁇ m.
  • the top layer 400 was made of YSZ (nominal composition (mol %); 8Y 2 O 3 -92ZrO 2 ).
  • the YSZ layer was deposited by an atmospheric plasma (APS) spray process.
  • the thickness of the YSZ layer was 300 ⁇ m.
  • Figs. 8 and 9 show the shape and size of the test piece for the cyclic oxidation test and the test piece for the creep test when (1) and (2) were used as the heat-resistant alloy base material 100.
  • the test piece was a multi-purpose alloy layer, a bond layer and a top layer (MPL for the multi-purpose alloy layer, and TBC for the bond layer and the top layer) on the upper end surface of a cylindrical substrate having a diameter of 20 mm and a height of 10 mm. ), and there are cases where the circumferential surface of the substrate is left as it is and cases where an Al-containing alloy film is formed.
  • the upper end surface of the base material is designated as a specific area to be heat-shielded.
  • Example 1 corresponds to the sixth embodiment.
  • a YSZ layer is formed thereon as a top layer 400 by APS thermal spraying.
  • a TGO-Al 2 O 3 layer was formed between the NiCrAlY layer and the YSZ layer during formation. Thus, a test piece was produced.
  • FIG. 11 shows a cross-sectional SEM photograph.
  • Example 2 corresponds to the seventh embodiment.
  • a test piece for a cyclic oxidation test was produced. First, in the same manner as in Example 1, as shown in FIG. 12, a Cr-based multi-purpose alloy layer 203 and an Al-containing alloy coating 150 ( ⁇ -NiAl coating) were formed on the entire surface of the test piece.
  • a YSZ layer was formed as the top layer 400 on the upper end surface of the test piece by APS thermal spraying, and a TGO-Al 2 O 3 layer was formed between the ⁇ -NiAl film and the YSZ layer during the formation of this YSZ layer.
  • FIG. 13 shows a cross-sectional SEM photograph.
  • Example 3 corresponds to the first embodiment.
  • a test piece for a cyclic oxidation test was produced. First, the surface of the test piece was polished smooth and degreased. Next, the lower end surface and the circumferential surface of the test piece were covered with an insulating tape for masking. Next, (Ni strike plating 1 ⁇ m) ⁇ (Ni Watt plating 1 ⁇ m) ⁇ (Re-Ni alloy plating 8 ⁇ m) ⁇ (Ni Watt plating 15 ⁇ m) ⁇ (Cr plating 7 ⁇ m) is performed in order, and the total thickness of the plating layer is 32 ⁇ m. formed. Next, heat treatment was performed at 1000° C. for 5 hours in vacuum. As a result, as shown in FIG. 14, a Re-based multi-purpose alloy layer 201 was formed on the top surface of the test piece. A Ni—Cr layer 201 a was formed on the Re-based multi-purpose alloy layer 201 .
  • a YSZ layer is formed thereon as a top layer 400 by APS thermal spraying.
  • a TGO-Al 2 O 3 layer was formed between the NiCrAlY layer and the YSZ layer to prepare a test piece.
  • FIG. 15 shows a cross-sectional SEM photograph.
  • Example 4 corresponds to the second embodiment.
  • a test piece for a cyclic oxidation test was produced. After forming the Re-based multi-purpose alloy layer 201 on the upper end surface of the test piece through the same treatment as in Example 3, Al-containing alloy coating 150 is formed on the lower end surface and the circumferential surface of the test piece by performing Al diffusion treatment. did. A Ni—Cr layer 201 a was formed on the Re-based multi-purpose alloy layer 201 .
  • a YSZ layer is formed thereon as a top layer 400 by APS thermal spraying.
  • a TGO-Al 2 O 3 layer was formed between the NiCrAlY layer and the YSZ layer during formation.
  • FIG. 16 shows the test piece thus produced.
  • Example 5 corresponds to the fourth embodiment in which a Cr-based multi-purpose alloy layer 203 is provided between the Re-based multi-purpose alloy layer 201 and the bond layer 300 .
  • Example 1 Using an ALLOY X base material as the heat-resistant alloy base material 100, a test piece for a cyclic oxidation test was produced. After forming the Re-based multi-purpose alloy layer 201 on the upper end surface of the test piece through the same treatment as in Example 3, the Cr-based multi-purpose alloy layer 203 and the Al-containing alloy coating 150 were formed in the same manner as in Example 1.
  • FIG. 17 shows the test piece thus produced.
  • Example 6 corresponds to the case where the W-based multi-purpose alloy layer 202 is used instead of the Re-based multi-purpose alloy layer 201 in the first embodiment.
  • a test piece for a cyclic oxidation test was produced.
  • a slurry was prepared by adding 25% by weight of W powder to a Ni-based self-fluxing alloy (nominal composition (wt%); Ni-15Cr-3Si-2B-5Fe), applied to the surface of the test piece, and then Ar + 3vol% H 2 Heat treatment was performed at 1150° C. for 6 hours in the atmosphere.
  • a W-based multi-purpose alloy layer 202 was formed on the surface of the heat-resistant alloy substrate 100 .
  • a Ni(Cr, Si) layer 202 a was formed on the W-based multi-purpose alloy layer 202 .
  • FIG. 18 shows the test piece thus produced.
  • FIG. 19 shows a cross-sectional SEM photograph.
  • Example 7 corresponds to the third embodiment.
  • Example 6 Using an ALLOY X base material as the heat-resistant alloy base material 100, a test piece for a cyclic oxidation test was produced. After forming the W-based multi-purpose alloy layer 202 on the surface of the heat-resistant alloy substrate 100 in the same manner as in Example 6, the Al-containing alloy coating 150 was formed on the lower end surface and the circumferential surface of the test piece in the same manner as in Example 1. did.
  • FIG. 20 shows the test piece thus produced.
  • Example 8 corresponds to the fifth embodiment in which a Cr-based multi-purpose alloy layer 203 is provided between the W-based multi-purpose alloy layer 202 and the bond layer 300 .
  • a test piece for a cyclic oxidation test was produced. After forming a W-based multi-purpose alloy layer 202 on the upper end surface of the test piece in the same manner as in Example 6, a Cr-based multi-purpose alloy layer 203 was formed on the entire surface of the test piece, and the lower end surface and the circumferential surface of the test piece were formed. An Al-containing alloy film 150 was formed on the .
  • FIG. 21 shows the test piece thus produced.
  • FIG. 23 shows a cross-sectional SEM photograph.
  • High temperature oxidation test High temperature oxidation tests were conducted in air under conditions of repeated heating and cooling. Specifically, the test piece was placed on a horizontally movable sample stage (alumina rod), inserted into an electric furnace controlled at 1100°C, and after 45 minutes had passed, it was cooled in the air for 15 minutes, and then put into the electric furnace again. This is a so-called cyclic oxidation test.
  • FIG. 24 summarizes the cycle number dependence of the amount of oxidation of the test pieces of Examples 1 to 8 and Comparative Example and the number of cycles (peeling cycle number) at which YSZ of the top layer is peeled off.
  • the weight change of the test piece was measured at room temperature, but the oxidation behavior differs between the MPL/TBC applied surface and other surfaces.
  • the amount of oxidation was measured as a value divided by the area of the entire test piece, and as a result, the amount of oxidation obtained strongly reflected the results of the other surface (surface without TBC).
  • FIG. 24 shows the cycle number dependence of the oxidation amount of the ALLOY X substrate.
  • the amount of oxidation begins to decrease around 200 cycles, and then decreases in proportion to the number of cycles.
  • the amount of oxidation begins to decrease around 200 cycles, which is similar to the dependence of the amount of oxidation on the ALLOY X substrate on the number of cycles.
  • the heat shield layer YSZ was peeled off after 600 to 700 cycles.
  • the peel resistance of the top layer 400 is is improved, and the formation of a protective oxide film by the Al-containing alloy film 150 formed on the surface of the heat-resistant alloy substrate 100 can simultaneously improve high-temperature oxidation resistance.
  • the test piece (substrate/TBC) of the comparative example was photographed after each cooling after 1 cycle, 217 cycles, 380 cycles, 450 cycles, and 593 cycles.
  • delamination of the YSZ layer occurred from the periphery of the test piece and progressed toward the center with the number of cycles.
  • the YSZ layer was entirely exfoliated in the course of cooling after 593 cycles.
  • Example 1 substrate/Cr-based MPL layer 203/TBC
  • the test piece of Example 1 was photographed after each cooling after 1 cycle, 656 cycles, 1002 cycles, 1476 cycles, 1674 cycles, 1791 cycles, and 1850 cycles.
  • the number of cycles exceeded 1000, it was found that the YSZ layer started to partially peel off from the periphery of the test piece and progressed toward the center as the number of cycles increased.
  • the YSZ layer was entirely peeled off during the holding at room temperature.
  • the Re-based multi-purpose alloy layer 201 by inserting the Re-based multi-purpose alloy layer 201, the W-based multi-purpose alloy layer 202, or the Cr-based multi-purpose alloy layer 203 between the heat-resistant alloy substrate 100 and the TBC, the separation of the YSZ layer is suppressed. Recognize.
  • the test piece of the comparative example (substrate/TBC) and the test piece of Examples 1 to 8 (substrate/MPL/TBC) were cut after a predetermined cycle, and the cross-sectional structure was observed and the concentration distribution of each element was measured. did FIG. 25 shows the cycle number dependency of the Al concentration (atomic %) of the bond layer 300 . From FIG. 25, in the substrate/TBC of the comparative example, the Al concentration of the bond layer 300 decreased from about 18 atomic % at the initial stage to several atomic % after 200 cycles, and then gradually decreased to 1 atomic % or less. The YSZ layer peeled off after about 600 cycles. On the other hand, in the base material/MPL/TBC of Examples 1 to 8, the Al concentration gradually decreased as the number of cycles increased, decreased to 1 atomic% or less around 1600 to 1800 cycles, and the YSZ layer was peeled off. .
  • oxides of Cr 2 O 3 and NiAl 2 O 4 are observed in the TGO in addition to Al 2 O 3 . , these oxides form from the perimeter of the bond layer 300 and progress toward the center so that when formed over the TGO, the YSZ layer exfoliates over the entire surface.
  • the MPL layer maintains a high Al concentration in the bond layer 300, forming and maintaining an Al 2 O 3 -based TGO, and Cr 2 O 3 from around 1000 cycles.
  • NiAl 2 O 4 and the like were formed on the periphery, and the delamination of the YSZ layer started from the periphery, propagated toward the center, and was completely delaminated at 1850 cycles.
  • the formation of the Cr-based multi-purpose alloy layer 203 by Al diffusion treatment in the case of using the base material composed of various Ni-based heat-resistant alloys including ALLOY X listed in Table 1 was investigated. Subsequently, 4-cycle and 100-cycle oxidation tests were performed, and the cross-sectional structure of the test piece was observed and the concentration distribution of each element was measured. The results obtained are described below.
  • Figure 26A (ALLOY X), Figure 26B (ALLOY 601), Figure 26C (ALLOY 20), Figure 26D (ALLOY 825), Figure 26E (ALLOY 800HT), Figure 27A ( ALLOY 625), FIG. 27B (ALLOY 718), FIG. 27C (ALLOY B2), FIG. 27D (ALLOY 22) and FIG. 27E (ALLOY C276). From these figures, formation of a layer corresponding to the Cr-based multi-purpose alloy layer 203 is not observed in any of the test pieces after the Al diffusion treatment.
  • Figure 28A ALLOY 22, 34.7 atomic %)
  • Figure 28B ALLOY 625, 32.7 atomic %)
  • Figure 28C ALLOY C276, 30.5 atomic %)
  • FIG. 28D ALLOY X, 30.1 atomic %)
  • FIG. 28E ALLOY 718, 26.2 atomic %)
  • FIG. 29A ALLOY 825, 25.2 atomic %)
  • FIG. 29B ALLOY 20, 23.4 atomic %)
  • FIG. 29C ALLOY 601, 24.5 atomic %)
  • FIG. 29D ALLOY 800HT, 21.7 atomic %)
  • FIG. 30A ALLOY 22, 34.7 atomic %)
  • Figure 30B ALLOY 625, 32.7 atomic %)
  • Figure 30C ALLOY C276, 30.5 atomic %)
  • FIG. 30D ALLOY X, 30.1 atomic %)
  • FIG. 30E ALLOY 718, 26.2 atomic %)
  • FIG. 31A ALLOY 825, 25.2 atomic %)
  • FIG. 31B ALLOY 20, 23.4 atomic %)
  • FIG. 31C ALLOY 601, 24.5 atomic %)
  • FIG. 31D ALLOY 800HT, 21.7 atomic %)
  • FIG. 31E ALLOY B2, 20.1 atomic %) shown.
  • These structural photographs are shown in the order of the total sum (atomic %) of the elements (Cr+Mo+Nb+W) contained in the substrate (Figs. 31B and 31C are exceptions).
  • Table 3 below shows the relationship between the sum of the concentrations of the elements Cr+Mo+Nb+W in the substrate and the Cr-based multi-purpose alloy layer. It is summarized as follows.
  • ALLOY 601, ALLOY 800HT The total concentration of Cr+Mo+Nb+W in these alloys is 24.5 atomic % or less.
  • the alloys forming the continuous layer of the Cr-based multi-purpose alloy layer are as follows. ALLOY 22, ALLOY 625, ALLOY C276 The total concentration of Cr+Mo+Nb+W in these alloys is 30.5 atomic % or more. Alloys in which the Cr-based multi-purpose alloy layer is discontinuously formed are as follows.
  • ALLOY X, ALLOY 718, ALLOY 825, ALLOY 20 The total concentration of Cr+Mo+Nb+W in these alloys is 23.4 atomic % or more and 30.1 atomic % or less.
  • the alloy base material on which the Cr-based multi-purpose alloy layer is not formed is as follows. ALLOY 601, ALLOY 800HT The total concentration of Cr+Mo+Nb+W in these alloys is 24.5 atomic % or less.
  • 31E (ALLOY B2, 2.1 at.%). represents the total sum (atomic %) of the elements (Fe + Nb) contained in the From these figures, the higher the concentration of Fe(+Nb), the less formation of the Cr-based multi-purpose alloy layer 203 is observed.
  • the concentration of Fe(+Nb) is desirably 29.9 atomic % or less.
  • Tables 4 and 5 show the elements and concentrations (atomic %) of the Re-based multi-purpose alloy layer 201 formed on the heat-resistant alloy substrate 100 made of each alloy shown in Table 1.
  • Al pack means after Al diffusion treatment, and 25cyc etc. means after 25 cycles of oxidation.
  • the Re-based multi-purpose alloy layer 201 is observed on all alloy substrates after Al diffusion treatment, after 4 cycles of oxidation, after 25 cycles of oxidation, and after 100 cycles of oxidation.
  • the total concentration of the elements (Re+Cr+Nb+Mo) contained in the Re-based multi-purpose alloy layer 201 is 51.8 atomic % to 73.5 atomic %.
  • the Re-based multi-purpose alloy layer 201 disappeared in ALLOY B2 and ALLOY 201. This is because ALLOY 201 is industrially pure Ni, and ALLOY B2 has an extremely low Cr concentration of 0.2 atomic %.
  • the breaking time of the ALLOY X substrate on which the Cr-based multi-purpose alloy layer 203 is formed is the same as that of the ALLOY X substrate, and the ALLOY X substrate on which the Re-based multi-purpose alloy layer 201 or the W-based multi-purpose alloy layer 202 is applied. is on the long side. That is, in the ALLOY X base material on which three types of multi-purpose alloy layers (Re-based, W-based, and Cr-based) were formed, no decrease in strength was observed. It became clear that it contributed to high strength.
  • FIGS. 33A and 33B The creep curve of the ALLOY X substrate on which the Re-based multi-purpose alloy layer 201 is formed (970°C; In air, stress 22.5 MPa, 27.5 MPa, 40 MPa) are shown in FIGS. 33A and 33B.
  • FIG. 33A shows the time course of strain
  • FIG. 33B shows the time course of strain rate. From FIGS. 33A and 33B, when comparing at a stress of 27.5 MPa, the rupture time of the ALLOY X substrate is 220 hours, while that of the substrate/Re-based multi-purpose alloy layer 201 is 380 hours. It was found that the steady creep rate is lower in the substrate/Re-based multi-purpose alloy layer 201 compared to the ALLOY X substrate.
  • FIGS. 34A and 34B the creep test at a stress of 22.5 MPa was interrupted at a strain of 3.5% for 190 hours, and the results of observing the surface and cross-sectional structure of the test piece are shown in FIGS. 34A and 34B. and FIG. 34C.
  • FIG. 34A shows the entire test piece
  • FIG. 34B shows an enlarged view of the region surrounded by the dashed line in FIG. 34A
  • FIG. 34C shows the structure of the cross section of the test piece.
  • 34A, 34B and 34C ⁇ -Al 2 O 3 is formed on the surface of the test piece, and longitudinal cracks (perpendicular to the stress axis) and partial delamination are observed.
  • 35A and 35B respectively show an enlarged photograph of the Re-based multi-purpose alloy layer 201/ ⁇ -NiAl coating and the concentration distribution of each element in the cross-sectional structure shown in FIG. 34C.
  • the composition (atomic %) of the Re-based multi-purpose alloy layer 201 is 25 atomic % Re-35 atomic % Cr-16 atomic % Ni-10 atomic % Fe-10 atomic % Mo.
  • Part of the ⁇ -Al 2 O 3 formed on the surface of the test piece is peeled off, but defects such as cracks are not observed in the Re-based multi-purpose alloy layer 201 and the ⁇ -NiAl coating.
  • Al in the ⁇ -NiAl film did not diffuse into the base material, and despite the creep deformation, the Re-based multi-purpose alloy layer 201 functions as an Al diffusion barrier.
  • FIG. 36 shows the results of investigating the creep behavior of the SUS310 base material on which the Re-based multi-purpose alloy layer 201 is formed at 900°C in the air at a stress of 22.5 MPa.
  • FIG. 36 also shows the results of investigating the creep behavior of the SUS310 base material. From FIG. 36, for example, when the strain (%) at a creep time of 200 hours is compared, the SUS310 substrate is 21%, while the SUS310 with the Re-based multi-purpose alloy layer 201 having a thickness of 10 ⁇ m and 20 ⁇ m. The base material is 11% and 8.5%, respectively. It can be seen that the creep resistance of the SUS310 substrate is improved by forming the Re-based multi-purpose alloy layer 201 .
  • FIGS. 37A, 37B, 37C, 37D, 37E and 37F show the cross-sectional structure of the test piece after fracture in the creep test shown in FIG.
  • FIGS. 37A and 37B show the cross-sectional structure of the SUS310 base material after the creep test
  • FIG. 37B is a partially enlarged view of FIG. 37A
  • FIGS. 37C and 37D show the cross-sectional structure after the creep test of the SUS310 substrate on which the Re-based multi-purpose alloy layer 201 having a thickness of 10 ⁇ m is formed
  • FIG. 37D is a partially enlarged view of FIG. 37C.
  • FIG. 37E and 37F show the cross-sectional structure after the creep test of the SUS310 substrate on which the 20 ⁇ m thick Re-based multi-purpose alloy layer 201 is formed, and FIG. 37F is a partially enlarged view of FIG. 37E. From these figures, many fine intergranular cracks are observed in the SUS310 substrate, whereas intergranular fractures occur less frequently in the substrate/Re-based multi-purpose alloy layer 201 .
  • a Cr-based multi-purpose alloy layer 203 or a Re-based multi-purpose alloy layer 201 was formed on an ALLOY X substrate, and their fatigue resistance properties were investigated under the conditions shown in Table 6.
  • the number of fatigue fracture cycles is 1.16 to 1.24 for the substrate/Cr-based multipurpose alloy layer 203 and 2.59 to 2 for the substrate/Re-based multipurpose alloy layer 201, as relative values to the alloy substrate. 0.75.
  • the substrate/Cr-based multi-purpose alloy layer 203 has almost the same fatigue resistance as the substrate, and the substrate/Re-based multi-purpose alloy layer 201 has improved by more than double.

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PCT/JP2021/014268 2021-04-02 2021-04-02 耐熱合金部材およびその製造方法ならびに高温装置およびその製造方法 Ceased WO2022208861A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004035911A (ja) * 2002-06-28 2004-02-05 Japan Science & Technology Corp レニウム含有合金皮膜を被着してなる耐高温酸化性耐熱合金部材の製造方法
JP2005526907A (ja) * 2002-04-10 2005-09-08 シーメンス　アクチエンゲゼルシヤフト 遮蔽層を有する構成部材
JP3857690B2 (ja) * 2001-10-31 2006-12-13 独立行政法人科学技術振興機構 拡散障壁用Ｒｅ合金皮膜
JP4753720B2 (ja) * 2004-01-15 2011-08-24 株式会社荏原製作所 拡散バリヤ用合金皮膜及びその製造方法、並びに高温装置部材
JP5905336B2 (ja) * 2012-05-30 2016-04-20 三菱日立パワーシステムズ株式会社 発電用ガスタービン翼、発電用ガスタービン

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3857690B2 (ja) * 2001-10-31 2006-12-13 独立行政法人科学技術振興機構 拡散障壁用Ｒｅ合金皮膜
JP2005526907A (ja) * 2002-04-10 2005-09-08 シーメンス　アクチエンゲゼルシヤフト 遮蔽層を有する構成部材
JP2004035911A (ja) * 2002-06-28 2004-02-05 Japan Science & Technology Corp レニウム含有合金皮膜を被着してなる耐高温酸化性耐熱合金部材の製造方法
JP4753720B2 (ja) * 2004-01-15 2011-08-24 株式会社荏原製作所 拡散バリヤ用合金皮膜及びその製造方法、並びに高温装置部材
JP5905336B2 (ja) * 2012-05-30 2016-04-20 三菱日立パワーシステムズ株式会社 発電用ガスタービン翼、発電用ガスタービン

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