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WO2013061945A1 - Élément d'alliage résistant à la chaleur et son procédé de fabrication - Google Patents

Élément d'alliage résistant à la chaleur et son procédé de fabrication Download PDF

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Publication number
WO2013061945A1
WO2013061945A1 PCT/JP2012/077298 JP2012077298W WO2013061945A1 WO 2013061945 A1 WO2013061945 A1 WO 2013061945A1 JP 2012077298 W JP2012077298 W JP 2012077298W WO 2013061945 A1 WO2013061945 A1 WO 2013061945A1
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Prior art keywords
layer
heat
resistant alloy
alloy member
stress relaxation
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English (en)
Japanese (ja)
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成田　敏夫
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DBC System Co Ltd
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DBC System Co Ltd
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Priority to JP2013540776A priority Critical patent/JP6083710B2/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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • 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
    • F01D5/288—Protective coatings for blades
    • 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

Definitions

  • the present invention relates to a heat-resistant alloy member and a method for producing the same, and is particularly suitable for application to a heat-resistant alloy member used in an environment to which a heat cycle that repeats heating and cooling is added in a high-temperature corrosive atmosphere.
  • high temperature apparatus members such as boiler heat transfer tubes are often used by forming a heat and corrosion resistant alloy film on the surface of a metal substrate.
  • the heat-resistant and corrosion-resistant alloy film include diffusion aluminide coating and Ni—Cr alloy overlay coating, and protective oxidation such as alumina (Al 2 O 3 ) and chromia (Cr 2 O 3 ) on the surface thereof.
  • a physical film is formed to protect the high temperature device member.
  • the alloy member is protected by forming an O 3 film.
  • a Ni—Al alloy, a Ni—Al—Pt alloy with Pt added, or the like is used, and a protective Al 2 O 3 film is formed to protect the alloy member.
  • the environment in which the high-temperature device member is used is an extremely high temperature of about 800 to 1300 ° C.
  • elements contained in the metal substrate constituting the high-temperature device member for example, Ni, Co, Fe, Ti, Mo, W, W) Etc.
  • elements (Al, Cr, etc.) added to the coating layer to form a protective oxide film diffuse and move to the metal substrate side.
  • the concentration of Al, Cr, etc. in the coating layer decreases, and cracking or peeling of the protective oxide film (eg, Al 2 O 3 or Cr 2 O 3 ) formed on the surface of the coating layer proceeds.
  • it changes to a non-protective oxide film for example, NiO, NiAl 2 O 4 , NiCr 2 O 4, etc.
  • TBC Thermal Barrier Coating Coat
  • This TBC is composed of at least two layers of a bond coat and a top coat.
  • MCrAlY alloy Ni, Co
  • Ni-Al alloy Ni-Al-Pt alloy, etc.
  • thermally grown oxide Thermal Grown Oxide: TGO
  • TGO Thermally grown oxide
  • An oxide having low thermal conductivity is used for the top coat.
  • An example is yttria-stabilized Zirconia (YSZ).
  • the YSZ of the top coat functions as a heat shielding layer against the high-temperature combustion gas, and maintains the metal substrate and the bond coat at a relatively low temperature by air-cooling the inside of the metal substrate.
  • the above coating layer and TBC bond coat contain a higher concentration of Al compared to the metal substrate, so during use at high temperatures, Al diffuses from the coating layer or bond coat to the metal substrate. Then, a secondary reaction zone (SRZ) is formed in the metal substrate to reduce the strength of the metal substrate.
  • SRZ secondary reaction zone
  • a decrease in the Al concentration of the coating layer or bond coat may result in non-protective oxide films (eg, NiAl 2 O 4 , NiO, etc.) Or loss of TGO protection.
  • a diffusion barrier layer 40 is formed between the metal substrate 10 and the reservoir layer 20, and a protective oxide film 30 is formed on the surface of the reservoir layer 20.
  • the diffusion barrier layer 40 has a conjugated composition relationship with the crystal phase constituting the metal substrate 10 and the reservoir layer 20 (or bond coat), and is considered to be thermodynamically stable. Thus, the function as a diffusion barrier layer can be maintained (see Non-Patent Documents 1 and 2).
  • the inventor refers to the diffusion barrier coating including the diffusion barrier layer 40 and the reservoir layer 20, and names the diffusion barrier coating system (Diffusion Barrier CoatingDSystem: DBC system) including the metal substrate 10 and the diffusion barrier coating. is doing.
  • the DBC system is based on metal substrates (for example, second generation Ni-based single crystal superalloy (TMS-82), third generation single crystal superalloy (CMSX-4), fourth Generation single crystal superalloy (TMS-138), stainless steel (SUS310S), Ni—Cr—Mo alloy (Hastelloy-X) and Al reservoir layer (eg, Ni—Al—Cr alloy, Pt-added Ni—Cr—Al alloy) )
  • a protective oxide film eg, Al 2 O 3
  • Narita Diffusion barrier coating system concept for high temperature applications, Canadian Metallurgical Quarterly, Vol.50, No.3 (2011), pp.278-290 T. Narita: Compatible Coating System to Provide Long-Life and High-Reliability, Materials Science Forum, Vol.696 (2011), pp.12-27 Sudhangshu Bose, High Temperature Coatings, pp.171-172 (2007) Elsevier
  • TIT bine Inlet Temperature
  • the present inventor has examined the effects of thermal cyclic oxidation on the adhesion, crack formation and delamination of protective oxide films (eg, Al 2 O 3 films) formed on DBC systems as metal substrates.
  • protective oxide films eg, Al 2 O 3 films
  • CMSX-4 Ni-based single crystal superalloy
  • Al 2 O 3 film formed on a conventional coating layer was also examined.
  • the Al 2 O 3 film was peeled off by 100 cycles in the conventional coating layer.
  • the diffusion barrier coating composed of the diffusion barrier layer and the Ni—Cr—Al-based reservoir layer was found to start peeling at a higher cycle number of 150 to 200 cycles.
  • Non-Patent Document 1 in a diffusion barrier coating composed of a diffusion barrier layer having a three-layer structure and a Pt-added Ni—Al—Pt-based reservoir layer, no peeling of the Al 2 O 3 film is observed up to 400 cycles. It has been reported.
  • the Al 2 O 3 film formed on the DBC system has better adhesion, crack resistance, and resistance to the oxide film mainly composed of Al 2 O 3 formed on the conventional coating layer. It confirmed that it had peelability. Furthermore, it has been clarified that addition of Pt to the reservoir layer improves the adhesion resistance and peel resistance of Al 2 O 3 .
  • the problem to be solved by the present invention is that cracking and peeling of the protective oxide film formed on the reservoir layer can be suppressed even when used in an environment where a thermal cycle is added in a high temperature corrosive atmosphere. And it is providing the heat-resistant alloy member which does not require the significant reduction of the addition amount of expensive Pt to a reservoir layer, or addition, and its manufacturing method.
  • the present inventor has conducted earnest research in order to solve the above problems.
  • a diffusion barrier layer is provided between the metal substrate and the reservoir layer and a stress relaxation layer made of an oxide ceramic such as YSZ is provided on the reservoir layer
  • the thermal cycle is performed in a high-temperature corrosive atmosphere. It has been found that even when used in an added environment, cracking and peeling of the protective oxide film formed on the reservoir layer can be suppressed. This is an effect that can hardly be obtained when only the diffusion barrier layer or the stress relaxation layer is used, and is an unexpected effect.
  • the present invention has been devised as a result of intensive studies based on the above-mentioned knowledge obtained independently by the present inventor. That is, in order to solve the above problems, the present invention provides: A metal substrate; A heat-resistant alloy member having a diffusion barrier layer, a reservoir layer, and a stress relaxation layer made of oxide ceramics laminated in order on the surface of the metal substrate.
  • this invention Forming a diffusion barrier layer on the surface of the metal substrate; Forming a reservoir layer on the diffusion barrier layer; And a step of forming a stress relaxation layer made of an oxide ceramic on the reservoir layer.
  • the oxide ceramic constituting the stress relaxation layer typically contains at least one metal different from the metal constituting the oxide ceramic, for example, a metal that contributes to a decrease in the thermal conductivity of the oxide ceramic.
  • the at least one metal include nickel (Ni), aluminum (Al), chromium (Cr), titanium (Ti), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), and cobalt.
  • Ni nickel
  • Al aluminum
  • Cr chromium
  • Ti titanium
  • Ta tantalum
  • cobalt cobalt
  • it is at least 1 type of metal chosen from the group which consists of (Co) and molybdenum (Mo)
  • the content of these metals is selected as necessary, but the total content is generally greater than 0% and 6% or less, typically 1% or more and 5% or less, more typically 2%. % Or more and 5% or less.
  • the metal substrate may be made of various conventionally known materials, and is selected as necessary. Specifically, for example, a Ni-base superalloy, stainless steel, Ni— An alloy made of a Cr—Mo base alloy (Hastelloy alloy), a Co base alloy, or the like can be used.
  • the diffusion barrier layer is for suppressing interdiffusion of elements contained in the metal base material and the reservoir layer, and includes an alloy containing Re, such as a Re—Cr—Ni alloy, Re—W—Cr—. It is made of Ni alloy, Re—Cr—Mo—Ni alloy or the like.
  • the reservoir layer forms and maintains a protective oxide film, and has the ability to regenerate when the protective oxide film peels off, specifically, for example, an alloy containing Al or further Cr
  • an alloy containing Al or further Cr For example, Ni—Al alloy, Ni—Pt—Al alloy, MCrAlY alloy (M is at least one metal selected from the group consisting of Fe, Ni and Co).
  • the stress relaxation layer prevents the protective oxide film formed on the reservoir layer side of the interface between the reservoir layer and the stress relaxation layer from cracking or peeling due to thermal stress generated during heating and cooling. It is for preventing.
  • the stress relaxation layer is preferably one that is thermally stable at a high temperature (for example, 800 ° C. or higher and 1700 ° C.
  • the stress relaxation layer includes, for example, oxide ceramics containing zirconium, yttrium and oxygen, oxide ceramics containing aluminum, yttrium and oxygen, oxide ceramics containing aluminum, lanthanum and oxygen, aluminum and samarium, It consists of oxide ceramics containing oxygen, oxide ceramics containing cerium and oxygen, oxide ceramics containing thorium and oxygen, and the like.
  • the oxide ceramic containing zirconium, yttrium and oxygen is most preferably yttria stabilized zirconia (YSZ).
  • the thickness of the stress relaxation layer is appropriately selected as necessary.
  • the lower limit is the same thickness as that of the protective oxide film, for example, 1 ⁇ m.
  • the upper limit of the thickness of the stress relaxation layer is not particularly limited, but is generally 200 ⁇ m. That is, the thickness of the stress relaxation layer is generally 1 ⁇ m to 200 ⁇ m, but from the viewpoint of obtaining a sufficient stress relaxation effect, it is preferably 3 ⁇ m to 100 ⁇ m, and more preferably 3 ⁇ m to 50 ⁇ m. Hereinafter, it is more preferably 3 ⁇ m or more and 20 ⁇ m or less. From the viewpoint of obtaining the effect of reducing thermal conductivity in addition to the effect of stress relaxation, the stress relaxation layer is preferably a low density porous material.
  • the thermal conductivity depends on the porosity of YSZ, from 1.1 W / mK at a porosity of about 7.5% to about 0.00 at a porosity of about 15%. It changes in the range of 77 W / mK (for example, refer pp.171-172 of nonpatent literature 3).
  • a method for forming the diffusion barrier layer, the reservoir layer, and the stress relaxation layer various conventionally known methods can be used and are selected as necessary.
  • a method for forming the stress relaxation layer for example, at least one method selected from the group consisting of an electron beam evaporation method, an electrophoresis method, a slurry coating method, and a thermal spraying method is used.
  • an electrophoresis method is preferably used.
  • the heat-resistant alloy member is not particularly limited, and specific examples include turbine rotor blades and stationary blades, jet engines using them, industrial gas turbines, micro gas turbines, and the like.
  • a thermal cycle is added in a high-temperature corrosive atmosphere due to the synergistic effect of providing a diffusion barrier layer between the metal substrate and the reservoir layer and providing a stress relaxation layer on the reservoir layer. Even when used in a dry environment, cracking and peeling of the protective oxide film formed on the reservoir layer can be effectively suppressed. Further, the amount of expensive Pt added to the reservoir layer can be greatly reduced, or the addition of Pt is not necessary.
  • FIG. 1 is a drawing-substituting photograph showing a cross-sectional structure of the heat-resistant alloy member of Example 1.
  • FIG. 7 is a drawing substitute photograph showing an enlarged structure of a portion where a diffusion barrier layer is sandwiched between a metal substrate and a reservoir layer in the heat resistant alloy member shown in FIG. 6. It is a drawing substitute photograph which shows the cross-section of the heat-resistant alloy member of the comparative example 1 which does not form a stress relaxation layer.
  • 2 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Example 1.
  • FIG. It is a basic diagram which shows the mass increase with respect to the cycle number of the heat-resistant alloy member of Example 1 which performed thermal cycle oxidation on two conditions.
  • FIG. It is a basic diagram which shows the change of the density
  • FIG. It is a basic diagram which shows the change of the density
  • FIG. It is a basic diagram which shows the change of the density
  • FIG. It is a basic diagram which shows the change of the density
  • FIG. 6 is a cross-sectional view showing a configuration of a heat resistant alloy member of Comparative Example 4.
  • FIG. It is a basic diagram which shows the mass increase with respect to the cycle number of the heat-resistant alloy member of Example 2, 3 which performed thermal cycle oxidation on the conditions 1, and the comparative example 4.
  • FIG. 6 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Example 2.
  • FIG. 4 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Example 3.
  • FIG. 6 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Comparative Example 4.
  • FIG. It is a basic diagram which shows the change of the density
  • FIG. 4 shows a heat-resistant alloy member according to one embodiment.
  • a diffusion barrier layer 40 As shown in FIG. 1, in this heat-resistant alloy member, a diffusion barrier layer 40, a reservoir layer 20, and a stress relaxation layer 50 are laminated on the surface of a metal base 10 in order.
  • Examples of the metal base 10 include, but are not limited to, a Ni base superalloy, a stainless steel, a Ni—Cr—Mo base alloy (Hastelloy alloy), a Co base alloy, and the like.
  • the diffusion barrier layer 40 is made of an alloy containing Re, for example, a Re—Cr—Ni alloy, a Re—W—Cr—Ni alloy, a Re—Cr—Mo—Ni alloy, or the like.
  • the reservoir layer 20 is an alloy containing an element (Al, Cr, etc.) that forms a protective oxide film, for example, a Ni—Al alloy, a Ni—Pt—Al alloy, a MCrAlY alloy (M is made of Fe, Ni, and Co). At least one metal selected from the group).
  • the stress relaxation layer 50 is an oxide ceramic, for example, an oxide ceramic containing Zr, Y and O, an oxide ceramic containing Al, Y and O, an oxide ceramic containing Al, La and O, It consists of oxide ceramics containing Al, Sm and O, oxide ceramics containing Ce and O, oxide ceramics containing Th and O, and the like.
  • the thickness of the stress relaxation layer 50 is 1 ⁇ m or more and 200 ⁇ m or less, preferably 3 ⁇ m or more and 100 ⁇ m or less.
  • the oxide ceramic constituting the stress relaxation layer 50 is typically at least one metal different from the metal constituting the oxide ceramic, for example, Ni, Al, Cr, Ti, Hf, Ta, W, Re, It contains at least one metal selected from the group consisting of Cr and Mo.
  • a specific example of the oxide ceramic constituting the stress relaxation layer 50 is an oxide ceramic containing Zr, Y and O. Typically, this oxide ceramic is composed of this oxide ceramic. In addition to Zr and Y to be contained, it contains at least one metal selected from the group consisting of Ni, Al, Cr, Ti, Hf, Ta, W, Re, Cr and Mo. As a typical example, the oxide ceramic constituting the stress relaxation layer 50 is at least one metal selected from the group consisting of Ni, Al, Cr, Ti, Hf, Ta, W, Re, Cr, and Mo. Containing YSZ.
  • FIG. 5 shows a state in which a protective oxide film 30 such as Al 2 O 3 is formed on the reservoir layer 20.
  • the thickness of the protective oxide film 30 is typically about several ⁇ m, for example, but is not limited thereto.
  • the diffusion barrier layer 40, the reservoir layer 20, and the stress relaxation layer 50 are sequentially formed on the surface of the metal substrate 10 by a conventionally known method.
  • the heat-resistant alloy member is manufactured as follows. That is, first, a Re film is formed on the surface of the metal substrate 10 by a plating method. Next, a Cr diffusion treatment (chromizing treatment) is performed on the Re film, and then a high temperature heat treatment is performed. Thus, the diffusion barrier layer 40 is formed. Next, a Ni film is formed on the diffusion barrier layer 40 by plating. Next, an Al diffusion process (aluminizing process) is performed on the Ni film. Thus, the reservoir layer 20 made of a Ni—Al alloy is formed. Thereafter, a stress relaxation layer 50 made of an oxide ceramic such as YSZ is formed on the reservoir layer 20 by electron beam evaporation.
  • Example 1 will be described. A round bar made of Ni-based single crystal superalloy (CMSX-4) having a diameter of 12.5 mm is cut perpendicularly to the central axis to form a disc having a thickness of about 1.5 mm. did. The surface of the disk-shaped metal substrate 10 was polished with No. 220 SiC water-resistant abrasive paper and then degreased by ultrasonic cleaning in acetone.
  • CMSX-4 Ni-based single crystal superalloy
  • a Ni film is formed on the entire surface of the metal substrate 10 (both surfaces and side surfaces of the metal substrate 10) by an electrolytic plating method, then washed with distilled water, and subsequently electrolytically plated on the Ni film.
  • a Re (Ni) film was formed.
  • the formation of the Ni film and Re (Ni) film was repeated three times to form a total of three layers of Ni / Re (Ni) films.
  • the thicknesses of the Ni film and the Re (Ni) film were each about 2 ⁇ m.
  • Cr diffusion treatment chromizing treatment
  • the metal substrate 10 on which the Ni / Re (Ni) film was formed was placed in an alumina crucible and embedded in a Cr + Al 2 O 3 + NH 4 Cl mixed powder.
  • the mixture was heated in an argon (Ar) gas atmosphere, held at 800 ° C. for 2 hours, and then cooled in the furnace.
  • the metal substrate 10 was buried in a mixed powder of Ni-5Cr-15Al alloy powder + Al 2 O 3 , heated in vacuum (10 ⁇ 3 Pa) at 1280 ° C. for 2 hours, and then cooled in the furnace.
  • the diffusion barrier layer 40 was formed on the entire surface of the disk-shaped metal substrate 10 (both surfaces and side surfaces of the metal substrate 10).
  • the Ni film is buried in an Al + NH 4 Cl + Al 2 O 3 mixed powder, and then at 700 ° C. for 30 minutes in an Ar atmosphere. Al diffusion permeation treatment was performed.
  • the reservoir layer 20 was formed on the entire diffusion barrier layer 40 on the surface of the disk-shaped metal substrate 10 (both surfaces and side surfaces of the metal substrate 10).
  • stress made of YSZ on the reservoir layer 20 is deposited on one surface of the metal substrate 10 by electron beam evaporation using YSZ (ZrO 2 ceramics with 8 mol% of Y 2 O 3 added) as oxide ceramics.
  • a relaxation layer 50 was formed.
  • the thickness of the stress relaxation layer 50 was about 200 ⁇ m.
  • the stress relaxation layer 50 was not formed on the other surface and side surface of the metal substrate 10.
  • the stress relaxation layer 50 made of YSZ is exposed on one surface of the metal substrate 10, and the reservoir layer 20 is exposed on the other surface and side surfaces.
  • the metal substrate 10 in which the stress relaxation layer 50 is formed on one surface of the metal substrate 10 is referred to as a test piece.
  • the surface side of the test piece on which the stress relaxation layer 50 is formed is the heat resistant alloy member of Example 1, and the other surface side where the stress relaxation layer 50 is not formed and the reservoir layer 20 is exposed is the heat resistant alloy member of Comparative Example 1. It is.
  • FIG. 6 shows a cross-sectional scanning electron micrograph (cross-sectional SEM photograph) of the heat-resistant alloy member of Example 1 on the surface side where the stress relaxation layer 50 of this test piece was formed.
  • a diffusion barrier layer 40, a reservoir layer 20, a protective oxide film 30 and a stress relaxation layer 50 are formed in this order on the metal substrate 10.
  • a protective copper (Cu) plating layer 999 was formed on the surface of the stress relaxation layer 50 in taking a cross-sectional SEM photograph.
  • the concentration (atomic%) of each element at the position (001 to 007) designated on the photograph of FIG. 6 was measured using a SEM-EDAX apparatus (scanning electron microscope-energy dispersive spectrometer). Table 1 shows the results.
  • FIG. 8 shows a cross-sectional SEM photograph of the heat-resistant alloy member of Comparative Example 1, in which the stress relaxation layer 50 of this test piece is not formed and the reservoir layer 20 is exposed.
  • a diffusion barrier layer 40, a reaction layer 41, a reservoir layer 20, and a protective oxide film 30 are sequentially formed on the metal substrate 10.
  • a protective copper (Cu) plating layer 999 was formed on the surface of the protective oxide film 30 in taking a cross-sectional SEM photograph.
  • Table 3 shows the concentration (atomic%) of each element analyzed along the line shown in FIG.
  • thermal cycle oxidation test In order to confirm the effect of providing the stress relaxation layer 50 on the reservoir layer 20 in the heat-resistant alloy member of Example 1, evaluation was performed by a thermal cycle oxidation test.
  • a test piece In the thermal cycle oxidation test, a test piece is directly inserted into an electric furnace maintained at a predetermined temperature in the air, and after a predetermined time has passed, the test piece is pulled out of the furnace and cooled. More specifically, the thermal cycle oxidation test was performed under the following two conditions. Condition 1: Hold for 1 hour at a temperature of 1100 ° C. and hold for 20 minutes at room temperature alternately. Condition 2: 1 hour holding at a temperature of 1200 ° C. and 20 minutes holding at room temperature are alternately performed.
  • the weight change of the test piece was measured, the concentration of each element was measured with an X-ray element analyzer (oxygen O cannot be analyzed), and the test piece was photographed with an optical camera.
  • FIG. 9A shows a photograph of the appearance of the heat-resistant alloy member of Example 1 on one surface side where the stress relaxation layer 50 of the test piece after applying 700 cycles of thermal cycle oxidation under condition 1, is exposed.
  • FIG. 9B shows an appearance photograph of the other surface side of the test piece where the reservoir layer 20 is exposed, that is, the surface and side surfaces of the heat-resistant alloy member of Comparative Example 1.
  • 9A corresponds to the part indicated by the arrow in FIG. 9B.
  • the concentration (atomic%) of each element of points (1) to (4) described in the photograph of FIG. 9A was measured. The results are shown in Table 4.
  • FIG. 10 shows a change in mass increase of the heat-resistant alloy member with respect to the square root of the number of cycles when thermal cycle oxidation is added under conditions 1 and 2.
  • the number of cycles is about 200 (point C indicated by an arrow)
  • the number of cycles is about 30 (arrow).
  • FIG. 11 shows the result of measuring the concentration of each element on the surface of the stress relaxation layer 50 with respect to the square root of the number of cycles when thermal cycle oxidation is added under the condition 1 with an X-ray element analyzer.
  • the Zr and Y concentrations are in agreement with the results shown in Table 4, and change with the number of cycles is small.
  • FIG. 12 shows the concentration of each element on the surface of the reservoir layer 20 (including the protective oxide film 30) with respect to the square root of the number of cycles when thermal cycle oxidation was added under the condition 1 was measured with an X-ray element analyzer. Results are shown.
  • Al and Ni are observed at the initial stage of oxidation, and the Al concentration tends to increase and the Ni concentration tends to decrease as the number of cycles increases.
  • the Al concentration started to decrease, the Ni concentration started to increase, and other elements were also detected.
  • FIG. 13 shows the result of measuring the concentration of each element on the surface of the stress relaxation layer 50 with respect to the square root of the number of cycles when thermal cycle oxidation is added under the condition 2 with an X-ray element analyzer.
  • concentrations of Al and Ni which were hardly observed in the initial stage of oxidation, increased as the number of cycles increased.
  • FIG. 14 shows the result of measuring the concentration of each element on the surface of the reservoir layer 20 with respect to the square root of the number of cycles when thermal cycle oxidation is added under the condition 2 with an X-ray element analyzer.
  • Al and Ni are observed at the initial stage of oxidation, and the Al concentration tends to increase and the Ni concentration tends to decrease as the number of cycles increases.
  • the Al concentration started to decrease, the Ni concentration started to increase, and other elements were also detected. This means that peeling of the protective oxide film 30 from the reservoir layer 20 has started at point C.
  • Example 2 will be described.
  • the Ar gas atmosphere is heated after the metal base material 10 on which the Ni / Re (Ni) film is formed is placed in an alumina crucible and embedded in a Cr + Al 2 O 3 + NH 4 Cl mixed powder.
  • the condition is 800 ° C. for 3 hours, and the condition of heating in vacuum after the metal substrate 10 is embedded in the mixed powder of Ni-5Cr-15Al alloy powder + Al 2 O 3 is 1300 ° C. for 2 hours.
  • a test piece was formed in the same manner as in Example 1.
  • the surface side of the test piece on which the stress relaxation layer 50 is formed is the heat resistant alloy member of Example 2, and the other surface side where the stress relaxation layer 50 is not formed and the reservoir layer 20 is exposed is the heat resistant alloy of Comparative Example 2. It is a member.
  • Example 3 Example 3 will be described.
  • a test piece was formed in the same manner as in Example 2.
  • the surface side of the test piece on which the stress relaxation layer 50 is formed is the heat resistant alloy member of Example 3, and the other surface side where the stress relaxation layer 50 is not formed and the reservoir layer 20 is exposed is the heat resistant alloy of Comparative Example 3. It is a member.
  • Comparative Example 4 Comparative example 4 will be described.
  • a test piece was formed in the same manner as in Example 1 except that the reservoir layer 20 was not formed and the stress relaxation layer 50 was formed directly on the diffusion barrier layer 40.
  • the cross-sectional structure of this test piece is shown in FIG.
  • FIG. 16 shows a change in mass increase of the heat-resistant alloy members of Examples 2 and 3 and Comparative Example 4 with respect to the square root of the number of cycles when thermal cycle oxidation is added under condition 1. From the cycle number dependency of the oxidation amount shown in FIG. 16, when thermal cycle oxidation is added under condition 1, the oxidation amount initially increases with the cycle number, but variation or decrease is observed in the middle. This is because the oxidation of the surface or end surface on which the stress relaxation layer 50 is not formed becomes significant, and a part of the oxide film is peeled off. This critical cycle number is 225 cycles in the second embodiment and 182 cycles in the third embodiment. 17A-E (FIG. 17A before oxidation, FIG. 17B after 1 cycle, FIG.
  • FIGS. 18A-D FIGS. 18A Before oxidation, as shown in FIG. 18B after 1 cycle, FIG. 18C after 182 cycles, and FIG. 18D after 412 cycles), from the surface morphology photograph of the stress relaxation layer 50 made of the YSZ layer, 450 cycles in Example 2, In Example 3, in 412 cycles, no separation of the stress relaxation layer 50 is observed. However, in Example 2, the stress relaxation layer 50 was peeled in 505 cycles.
  • Example 1 In the result of Example 1 shown in FIG. 10, the critical cycle number is about 200 cycles, which matches the values of Examples 2 and 3. However, in Example 1, no peeling occurred even after 700 cycles. These differences are likely to be within experimental error.
  • the amount of oxidation at the critical cycle number was 2 mg / cm 2 in Example 1, whereas it was about 0.6 mg / cm 2 in Examples 2 and 3.
  • the protective oxide film 30 made of Al 2 O 3 is formed between the reservoir layer 20 and the stress relaxation layer 50 and has the structure shown in FIG.
  • the peel resistance of the protective oxide film 30 can be improved (twice or more as the number of cycles).
  • the reservoir layer 20 that forms the protective oxide film is not formed. Therefore, the protective oxide film is peeled off from the initial stage of the thermal cycle oxidation on the surface where the stress relaxation layer 50 is not formed. On the other hand, the stress relieving layer 50 was in sound contact with each other, and peeling was observed after 167 cycles. Thus, even in a diffusion barrier coating in which the reservoir layer 20 is not formed, the stress relaxation layer 50 can remarkably improve the peeling resistance of the protective oxide film 30 (100 times or more as the number of cycles).
  • the stress relaxation layer 50 showed excellent peeling resistance, which is considered as follows. That is, the diffusion barrier layer 40 contains (20-40) atomic% Cr and 20 atomic% Ni in addition to Re, and a Cr 2 O 3 or NiCr 2 O 4 film is formed. It is considered that the formation of the non-protective oxide vapor of Re (for example, Re 2 O 7 ) is suppressed by the stress relaxation layer 50 made of
  • FIG. 3 shows a conventional TBC.
  • a bond coat layer 60, a protective oxide film 30, and a top coat layer 70 made of ceramic are sequentially laminated on the surface of the metal substrate 10.
  • the top coat layer 70 an oxide having a low thermal conductivity, for example, YSZ, is used, and its thickness is generally 250 ⁇ m to 1000 ⁇ m, and in many applications, it is necessary to have a thickness of ⁇ 1000 ⁇ m. (For example, see pp.
  • YSZ constituting the top coat layer 70 functions as a heat shield layer against high-temperature combustion gas, and the inside of the metal substrate 10 is air-cooled, so that the metal substrate 10 and the bond coat layer 60 are relatively It is kept at a low temperature. What is important here is that the diffusion barrier layer 40 is not formed between the metal substrate 10 and the bond coat layer 60. For this reason, even if the top coat layer 70 made of YSZ is formed in the same manner as the stress relaxation layer 50, the protective oxide film 30 formed on the bond coat layer 60 can be prevented from cracking or peeling. In other words, the top coat layer 70 cannot be prevented from cracking or peeling.
  • the diffusion barrier layer 40 made of an alloy containing Re between the metal substrate 10 and the reservoir layer 20 made of an alloy containing Al or Cr.
  • the stress relaxation layer 50 made of oxide ceramics such as YSZ is provided on the reservoir layer 20, so that the reservoir layer can be used even when used in an environment where a thermal cycle is added in a high temperature corrosive atmosphere.
  • the protective oxide film 30 formed on 20 can be very effectively prevented from cracking and peeling.
  • the heat-resistant alloy member is suitable for application to, for example, a moving blade and a stationary blade of a turbine, a jet engine using this turbine, an industrial gas turbine, and the like.
  • the present invention is not limited to the above-described embodiment and example, and various types based on the technical idea of the present invention. Deformation is possible.

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Abstract

L'invention propose : un élément d'alliage résistant à la chaleur qui est apte à diminuer des fissurations ou une séparation d'un film de revêtement d'oxyde protecteur qui est formé sur une couche réservoir même lorsqu'il est utilisé dans un environnement où un cycle thermique est appliqué à celui-ci dans une atmosphère corrosive à température élevée, dans ledit élément d'alliage résistant à la chaleur, la quantité de Pt coûteux ajouté dans la couche réservoir étant significativement réduite ou l'addition de Pt n'étant pas nécessaire ; et un procédé de fabrication de l'élément d'alliage résistant à la chaleur. Un élément d'alliage résistant à la chaleur est configuré par laminage de manière séquentielle d'une couche barrière de diffusion (40), d'une couche réservoir (20) et d'une couche de relaxation des contraintes (50) sur la surface d'une base métallique (10). La couche barrière de diffusion (40) est formée d'un alliage qui contient Re. La couche réservoir (20) est formée d'un alliage qui contient Al. La couche de relaxation des contraintes (50) est formée, par exemple, d'une céramique d'oxyde qui contient Zr, Y, O et au moins un métal choisi dans le groupe consistant en Ni, Al, Cr, Ti, Hf, Ta, W, Re, Co et Mo. Un film de revêtement d'oxyde protecteur est formé sur la couche réservoir (20).
PCT/JP2012/077298 2011-10-26 2012-10-23 Élément d'alliage résistant à la chaleur et son procédé de fabrication Ceased WO2013061945A1 (fr)

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Cited By (2)

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JP2020033589A (ja) * 2018-08-29 2020-03-05 株式会社ディ・ビー・シー・システム研究所 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ならびに耐熱合金部材製造用部材
US10934860B2 (en) 2016-06-21 2021-03-02 Rolls-Royce Plc Gas turbine engine component with protective coating

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JPH11507101A (ja) * 1995-05-08 1999-06-22 アライド・シグナル・インコーポレーテツド 多孔質熱障壁被覆体
JP2008266698A (ja) * 2007-04-18 2008-11-06 Hitachi Ltd 遮熱被覆を有する耐熱部材
JP2009270199A (ja) * 2008-05-02 2009-11-19 General Electric Co <Ge> 保護皮膜を有する物品及び方法
WO2010069912A1 (fr) * 2008-12-15 2010-06-24 Alstom Technology Ltd Système d'enduction avec barrière thermique, composants ainsi revêtus et procédé d'application d'un système d'enduction avec barrière thermique à des composants
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

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JPH11507101A (ja) * 1995-05-08 1999-06-22 アライド・シグナル・インコーポレーテツド 多孔質熱障壁被覆体
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
JP2008266698A (ja) * 2007-04-18 2008-11-06 Hitachi Ltd 遮熱被覆を有する耐熱部材
JP2009270199A (ja) * 2008-05-02 2009-11-19 General Electric Co <Ge> 保護皮膜を有する物品及び方法
WO2010069912A1 (fr) * 2008-12-15 2010-06-24 Alstom Technology Ltd Système d'enduction avec barrière thermique, composants ainsi revêtus et procédé d'application d'un système d'enduction avec barrière thermique à des composants

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10934860B2 (en) 2016-06-21 2021-03-02 Rolls-Royce Plc Gas turbine engine component with protective coating
JP2020033589A (ja) * 2018-08-29 2020-03-05 株式会社ディ・ビー・シー・システム研究所 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ならびに耐熱合金部材製造用部材
JP7138339B2 (ja) 2018-08-29 2022-09-16 株式会社ディ・ビー・シー・システム研究所 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

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