JP5794537B2 - Heat-resistant alloy member and method for producing the same, alloy film and method for producing the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a heat-resistant alloy member, a manufacturing method thereof, an alloy film, and a manufacturing method thereof. For example, a gas turbine member, a jet engine member, a rocket member, an industrial furnace member, a chemical plant It is suitable to be applied to a heat-resistant alloy member suitable for use as a high-temperature heat-resistant member for energy conversion equipment and energy conversion equipment.

In order to improve heat resistance and corrosion resistance, gas turbine members, jet engine members, rocket members, industrial furnace members, chemical plant members, high-temperature heat-resistant members of energy conversion equipment, etc. In many cases, a heat resistant and hot corrosion resistant alloy film is formed on the surface of the member. Examples of the heat-resistant and high-temperature corrosion-resistant alloy film include diffusion aluminide coating, diffusion chrome coating, diffusion silicon coating, and Ni—Cr alloy overlay coating. Alumina (Al ₂ O ₃ ), chromia (Cr ₂ O ₃ ) A film made of silica (SiO ₂ ) or the like is formed to protect the high-temperature device member. As an example, turbochargers have a diffusion chromium coating applied to form a protective Cr ₂ O ₃ scale to protect the alloy members. In the gas turbine, in order to protect the alloy member from high-temperature combustion gas, an overlay coating of MCrAlY alloy (M = Ni, Co, Fe) is applied, and an Al ₂ O ₃ film is formed to protect the alloy member. . In a jet engine, a Ni—Al alloy, a Ni—Al—Pt alloy with Pt added, or the like is used, and a protective Al ₂ O ₃ scale is formed to protect the alloy member. In the satellite thruster, a niobium silicide coating is applied, and a protective SiO ₂ film protects the Nb-based alloy from a high-temperature combustion gas atmosphere.

  In recent gas turbine parts, jet engine parts, rocket parts, industrial furnace parts, chemical plant parts, high-temperature heat-resistant parts for energy conversion equipment, etc., diversification of fuels and higher operating temperatures are being promoted. ing.

When the environment in which the high-temperature heat-resistant member is used is an extremely high temperature of about 800 to 1500 ° C., the concentration of elements (Cr, Al, Si) added to the coating layer to form a protective oxide film depends on the high-temperature oxidation. Reduced due to oxide film formation. The increase in the operating temperature reveals the diffusion movement of the above elements (Cr, Al, Si) to the alloy substrate side, and further, the elements (for example, Ni, Co) included in the alloy substrate constituting the high temperature device member , Fe, Ti, Mo, W, Re, Ru, C, Si, Al, S, etc.) diffuse and move to the coating layer side, and the concentration of Cr, Al, Si, etc. in the coating layer decreases. As a result, the protective oxide film (for example, Cr ₂ O ₃ , Al ₂ O ₃ , SiO _2, etc.) formed on the surface undergoes cracking, peeling, or non-protective oxide film (for example, FeO , CoO, NiO, FeAl ₂ O ₄ , CoAl ₂ O ₄ , NiAl ₂ O ₄ , FeCr ₂ O ₄ , NiCr ₂ O ₄ , CoCr ₂ O _4, etc.) and the protective performance of the coating layer is lost become.

  Thermal barrier coating (TBC) is applied to alloy members such as turbine blades and stationary blades. This TBC is composed of at least two layers of a bond coat and a top coat. For the bond coat, MCrAlY alloy (M = Ni, Co), Ni—Al alloy, Ni—Al—Pt alloy, etc. are used. Thermally grown oxide (TGO) is formed on the surface of the substrate to protect the substrate from oxidizing and corrosive environments. 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 high-temperature combustion gas, and the base alloy and the bond coat are maintained at a relatively low temperature by air-cooling the inside of the base alloy.

Since the coating layer and the TBC bond coat contain a higher concentration of Al compared to the substrate, during use at high temperatures, Al diffuses from the coating layer or bond coat to the substrate, A secondary reaction zone (SRZ) is formed in the base material to reduce the strength of the base material. Furthermore, a reduction in the Al concentration of the coating layer or bond coat loses the formation of non-protective oxide scale (eg, NiAl ₂ O ₄ , NiO, etc.) and the protective performance of TGO.

  In order to solve these problems, the present inventors proposed a diffusion barrier layer that suppresses interdiffusion of elements between the substrate and the coating layer or bond coat, and as a result of earnest search, rhenium (Re) It has been found that an alloy phase to be contained (for example, a Re—Cr—Ni-based σ phase) has excellent diffusion barrier properties and disclosed to be used as a diffusion barrier layer (see Patent Documents 1 to 10).

  According to Non-Patent Documents 1 and 2, the diffusion barrier layer (for example, the Re—Cr—Ni-based σ phase) is a crystal that forms a coating layer or bond coat with the Ni—Al—Cr-based (γ + γ ′) phase of the base material. The Ni-Al-Cr phase (γ, γ ', β) phase has a conjugated composition and is considered to be thermodynamically stable, maintaining its function as a diffusion barrier layer at high temperatures for a long time. It can be done. The present inventor refers to the diffusion barrier coating including the diffusion barrier layer and the Al reservoir layer, and includes the base material and the diffusion barrier coating as the diffusion barrier coating system (DBC system). Yes.

According to Non-Patent Documents 1 and 2, the DBC system is based on a base material (for example, a second generation Ni-based single crystal superalloy (TMS-82), a third generation single crystal superalloy (CMSX-4), 4th generation single crystal superalloy (TMS-138), stainless steel (SUS310S), Ni—Cr—Mo alloy (Hastelloy-X)) and Al reservoir (for example, Ni—Cr—Al alloy, Ni—Cr—Al—) Applied to (Pt alloy), the interdiffusion between the base material and the Al reservoir is effectively suppressed and a protective oxide scale (Al ₂ O ₃ ) is formed and maintained.

  Furthermore, the present inventors interpose an Ni—Cr-based α-Cr phase inner layer as a diffusion barrier layer on the surface of a Ni—Cr base alloy base material, and an outer layer having a high Al concentration (for example, Ni—Al— By forming a Cr-based β-phase and γ′-phase), it has been found that the original excellent high-temperature characteristics of the Ni-based alloy of the base material can be sustained. And Non-Patent Document 3.

  Non-Patent Document 4 proposes a W (Ni) -based barrier layer formed by plating a Ni-W alloy on a Ni-based single crystal superalloy and then heat-treating it. The formed W (Ni) alloy phase is mainly composed of 88.18 atomic% W and 9.79 atomic% Ni, and contains 1.49 atomic% Re and 0.3 atomic% Cr. Non-Patent Document 5 discloses a Re—W—Ni-based barrier layer formed by plating Re and a Ni—W alloy, followed by heat treatment. The following three points are disclosed as the composition of this Re-W-Ni alloy. That is, 43.7 atomic% Re, 30.7 atomic% W, 13.6 atomic% Ni, 3.49 atomic% Cr, 3.21 atomic% Al, or 43.5 atomic% Re, 29.2 atoms % W, 14.9 atomic% Ni, 3.66 atomic% Cr, 6.95 atomic% Al, or 3.66 atomic% Re, 62.9 atomic% W, 18.0 atomic% Ni, 0.20 Atomic% Cr and 11.9 atomic% Al are contained.

  Non-Patent Documents 4 and 5 propose a barrier layer for a Ni-based single crystal superalloy, which contains W, Re, and Ni as main components and a Cr content of 3.66 atomic% or less.

Japanese Patent No. 3,857,689 Japanese Patent No. 3857690 Japanese Patent No. 3910588 Japanese Patent No. 3944437 Japanese Patent No. 4271399 Japanese Patent No. 4323816 Japanese Patent No. 4753720 International Publication 2008/059971 Pamphlet Japanese Patent No. 4896702 Japanese Patent No. 3916484

T. 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 T. Narita, T. Izumi, T. Nishimoto, Y. Shibata, K. Zaini Thosin, S. Hayashi; Advanced Coatings on High Temperature Applications, Materials Science Forum, Vols. 525-523 (August 2006), pp.1- 14 E. Cavaletti, S. Mercier, D. Boivin, M-. P. Bacos, P. Josso, D. Monceau; Development of a NiW in-situ diffusion barrier on a fourth generation nickel-base superalloy, Materials Science Forum, Vols .595-598 (2008), pp.23-32 S. Mercier, D. Boivin, M-. P. Bacos, P. Josso; A novel duplex Re-NiW based diffusion barrier on a nickel-based superalloy, Materials Science Forum, Vols. 595-598 (2008), pp. 127-134

  Iron (Fe) -based alloy, cobalt, which has excellent high-temperature strength and formability, as a gas turbine member, jet engine member, rocket member, industrial furnace member, chemical plant member, and high-temperature heat-resistant member for energy conversion equipment Heat-resistant materials such as (Co) -based alloys and nickel (Ni) -based alloys are used.

  Examples of the above-mentioned various coatings (diffusion aluminide coating, diffusion chrome coating, diffusion silicon coating, Ni—Cr alloy overlay coating, MCrAlY alloy (M = Co, Ni) overlay coating) applied to these heat-resistant materials. It has been reported. However, in a high temperature corrosive environment, the protective function of the coating is lost early, and further, the strength of the base material is reduced due to interdiffusion of elements between the base material and the coating.

  On the other hand, the diffusion barrier type coating using the Re—Cr—Ni system σ phase proposed in Patent Documents 1 to 9 as a diffusion barrier layer is an optimum coating applied to a Ni-base superalloy, but expensive Re I need. Further, the coating proposed in Patent Document 10 has a problem that the Ni—Cr-based α-Cr phase is used as a diffusion barrier layer and is limited to a Ni-based alloy. In the coating used as a W—Re—Ni diffusion barrier proposed in Non-Patent Documents 4 and 5, the coating is limited to a Ni-based single crystal superalloy, and the Cr concentration is limited to several percent or less.

  Therefore, the problem to be solved by the present invention is to provide a heat-resistant alloy member having excellent oxidation resistance and long life in a high-temperature corrosive atmosphere, a manufacturing method thereof, an alloy film, and a manufacturing method thereof.

The present inventors have studied in detail a diffusion barrier coating having a multilayer structure of an inner layer and an outer layer, which is optimally applied to the surface of an alloy substrate made of an Fe-based alloy. As a result, as the inner layer, for example, an Fe—Cr—W alloy and an element X (for example, nickel (Ni)), tantalum (Ta), rhenium (Re), molybdenum (Mo)) added Fe—Cr— It has been found that a W—Ni—Ta—Re—Mo alloy is a candidate. Further, as an outer layer, a Fe—Al alloy, a Fe—Cr—Al alloy, a Fe—Ni—Cr—Al alloy, and a Ni—Fe—Cr—Al—Si alloy form a protective Al ₂ O ₃ film. It has been found that Fe—Cr alloys and Fe—Ni—Cr alloys are effective for forming a protective Cr ₂ O ₃ film. From the above results, an optimum diffusion barrier coating system (for example, Fe-based alloy / inner layer / outer layer / protective oxide film) can be obtained when applied to an Fe-based alloy. That is, the α-Cr (W, Fe) phase and α-W (Cr, Fe) phase of the Fe-Cr-W-based alloy, and various (Fe, Cr) W phases were excellent for Al diffusion. It has been found that it has diffusion barrier properties, and has found a diffusion barrier coating system having at least a multilayer structure in which these alloy phases are used as an inner layer and an alloy containing Al is used as an outer layer. Furthermore, it discovered that each alloy layer which comprises the said inner layer can suppress effectively the spreading | diffusion to the outer layer of Fe. That is, since Fe is an element that degrades oxidation resistance, by suppressing the penetration of this Fe, by suppressing the decrease in the concentration of Al and Cr in the outer layer, excellent oxidation resistance can be achieved over a long period of time. It can be maintained over time. Further, the α-Cr (W, Fe) phase constituting the inner layer has an effect of effectively suppressing the diffusion of the alloy element (for example, Fe) to the outer layer, and the outer layer (for example, Fe—Cr alloy, Fe It also acts as a supply source of Cr to (Ni—Cr alloy). As a result of applying this multi-layer coating on the surface of an alloy base made of an Fe-based alloy and performing an oxidation test at a high temperature, the multi-layer structure is maintained over a long period of time and a long-life protective Al ₂ O ₃ film In addition, this inventor has demonstrated the formation of a protective Cr ₂ O ₃ film, and the present inventor has developed a novel diffusion barrier coating with excellent oxidation resistance and coating structure / structure stability applied to Fe-based alloys It came to do.

In addition, the present inventors have studied in detail a diffusion barrier coating having a multilayer structure of an inner layer and an outer layer, which is optimally applied to the surface of an alloy substrate made of a Co-based alloy. As a result, a Co—Cr—W alloy and a Co—Cr—W—Ni—Ta—Re—Mo alloy to which an element X (eg, Ni, Ta, Re, Mo) is added as an inner layer are candidates. I found. Furthermore, as an outer layer, a Ni—Al alloy, a Ni—Al—Cr alloy, a Ni—Co—Al—Cr—Si alloy, a protective Al ₂ O ₃ coating, a Ni—Cr alloy, a Ni—Co alloy It has been found that a -Cr alloy is effective for forming a protective Cr ₂ O ₃ film. From the above results, it was possible to develop an optimum diffusion barrier coating system (for example, Co-based alloy / inner layer / outer layer / protective oxide film) applied to a Co-based alloy. That is, the σ-Co ₂ Cr phase, the α-Cr phase and the α-W phase, the (Co, W) ₂ Cr ₃ phase and the Co-Cr-W phase of the Co-Cr-W alloy are used as the inner layer, and Al is contained. We have found a diffusion barrier coating system having at least a multi-layer structure with an alloy as an outer layer. Furthermore, it has been found that the α-Cr (W, Co) phase constituting the inner layer can effectively suppress diffusion of the alloy element (for example, Co) to the outer layer. That is, since Co is an element that deteriorates oxidation resistance, by suppressing the intrusion of Co, the outer layer (for example, Ni—Al alloy, Ni—Al—Cr alloy, Ni—Co—Al—) is suppressed. The excellent oxidation resistance of the Cr—Si alloy, Ni—Cr alloy, Ni—Co—Cr alloy) can be maintained over a long period of time. Furthermore, the α-Cr (W, Co) phase constituting the inner layer has an effect of effectively suppressing the diffusion of the alloy element (for example, Co) to the outer layer, and the outer layer (for example, Ni—Cr alloy, Ni It also acts as a supply source of Cr to (-Co-Cr alloy). This multi-layer coating is applied to the surface of a Co-based alloy and subjected to an oxidation test at a high temperature. As a result, the multi-layer structure is maintained over a long period of time, and a long-life protective Al ₂ O ₃ scale or protective Cr ₂ Having demonstrated the formation of O ₃ scale, the present inventor has applied to a Co-based alloy and has developed a novel diffusion barrier coating having excellent oxidation resistance and coating structure / structure stability.

In addition, the present inventors have studied in detail a diffusion barrier coating having a multilayer structure of an inner layer and an outer layer, which is optimally applied to the surface of a Ni-based alloy. As a result, a Ni—Cr—W alloy and an Ni—Cr—W—Fe—Ta—Re—Mo alloy to which an element X (eg, Fe, Ta, Re, Mo) is added as an inner layer are candidates. I found. Further, as an outer layer, a Ni—Al alloy, a Ni—Cr—Al alloy, a Ni—Co—Cr—Al alloy, and a Ni—Co—Cr—Al—Si alloy form a protective Al ₂ O ₃ film. It has been found that Ni—Cr alloy and Ni—Cr—Al alloy are effective for forming a protective Cr ₂ O ₃ film. From the above results, it was possible to develop an optimum diffusion barrier coating system (for example, Ni-based alloy / inner layer / outer layer / protective oxide film) applied to a Ni-based alloy. That is, the α-Cr (W, Ni) phase and α-W (Cr, Ni) phase of the Ni-Cr-W alloy, and the (Cr, W) Ni phase are excellent diffusion barriers against Al diffusion. It has been found that the diffusion barrier coating system has at least a multilayer structure in which these alloy phases are used as an inner layer and an alloy containing Al is used as an outer layer. Furthermore, it has been found that each alloy layer constituting the inner layer can effectively suppress the diffusion of Ni to the outer layer. That is, by suppressing the intrusion of Ni, it is possible to maintain excellent oxidation resistance over a long period of time by suppressing a decrease in the concentration of Al and Cr in the outer layer. Further, the α-Cr (W, Ni) phase constituting the inner layer has an effect of effectively suppressing the diffusion of the alloy element (for example, Ni) to the outer layer, and the outer layer (for example, a Ni—Cr alloy, Ni It also acts as a supply source of Cr to (-Cr-Al alloy). This multi-layer coating is applied to the surface of a Ni-based alloy. From the results of high-temperature stability evaluation and oxidation test, the multi-layer structure is maintained over a long period of time, and a long-life protective Al ₂ O _The present inventors have demonstrated the formation of _three coatings and a protective Cr ₂ O ₃ coating, and the present inventor has applied a Ni-based alloy to a novel diffusion barrier coating having excellent oxidation resistance and coating structure / structure stability. I found.

  The present invention has been devised as a result of intensive studies based on the above-mentioned findings obtained independently by the present inventors.

That is, in order to solve the above problems, the present invention provides:
An alloy base material containing at least 10 atomic% or more of Cr at the surface layer part;
Having an alloy film formed on the surface of the alloy substrate,
The alloy film has at least one inner layer and at least one outer layer,
At least one inner layer is a heat-resistant alloy member containing at least one element selected from the group consisting of Fe, Co, and Ni, and W and Cr.

  Here, the inner layer serves as a diffusion barrier layer, and the outer layer serves as a reservoir layer, and the entire inner layer and outer layer constitute a diffusion barrier coating. Here, typically, the crystal phases constituting the inner layer and the outer layer have a conjugated composition relationship between the alloy base material and the inner layer and between the inner layer and the outer layer, respectively. The material constituting the alloy base material is, for example, an Fe-based alloy, a Co-based alloy, a Ni-based alloy, or the like, but is not limited thereto.

  There are various combinations of the inner layer and the outer layer. For example, the inner layer is a Cr—W alloy layer and the outer layer is an alloy layer containing Al. Further, the inner layer is a Cr—W alloy layer, a Cr—W—Ta alloy layer, a Cr—W—Mo alloy layer, a Cr—W—Ta—Mo alloy layer and a Cr—W—Ta—Mo—Re alloy layer. At least one selected from the group consisting of alloy layers, the outer layer is an alloy layer containing Cr. When there are two inner layers, assuming the inner layer I and the inner layer II from the alloy substrate side, the combinations of the inner layer and the outer layer are as follows, for example. Inner layer I is Cr—W alloy layer, Cr—W—Ta alloy layer, Cr—W—Mo alloy layer, Cr—W—Ta—Mo alloy layer and Cr—W—Ta—Mo—Re alloy At least one selected from the group consisting of layers, the inner layer II is an α-Cr layer of a Cr—W alloy, and the outer layer is a Ni—Cr alloy layer. Further, the inner layer I is a Cr—W alloy layer, a Cr—W—Ta alloy layer, a Cr—W—Mo alloy layer, a Cr—W—Ta—Mo alloy layer, and a Cr—W—Ta—Mo—Re. At least one selected from the group consisting of alloy layers, the inner layer II is an α-Cr layer of a Cr—W alloy, and the outer layer is a Ni—Cr—Al—Si alloy layer.

FIG. 1 shows a Fe—Cr—W ternary phase diagram. In FIG. 1, regions A _{1 to} A ₅ are in a preferred composition range, and preferably at least one inner layer has a composition in this composition range. The composition of the regions A _{1 to} A ₅ is as follows.
Region A ₁ : W is contained in the range of 10 atomic% to 21 atomic%, Cr is contained in the range of 23 atomic% to 53% and Fe is contained in the range of 25 atomic% to 66 atomic% (total of 100 atomic%)
Region A ₂ : W is 30 atomic% to 45 atomic%, Cr is 10 atomic% to 40 atomic%, and Fe is 30 atomic% to 59 atomic% (total is 100 atomic%)
Region A ₃ : W is contained in the range of 35 atomic% to 45 atomic%, Cr is contained in the range of 0.1 atomic% to 50 atomic%, and Fe is contained in the range of 15 atomic% to 64 atomic% (total of 100 atomic%).
Region A ₄ : W is 0.1 atomic% or more and 20 atomic% or less, Cr is 70 atomic% or more and 99 atomic% or less, and Fe is 0.1 atomic% or more and 29 atomic% or less (total is 100 atomic%).
Region A ₅ : W is 77 atomic% to 99 atomic%, Cr is 0.1 atomic% to 20 atomic%, and Fe is 0.1 atomic% to 2 atomic% (total is 100 atomic%)

FIG. 2 shows a Co—Cr—W ternary phase diagram. In FIG. 2, regions B _{1 to} B ₆ are in a preferred composition range, and preferably at least one inner layer has a composition in this composition range. The composition of the regions B _{1 to} B ₆ is as follows.
Region B ₁ : W is contained in 0.1 atomic% or more and 3 atomic% or less, Cr is contained in 52 atomic% or more and 65 atomic% or less, and Co is contained in 30 atomic% or more and 54 atomic% or less (100 atomic% in total).
Region B ₂ : W is contained in 3 atomic% to 25 atomic%, Cr is contained in 30 atomic% to 65 atomic%, and Co is contained in 25 atomic% to 55 atomic% (total of 100 atomic%).
Region B ₃ : W is 25 atomic% to 35 atomic%, Cr is 20 atomic% to 40 atomic%, Co is 30 atomic% to 50 atomic% (total is 100 atomic%)
Region B ₄ : W is 30 atomic% to 55 atomic%, Cr is 0.1 atomic% to 50 atomic%, and Co is 20 atomic% to 60 atomic% (total is 100 atomic%)
Region B ₅ : W is 0.1 atomic% to 25 atomic%, Cr is 65 atomic% to 99 atomic%, and Co is 0.1 atomic% to 25 atomic% (total is 100 atomic%)
Region B ₆ : W is 75 atomic% to 99 atomic%, Cr is 0.1 atomic% to 25 atomic%, and Co is 0.1 atomic% to 3 atomic% (total is 100 atomic%)

FIG. 3 shows a Ni—Cr—W ternary phase diagram. In FIG. 3, regions C _{1 to} C ₃ are in a suitable composition range, and preferably at least one inner layer has a composition in this composition range. The composition of the regions C _{1 to} C ₃ is as follows.
Region C ₁ : W is contained in 2 atom% or more and 20 atom% or less, Cr is contained in 40 atom% or more and 65 atom% or less, and Ni is contained in 30 atom% or more and 40 atom% or less (100 atom% in total).
Region C ₂ : W is 0.1 atomic% or more and 20 atomic% or less, Cr is 70 atomic% or more and 99 atomic% or less, and Ni is 0.1 atomic% or more and 30 atomic% or less (total is 100 atomic%).
Region C ₃ : W is 80 atomic% to 99 atomic%, Cr is 0.1 atomic% to 20 atomic%, and Ni is 0.1 atomic% to 3 atomic% (total is 100 atomic%)

  The alloy film may include at least two inner layers having different compositions selected from the various inner layers described above.

FIG. 4 shows a Ni—Cr—Al ternary phase diagram. In FIG. 4, regions D _{1 to} D ₅ are in a suitable composition range, and preferably at least one outer layer has a composition within this composition range. The composition of the regions D _{1 to} D ₅ is as follows.
Region D ₁ : Cr is 0.1 atomic% to 50 atomic%, Al is 0.1 atomic% to 22 atomic%, and Ni is 51 atomic% to 99 atomic% (total is 100 atomic%)
Region D ₂ : Cr is contained in the range of 0.1 atomic% to 10 atomic%, Al is contained in the range of 23 atomic% to 29 atomic%, and Ni is contained in the range of 70 atomic% to 75 atomic% (total of 100 atomic%).
Region D ₃ : Cr is contained in an amount of 0.1 atomic% or more and 14 atomic% or less, Al and Si are added in a total of 30 atomic% or more and 55 atomic% or less, and Ni, Co, and Fe are added in a total of 45 atomic% or more and 65 atomic% or less ( 100 atomic percent in total)
Region D ₄ : Cr is contained in 0.1 atomic percent to 20 atomic percent, Al is contained in 58 atomic percent to 63 atomic percent, and Ni is contained in 36 atomic percent to 41 atomic percent (total of 100 atomic percent).
Region D ₅ : Cr is contained in an amount of 56 atom% to 99 atom%, Al is contained in an amount of 0.1 atom% to 43 atom%, and Ni is contained in an amount of 0.1 atom% to 25 atom% (total of 100 atom%).

FIG. 5 shows a Fe—Cr—Al ternary phase diagram. In FIG. 5, regions E _{1 to} E ₃ are in a preferred composition range, and preferably at least one outer layer has a composition within this composition range. The composition of the regions E _{1 to} E ₃ is as follows.
Region E ₁ : Cr is 0.1 atomic% or more and 15 atomic% or less, Al is 0.1 atomic% or more and 10 atomic% or less, and Fe is 86 atomic% or more and 99 atomic% or less (100 atomic% in total).
Region E ₂ : Cr is 0.1 atomic% to 99 atomic%, Al is 0.1 atomic% to 50 atomic%, and Fe is 0.1 atomic% to 99 atomic% (total is 100 atomic%).
Region E ₃ : Cr is 0.1 atomic% to 50 atomic%, Al is 55 atomic% to 65 atomic%, and Fe is 0.1 atomic% to 44 atomic% (total is 100 atomic%)

  At least one outer layer is composed of Al of 25 atomic% to 50 atomic%, Cr of 0.1 atomic% to 10 atomic%, Co of 0.1 atomic% to 10 atomic%, and Si of 0.1 atomic%. You may contain 10 atomic% or less and Ni 19.9 atomic% or more and 74 atomic% or less.

  The alloy film may include at least two outer layers having different compositions selected from the various outer layers described above.

  At least one inner layer has a total of 25 atoms of W at 10 atomic% to 21 atomic%, Cr at 23 atomic% to 53% atomic, and at least one element selected from the group consisting of Fe and Co and Ni. % Or more and 66 atomic% or less. In addition, at least one inner layer includes, in total, W in a range of 30 atomic% to 45 atomic%, Cr in a range of 10 atomic% to 40 atomic%, and at least one element selected from the group consisting of Fe, Co, and Ni. You may contain 30 atomic% or more and 59 atomic% or less. In addition, at least one inner layer contains at least one element selected from the group consisting of Fe, Co, and Ni, with W at 35 atomic% to 45 atomic%, Cr at 0.1 atomic% to 50 atomic%. You may contain 15 atomic% or more and 64 atomic% or less in total. Further, at least one inner layer contains at least one element selected from the group consisting of Fe, Co, and Ni, with W at 0.1 atomic% or more and 20 atomic% or less, Cr at 70 atomic% or more and 99 atomic% or less. You may contain 0.1 atomic% or more and 29 atomic% or less in total. Further, at least one inner layer contains W at least 77 atomic percent and not more than 99 atomic percent, Cr at least 0.1 atomic percent and not more than 20 atomic percent, and at least one element selected from the group consisting of Fe, Co, and Ni. You may contain 0.1 atomic% or more and 2 atomic% or less in total. In addition, at least one inner layer contains at least one element selected from the group consisting of Co, Fe, and Ni with W at 0.1 atomic% or more and 3 atomic% or less, Cr at 52 atomic% or more and 65 atomic% or less. You may contain 30 atomic% or more and 54 atomic% or less in total. In addition, at least one inner layer is a sum of at least one element selected from the group consisting of Co, Fe, and Ni, with W at 3 atomic% to 25 atomic%, Cr at 30 atomic% to 65 atomic%, and the like. You may contain 25 atomic% or more and 55 atomic% or less. In addition, at least one inner layer is a total of at least one element selected from the group consisting of Co, Fe, and Ni, with W at 25 atomic% to 35 atomic%, Cr at 20 atomic% to 40 atomic%, and the like. You may contain 30 atomic% or more and 50 atomic% or less. Further, at least one inner layer contains at least one element selected from the group consisting of Co, Fe and Ni, W at 30 atomic% to 55 atomic%, Cr 0.1 atomic% to 50 atomic%. You may contain 20 atomic% or more and 60 atomic% or less in total. In addition, at least one inner layer contains at least one element selected from the group consisting of Co, Fe and Ni, W at 0.1 atomic% to 25 atomic%, Cr 65 atomic% to 99 atomic%, You may contain 0.1 atomic% or more and 25 atomic% or less in total. Further, at least one inner layer contains at least one element selected from the group consisting of Co, Fe, and Ni, with W at 75 atomic% to 99 atomic%, Cr at 0.1 atomic% to 25 atomic%. You may contain 0.1 atomic% or more and 3 atomic% or less in total. In addition, at least one inner layer includes, in total, at least one element selected from the group consisting of Ni, Fe, and Co, with W at 2 atomic% to 20 atomic%, Cr at 40 atomic% to 65 atomic%, and the like. You may contain 30 atomic% or more and 40 atomic% or less. Further, at least one inner layer contains at least one element selected from the group consisting of Ni, Fe and Co, W at 0.1 atomic% to 20 atomic%, Cr at 70 atomic% to 99 atomic%. You may contain 0.1 atomic% or more and 30 atomic% or less in total. Further, at least one inner layer contains at least one element selected from the group consisting of Ni, Fe and Co, W at 80 atomic% or more and 99 atomic% or less, Cr at 0.1 atomic% or more and 20 atomic% or less. You may contain 0.1 atomic% or more and 3 atomic% or less in total. Further, at least one outer layer is at least one element selected from the group consisting of 0.1 atomic% to 50 atomic% Cr, 0.1 atomic% to 22 atomic% Al, Ni, Fe, and Co. May be contained in a total of 51 atomic% or more and 99 atomic% or less. Further, at least one outer layer contains at least one element selected from the group consisting of Cr, 0.1 atomic% to 10 atomic%, Al 23 atomic% to 29 atomic%, Ni, Fe and Co. You may contain 70 atomic% or more and 75 atomic% or less in total. In addition, at least one outer layer contains at least one element selected from the group consisting of Cr, 0.1 atomic% to 20 atomic%, Al 58 atomic% to 63 atomic%, and Ni, Fe, and Co. You may contain 36 atomic% or more and 41 atomic% or less in total. In addition, at least one outer layer contains at least one element selected from the group consisting of Ni, Fe, and Co, with Cr at 56 atomic% to 99 atomic%, Al at 0.1 atomic% to 43 atomic%, and the like. You may contain 0.1 atomic% or more and 25 atomic% or less in total. Further, at least one outer layer is at least one element selected from the group consisting of 0.1 atomic% to 15 atomic% Cr, 0.1 atomic% to 10 atomic% Al, Fe, Co, and Ni. May be contained in a total of 86 atomic% or more and 99 atomic% or less. Further, at least one outer layer is at least one element selected from the group consisting of Cr 0.1 atomic% to 99 atomic%, Al 0.1 atomic% to 50 atomic%, Fe, Co, and Ni. And may be contained in a total of 0.1 atomic% to 99 atomic%. In addition, at least one outer layer contains at least one element selected from the group consisting of Cr, 0.1 atomic% to 50 atomic%, Al 55 atomic% to 65 atomic%, and Fe, Co, and Ni. You may contain 0.1 atomic% or more and 44 atomic% or less in total. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 10 atomic% to 21 atomic%, Cr is 23 atomic% to 53% atomic, You may contain Fe 25 atomic% or more and 66 atomic% or less. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 30 atomic% to 45 atomic%, Cr is 10 atomic% to 40 atomic%, You may contain Fe 30 atomic% or more and 59 atomic% or less. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo and Ta in a total of 35 atomic% to 45 atomic%, and Cr is 0.1 atomic% to 50 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 15 atomic% to 64 atomic%. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 0.1 atomic% to 20 atomic%, and Cr is 70 atomic% to 99 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 0.1 atomic% to 29 atomic%. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 77 atomic% to 99 atomic%, and Cr is 0.1 atomic% to 20 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 0.1 atomic% to 2 atomic%. Further, at least one inner layer is composed of a total of at least one element selected from the group consisting of W and Re, Mo, and Ta in a range of 0.1 atomic% to 3 atomic% and Cr of 52 atomic% to 65 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 30 atomic% to 54 atomic%. In addition, at least one inner layer has a total of at least one element selected from the group consisting of W and Re, Mo, and Ta in a total of 3 atomic% to 25 atomic%, Cr is 30 atomic% to 65 atomic%, At least one element selected from the group consisting of Fe, Co and Ni may be contained in a total of 25 atomic% to 55 atomic%. Further, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 25 atomic% to 35 atomic%, Cr is 20 atomic% to 40 atomic%, At least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 30 atomic% to 50 atomic%. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 30 atomic% to 55 atomic%, and Cr is 0.1 atomic% to 50 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 20 atomic% to 60 atomic%. Further, at least one inner layer is composed of W and at least one element selected from the group consisting of Re, Mo and Ta in a total of 0.1 atomic% to 25 atomic%, and Cr is 65 atomic% to 99 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 0.1 atomic% to 25 atomic%. Further, at least one inner layer is composed of 75 atomic% to 99 atomic% in total of W and at least one element selected from the group consisting of Re, Mo, and Ta, and Cr is 0.1 atomic% to 25 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 0.1 atomic% to 3 atomic%. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo and Ta in a total of 2 atomic% to 20 atomic%, Cr is 40 atomic% to 65 atomic%, At least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 30 atomic% to 40 atomic%. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 0.1 atomic% to 20 atomic%, and Cr is 70 atomic% to 99 atomic%. Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni may be contained in a total amount of 0.1 atomic% to 30 atomic%. In addition, at least one inner layer includes W and at least one element selected from the group consisting of Re, Mo, and Ta in a total of 80 atomic% to 90 atomic%, and Cr is 0.1 atomic% to 20 atomic%. Hereinafter, Ni may be contained in an amount of 0.1 atomic% to 3 atomic%. Further, at least one outer layer may further contain at least one element selected from the group consisting of Y, Hf, Cs, Mg, and Ti in a total amount of 0.01 atomic% to 2 atomic%.

In addition, this invention
A first containing at least one element selected from the group consisting of Fe, Co, Ni, Cr, W, Re, Mo and Ta on the surface of an alloy base material containing at least 10 atomic% or more Cr in the surface layer portion Forming a layer of
Forming at least one inner layer by heating the alloy base material on which the first layer is formed to a temperature of 800 ° C. or higher and 1300 ° C. or lower;
Forming a second layer containing at least one element selected from the group consisting of Fe, Co, Ni, Cr, Al and Si on the inner layer;
And heating the alloy base material on which the second layer is formed to a temperature of 800 ° C. or higher and 1300 ° C. or lower to form at least one outer layer.

  The first layer and the second layer are formed by, for example, at least one method selected from the group consisting of a slurry method, a spray method, a plating method, a thermal spraying method, and an electron beam evaporation method, but is not limited thereto. It is not a thing.

  Specifically, the method for producing a heat-resistant alloy member includes, for example, an inner layer of a Cr—W-based alloy layer containing Cr and W on the surface of an alloy base material containing at least 10 atomic% or more of Cr in the surface layer portion. It has a step of forming a (barrier layer) and a step of forming an outer layer (reservoir layer) containing Al on its surface, and forms a coating film having a multilayer structure of at least an inner layer and an outer layer. Moreover, the manufacturing method of a heat-resistant alloy member is a Cr-W type alloy layer, a Cr-W-Ta type alloy layer, Cr- on the surface of the alloy base material in which the surface layer part contains Cr at least 10 atomic% or more, for example. Forming at least one inner layer (barrier layer) selected from the group consisting of a W—Mo alloy layer, a Cr—W—Ta—Mo alloy layer and a Cr—W—Ta—Mo—Re alloy layer; And forming a Cr-containing outer layer (reservoir layer) on the surface thereof, and forming a coating film having a multilayer structure of at least the inner layer and the outer layer. Moreover, the manufacturing method of a heat-resistant alloy member is a Cr-W type alloy layer, a Cr-W-Ta type alloy layer, Cr- on the surface of the alloy base material in which the surface layer part contains 10 atomic% or more of Cr, for example. Forming at least one inner layer (barrier layer) selected from the group consisting of a W—Mo alloy layer, a Cr—W—Ta—Mo alloy layer and a Cr—W—Ta—Mo—Re alloy layer; Forming an inner layer of a Cr-W-based α-Cr layer on the surface, the inner layer being a Cr-W-based alloy layer, a Cr-W-Ta-based alloy layer, a Cr-W-Mo-based alloy Layer, at least one inner layer (barrier layer) selected from the group consisting of a Cr—W—Ta—Mo alloy layer and a Cr—W—Ta—Mo—Re alloy layer, and α-Cr formed on the surface thereof It has a multilayer structure with layers. In addition, the method for producing a heat-resistant alloy member includes, for example, a step of forming an inner layer of a Cr-W-based α-Cr layer on the surface of an alloy substrate containing at least a surface layer of 10 atomic% or more of Cr. And the inner layer is a Cr—W alloy layer, a Cr—W—Ta alloy layer, a Cr—W—Mo alloy layer, a Cr—W—Ta—Mo alloy layer and a Cr—W—Ta—Mo—Re Forming a multi-layered inner layer (diffusion barrier layer) in which at least one inner layer selected from the group consisting of alloy layers and an inner layer of the α-Cr layer on the surface of the inner layer are formed, and on the surface of the inner layer Forming an outer layer (reservoir layer) of the Ni—Cr alloy.

In addition, this invention
Having at least one inner layer and at least one outer layer formed on the surface of an alloy substrate containing at least a surface layer of 10 atomic% or more of Cr,
The at least one inner layer is an alloy film containing at least one element selected from the group consisting of Fe, Co, and Ni, and W and Cr.

In addition, this invention
A first containing at least one element selected from the group consisting of Fe, Co, Ni, Cr, W, Re, Mo and Ta on the surface of an alloy base material containing at least 10 atomic% or more Cr in the surface layer portion Forming a layer of
Forming the inner layer by heating the alloy substrate on which the first layer is formed to a temperature of 800 ° C. or higher and 1300 ° C. or lower;
Forming a second layer containing at least one element selected from the group consisting of Fe, Co, Ni, Cr, Al and Si on the inner layer;
And forming the outer layer by heating the alloy base material on which the second layer is formed to a temperature of 800 ° C. or higher and 1300 ° C. or lower.

  In the invention of the alloy film and the method of manufacturing the alloy film, what has been described in relation to the invention of the heat-resistant alloy member and the method of manufacturing the heat-resistant alloy member is valid.

  Although the heat-resistant alloy member is not particularly limited, specifically, for example, a gas turbine member, a jet engine member, a rocket member, an industrial furnace member, a chemical plant member, a high-temperature heat-resistant member of an energy conversion device, etc. is there.

According to this invention, the inner layer functions as a diffusion barrier layer that prevents the diffusion of the base material component from the alloy base material to the outer layer and the diffusion of Al or Cr from the outer layer to the alloy base material. Thus, the outer layer is not diluted, and the outer layer is secured with the Al concentration necessary for forming the protective Al ₂ O ₃ film or the Cr concentration necessary for forming the protective Cr ₂ O ₃ film. Therefore, even when the Al ₂ O ₃ film or the Cr ₂ O ₃ film is damaged under use conditions, the film defect part is self-repaired by Al or Cr supplied from the outer layer. Therefore, high temperature corrosion and abnormal oxidation are suppressed, and the original excellent high temperature characteristics of the Fe-based alloy, Co-based alloy, and Ni-based alloy are maintained for a long period of time. For this reason, for example, a heat-resistant alloy member suitable as a gas turbine member, a jet engine member, a rocket member, an industrial furnace member, a chemical plant member, a high-temperature heat-resistant member of an energy conversion device, or the like can be obtained.

It is a Fe-Cr-W ternary phase diagram. It is a Co-Cr-W ternary phase diagram. It is a Ni-Cr-W ternary phase diagram. It is a Ni-Cr-Al ternary phase diagram. It is a Fe-Cr-Al ternary phase diagram. It is sectional drawing which shows the manufacturing method of the heat-resistant alloy member by one Embodiment of this invention. 3 is a drawing-substituting photograph showing a cross-sectional structure of the heat-resistant alloy member of Example 1. FIG. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 1. FIG. FIG. 4 is a schematic diagram showing the concentration of each element in the cross section of the heat-resistant alloy member of Example 1. 6 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 2. FIG. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 2. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 2. FIG. 4 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 3. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 3. FIG. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 3. FIG. 6 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 4. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 4. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 4. FIG. 6 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 5. It is a basic diagram which shows the measurement result of the density | concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 5. FIG. 6 is a schematic diagram showing the concentration of each element in the cross section of the heat-resistant alloy member of Example 5. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 6. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 6. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 6. FIG. 6 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 7. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 7. FIG. 10 is a schematic diagram showing the concentration of each element in the cross section of the heat-resistant alloy member of Example 7. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 8. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 8. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 8. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 9. It is an approximate line figure showing a measurement result of concentration distribution of each element in a section of a heat-resistant alloy member of Example 9. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 9. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 10. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 10. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 10. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 11. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 11. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 11. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 12. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 12. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 12. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 13. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 13. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 13. FIG. It is a drawing substitute photograph which shows the cross-section of the heat-resistant alloy member of Example 14. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 14. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 14. FIG. 14 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 15. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 15. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 15. FIG. 10 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 16. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 16. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 16. FIG. 14 is a drawing-substituting photograph showing a cross-sectional structure of a heat-resistant alloy member of Example 17. It is a basic diagram which shows the measurement result of the concentration distribution of each element in the cross section of the heat-resistant alloy member of Example 17. It is a basic diagram which shows the density | concentration of each element in the cross section of the heat-resistant alloy member of Example 17. FIG.

Hereinafter, modes for carrying out the invention (hereinafter simply referred to as “embodiments”) will be described.
6A to 6D show a method for manufacturing a heat-resistant alloy member according to one embodiment of the present invention.

  As shown in FIG. 6A, first, a coating layer 12 that finally becomes an inner layer is formed on an alloy base material 11 in which at least the surface layer portion contains 10 atomic% or more of Cr. As a method for forming the coating layer 12, various methods such as electroplating, electroless plating, slurry coating, spraying, thermal spraying, and electron beam evaporation can be used. The coating layer 12 includes a kind and amount of metal corresponding to the composition of the inner layer to be formed.

  Next, for example, the alloy base 11 on which the coating layer 12 is formed is heat-treated at a temperature of 800 ° C. or higher and 1300 ° C. or lower. This heat treatment can be performed in an atmosphere such as vacuum, argon, or various pack treatments. Cr diffusion treatment can also be performed during this heat treatment. By this heat treatment, as shown in FIG. 6B, a single-layer or multi-layer inner layer 13 is formed using the coating layer 12 as a starting material.

  Next, as shown in FIG. 6C, a coating layer 14 that finally becomes an outer layer is formed on the inner layer 13. As a method for forming the coating layer 14, for example, various methods such as electroplating, electroless plating, slurry coating, spraying, thermal spraying, and electron beam evaporation can be used. The coating layer 14 includes a kind and amount of metal corresponding to the composition of the outer layer to be formed.

  Next, for example, the alloy base 11 on which the coating layer 14 is formed is heat-treated at a temperature of 800 ° C. or higher and 1300 ° C. or lower. This heat treatment can be performed in an atmosphere such as vacuum, argon, or various pack treatments. By this heat treatment, as shown in FIG. 6D, a single-layer or multilayer outer layer 15 is formed using the coating layer 14 as a starting material.

After the outer layer 15 is formed, the structure or composition of the inner layer 14 and the outer layer 15 is tempered by performing a heat treatment as necessary.
Thus, the intended heat resistant alloy member is manufactured.

Examples will be described.
Table 1 shows Fe-base alloy A (trade name: SUS310S), Fe-base alloy B (trade name: SCH22), Co-base alloy A, Co-base alloy B, and Co-base alloy used as alloy base materials in the following examples. The composition of C (trade name: FSX414) and Ni-based alloy (trade name: Hastelloy-X) is shown.

Table 1
Alloy name Nominal composition (atomic%)
FeCoNiCrWMoMnAlSiC
Fe-based alloy A 50.0… 18.5 26.1…… <2.0… <2.9 <0.3
Fe-based alloy B 52.4… 20 25…… 1.2… 1.4 0.4
Co-based alloy A… 80… 20………………
Co-based alloy B… 70… 30………………
Co-based alloy C… 53 10 34 2.3……………
Ni-base alloy 18.7 2.3 48.6 24.7 0.2 5.5…………

<Example 1>
Fe-based alloy A was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ).

  The test piece thus prepared is cut and polished, the cross-sectional structure is observed, and the thickness direction of each element contained in the surface portion of the alloy base material is measured using a micro-element analyzer (EPMA; Electron-Probe Micro Analyzer). The concentration distribution of was measured. FIG. 7 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 8 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 of the photograph shown in FIG. 7) measured using EPMA. FIG. 9 shows the measurement results of the concentration of each element.

  As shown in FIGS. 7 to 9, the coating layer [200] is at least three layers, and from the surface side, the layer [280] with a high Cr concentration, the inner layer II, and the lower side thereof, Cr, W, Fe, Ni, etc. An intermediate layer [240] including the inner layer I, and a transition layer [220] are formed in contact with the substrate.

<Example 2>
Fe-based alloy A was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after Ni plating (30 μm), Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 1100 ° C. for 4 hours.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 10 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 11 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 10). FIG. 12 shows the measurement results of the concentration of each element.

  As shown in FIGS. 10 to 12, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer has an outer layer II [380] having a high Cr concentration and a Ni—Cr outer layer I from the surface side. [320] and the inner layer [200] are formed with an inner layer II [240] and an inner layer II [220] containing Cr, W, Fe, Ni and the like.

<Example 3>
Fe-based alloy A was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after performing Ni plating (30 μm), an Al pack treatment (Al + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 700 ° C. for 90 minutes.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 13 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 14 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 13). FIG. 15 shows the measurement results of the concentration of each element.

  As shown in FIG. 13 to FIG. 15, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is Ni-Al outer layer II [340] and Ni outer layer I [ 310], and further, the inner layer [200] is formed with an inner layer II [280] having a high Cr concentration and an inner layer I [240] containing Cr, W, Fe, Ni and the like.

<Example 4>
Fe-based alloy B (roll material) was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ).

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 16 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 17 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 16). FIG. 18 shows the measurement results of the concentration of each element.

  As shown in FIGS. 16 to 18, the coating layer is the inner layer [200], and from the surface side, the inner layer II [280] having a high Cr concentration and the inner layer I [240] containing Cr, W, Mo, Fe, Ni, and the like. ], And both are mixed.

<Example 5>
About the same test piece as Example 4, the cross-sectional structure | tissue of a site | part different from Example 4 was observed, and the concentration distribution of the thickness direction of each element contained in the alloy base-material surface layer part was measured. FIG. 19 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 20 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 19). FIG. 21 shows the measurement results of the concentration of each element.

  As shown in FIGS. 19 to 21, as in Example 4, the coating layer is the inner layer [200], and from the surface side, the inner layer II [280] with high Cr concentration and Cr, W, Mo, Fe, Ni The inner layer I [240] is formed, and both are mixed.

<Example 6>
Co-based alloy C was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ).

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 22 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 23 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 22). FIG. 24 shows the measurement results of the concentration of each element.

  As shown in FIGS. 22 to 24, the coating layer [200] is at least four layers, and from the surface side, the high Cr concentration layer [280], the inner layer II [260], and the lower side thereof are Cr, W, Fe. An intermediate layer [240] containing Ni, Ni, etc., an inner layer I, and a transition layer [220] are formed in contact with the substrate.

<Example 7>
Co-based alloy C was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after Ni plating (20 μm), Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 1000 ° C. for 4 hours.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 25 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 26 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 25). FIG. 27 shows the measurement results of the concentration of each element.

  As shown in FIGS. 25 to 27, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is an outer layer II [380] having a high Cr concentration and an outer layer of Ni—Cr from the surface side. I [320], and further the inner layer [200] is an inner layer II [280] having a high Cr concentration, an inner layer I [240] containing Cr, W, Fe, Ni, etc. Is formed.

<Example 8>
Co-based alloy C was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after Ni plating (20 μm) was performed, Al pack treatment (Al + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 700 ° C. for 90 minutes. Thereafter, homogenization heat treatment was performed at 1100 ° C. for 2 hours in an Ar gas atmosphere.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 28 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 29 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG2 in the photograph shown in FIG. 28). FIG. 30 shows the measurement results of the concentration of each element.

  As shown in FIGS. 28 to 30, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is an outer layer II [380] having a high Cr concentration and an outer layer of Ni—Al from the surface side. The inner layer I [240] + [220] containing Cr, W, Fe, Ni, etc. is formed on the I [320] and the inner layer [200].

<Example 9>
Co-based alloy C was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after Ni plating (20 μm), Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 1000 ° C. for 4 hours. Thereafter, homogenization heat treatment was performed at 1100 ° C. for 2 hours in an Ar gas atmosphere.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 31 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 32 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG4 in the photograph shown in FIG. 31). FIG. 33 shows the measurement results of the concentration of each element.

  As shown in FIGS. 31 to 33, the coating layers are an outer layer [300] and an inner layer [200] of Ni—Al, and the inner layer is made of an inner layer II [280] with high Cr concentration and Cr, W, Fe, Ni, etc. An inner layer I [240] + [220] is formed.

<Example 10>
Co-based alloy A was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after Ni plating (20 μm), Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 1000 ° C. for 4 hours. Thereafter, homogenization heat treatment was performed at 1100 ° C. for 2 hours in an Ar gas atmosphere.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 34 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 35 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 34). FIG. 36 shows the measurement results of the concentration of each element.

  As shown in FIGS. 34 to 36, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is an outer layer II [380] having a high Cr concentration and a Ni—Cr outer layer I from the surface side. [340] Further, the inner layer [200] is formed with an inner layer I [240] + [220] containing Cr, W, Fe, Ni and the like.

<Example 11>
Co-based alloy A was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after performing Ni plating (20 μm), an Al pack treatment (Al + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 700 ° C. for 75 minutes. Thereafter, homogenization heat treatment was performed at 1100 ° C. for 2 hours in an Ar gas atmosphere.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 37 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 38 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 37). FIG. 39 shows the measurement results of the concentration of each element.

  As shown in FIGS. 37 to 39, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is Ni-Al outer layer I [300] and further the inner layer [200] from the surface side. The inner layer II [280] having a high Cr concentration and the inner layer I [240] + [220] containing Cr, W, Fe, Ni, etc. are formed.

<Example 12>
Co-based alloy B was used as the alloy substrate. On this alloy base material, W powder was applied in a slurry state, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) in an Ar gas atmosphere at 1000 ° C. for 4 hours. Next, after Ni plating (20 μm), Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 1000 ° C. for 4 hours. Thereafter, homogenization heat treatment was performed at 1100 ° C. for 2 hours in an Ar gas atmosphere.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 40 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 41 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 40). FIG. 42 shows the measurement results of the concentration of each element.

  As shown in FIGS. 40 to 42, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is an outer layer II [380] having a high Cr concentration and an Ni—Cr outer layer I from the surface side. [340] Further, the inner layer [200] is formed with an inner layer I [240] + [220] containing Cr, W, Fe, Ni and the like.

<Example 13>
Co-based alloy B was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after performing Ni plating (20 μm), an Al pack treatment (Al + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 700 ° C. for 75 minutes. Thereafter, homogenization heat treatment was performed at 1100 ° C. for 2 hours in an Ar gas atmosphere.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 43 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 44 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 43). FIG. 45 shows the measurement results of the concentration of each element.

  As shown in FIGS. 43 to 45, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is Ni-Al outer layer I [300] and further the inner layer [200] from the surface side. The inner layer II [280] having a high Cr concentration and the inner layer I [240] + [220] containing Cr, W, Fe, Ni, etc. are formed.

<Example 14>
A Ni-based alloy was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ).

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 47 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 48 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG1 in the photograph shown in FIG. 47). FIG. 49 shows the measurement results of the concentration of each element.

  As shown in FIGS. 47 to 49, from the surface side, a high Cr concentration layer [280], an inner layer [200], and an intermediate layer [240] containing Cr, W, Mo, Fe, Ni, and the like below are provided. Is formed.

<Example 15>
About the same test piece as Example 14, the cross-sectional structure | tissue of a site | part different from Example 14 was observed, and the concentration distribution of the thickness direction of each element contained in the alloy base-material surface layer part was measured. FIG. 50 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 51 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG2 in the photograph shown in FIG. 50). FIG. 52 shows the measurement results of the concentration of each element.

  As shown in FIGS. 50 to 52, similarly to Example 14, from the surface side, a high Cr concentration layer [280], an inner layer [200], and Cr, W, Mo, Fe, Ni, and the like on the lower side thereof. An intermediate layer [240] is formed.

<Example 16>
A Ni-based alloy was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after performing Ni plating (30 μm), an Al pack treatment (Al + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 700 ° C. for 90 minutes.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 53 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 54 shows the measurement results of the concentration distribution of each element (concentration distribution along the line LG2 in the photograph shown in FIG. 53). FIG. 55 shows the measurement results of the concentration of each element.

  As shown in FIG. 53 to FIG. 55, the coating layer has two layers of an outer layer [300] and an inner layer [200], and the outer layer is Ni-Al outer layer II [360] and Ni outer layer I [320 from the surface side. In the inner layer [200], an inner layer II [280] having a high Cr concentration and an inner layer I [240] + [220] containing Cr, W, Mo, Fe, Ni, etc. are formed.

<Example 17>
A Ni-based alloy was used as the alloy substrate. On this alloy base material, a mixed powder of W powder and Ni powder was applied in a slurry form, dried, and then subjected to Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O for 4 hours at 1000 ° C. in an Ar gas atmosphere. ₃ ). Next, after Ni plating (30 μm), Cr pack treatment (Cr + NH ₄ Cl + Al ₂ O ₃ ) was performed in an Ar gas atmosphere at 1100 ° C. for 4 hours.

  In the same manner as in Example 1, the test piece was cut and polished, and the cross-sectional structure was observed and the concentration distribution in the thickness direction of each element contained in the surface portion of the alloy substrate was measured. FIG. 56 shows an optical micrograph of the cross-sectional structure of the test piece. FIG. 57 shows the measurement results of the concentration distribution of each element (concentration distribution along the line of the photograph shown in FIG. 56). FIG. 58 shows the measurement results of the concentration of each element.

  As shown in FIGS. 56 to 58, the coating layer is at least two layers of an inner layer [200] and an outer layer [300], and the outer layer is an outer layer II [380] having a high Cr concentration and a Ni—Cr outer layer I from the surface side. [330], and the inner layer [200] is formed with an inner layer I [240] + [220] containing Cr, W, Mo, Fe, Ni and the like.

  As described above, according to the heat-resistant alloy member according to this embodiment, the heat-resistant alloy member is formed on the surface of the alloy base material containing at least 10 atomic% or more of Cr and the surface of the alloy base material. The alloy film has at least one inner layer and at least one outer layer, and the at least one inner layer is at least one element selected from the group consisting of Fe, Co, and Ni, and W and Cr. Thus, it is possible to obtain a heat-resistant alloy member having excellent oxidation resistance and long life in a high-temperature corrosive atmosphere. This heat-resistant alloy member is suitable for application to, for example, a gas turbine member, a jet engine member, a rocket member, an industrial furnace member, a chemical plant member, a high-temperature heat-resistant member of an energy conversion device, and the like.

  Although one embodiment and example of the present invention have been specifically described above, 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.

  DESCRIPTION OF SYMBOLS 11 ... Alloy base material, 12 ... Coating layer, 13 ... Inner layer, 14 ... Coating layer, 15 ... Outer layer

Claims (14)

An alloy base material containing at least 10 atomic% or more of Cr at the surface layer part;
Having an alloy film formed on the surface of the alloy substrate,
The alloy film has at least one inner layer and at least one outer layer,
At least one of the inner layers is composed of at least one element selected from the group consisting of Fe, Co, and Ni and W and Cr (total of Fe, Co, Ni, W, and Cr is 100 atomic%), or And at least one element selected from the group consisting of Fe, Co and Ni, and at least one element selected from the group consisting of W, Cr, Mo and Ta (Fe, Co, Ni, W, Cr and The total of Mo and Ta is 100 atomic%),
At least one outer layer contains at least one element selected from the group consisting of Fe, Co and Ni, Al and Cr, but does not contain Re. At least one of the inner layers is made of an Fe—Cr—W alloy or an Fe—Cr—W—Ni—Ta—Mo alloy, and at least one of the outer layers is an Fe— Cr—Al alloy, Fe—Ni—Cr— Al-based alloy or Ni-Fe-Cr-Al-Si-based alloy , or at least one inner layer is made of Co-Cr-W-based alloy or Co-Cr-W-Ni-Ta-Mo-based alloy, At least one of the outer layers is made of a Ni— Al—Cr alloy or a Ni—Co—Al—Cr—Si alloy , or at least one of the inner layers is a Ni—Cr—W alloy or Ni—Cr—W—. It is made of an Fe—Ta—Mo alloy, and at least one outer layer is a Ni— Cr—Al alloy, Ni—Co—Cr—Al alloy, Ni—Co—Cr—Al— Si alloy or N The heat-resistant alloy member according to claim 1, comprising an i-Cr-Al-based alloy.   The inner layer of at least one layer contains W at 10 atomic% to 21 atomic%, Cr at 23 atomic% to 53 atomic%, and Fe 25 atomic% to 66 atomic% (the sum of W, Cr and Fe). 100 atom%) or W is contained in 30 atom% to 45 atom%, Cr is contained in 10 atom% to 40 atom%, and Fe is contained in 30 atom% to 59 atom% (sum of W, Cr and Fe). Or 100 to 45 atom% W, 0.1 to 50 atom% Cr, 15 to 64 atom% Fe (W, Cr and Fe) Or W in the range of 0.1 atomic% to 20 atomic%, Cr in the range of 70 atomic% to 99 atomic%, and Fe in the range of 0.1 atomic% to 29 atomic% ( The total of W, Cr and Fe is 100 atomic%) Or, W is 77 atomic% to 99 atomic%, Cr is 0.1 atomic% to 20 atomic%, and Fe is 0.1 atomic% to 2 atomic% (the sum of W, Cr and Fe). 100 atom%), or W containing 0.1 atomic% to 3 atomic%, Cr containing 52 atomic% to 65 atomic%, and Co containing 30 atomic% to 54 atomic% (W, Cr, Co and Or W in a range of 3 to 25 atomic%, Cr in a range of 30 to 65 atomic%, and Co in a range of 25 to 55 atomic% (W, Cr, and Co). Or W in an amount of 25 atomic% to 35 atomic%, Cr in an amount of 20 atomic% to 40 atomic%, and Co in an amount of 30 atomic% to 50 atomic% (W and Cr). 100 atomic% in total with Co) or W is 30 atomic% or more 5 atomic% or less, Cr 0.1 atomic% or more and 50 atomic% or less, Co 20 atomic% or more and 60 atomic% or less (100 atomic% in total of W, Cr and Co), or W 0 .1 atomic% to 25 atomic%, Cr 65 atomic% to 99 atomic%, Co 0.1 atomic% to 25 atomic% (total of W, Cr and Co is 100 atomic%), Alternatively, W is 75 atomic% to 99 atomic%, Cr is 0.1 atomic% to 25 atomic%, and Co is 0.1 atomic% to 3 atomic% (total of W, Cr, and Co is 100%). Or 2 to 20 atomic percent W, Cr 40 to 65 atomic percent, Ni 30 to 40 atomic percent (the sum of W, Cr and Ni). 100 atomic%) or W is 0.1 atomic% or more and 20 atomic% or less, Cr 70 atom% or more and 99 atom% or less, Ni 0.1 atom% or more and 30 atom% or less (total of W, Cr and Ni is 100 atom%) or W is 80 atom% or more and 99 atom% The content of Cr is 0.1 atomic percent or more and 20 atomic percent or less, and Ni is 0.1 atomic percent or more and 3 atomic percent or less (total of W, Cr, and Ni is 100 atomic percent). Heat-resistant alloy member.   The heat-resistant alloy member according to any one of claims 1 to 3, wherein the alloy film includes at least two inner layers having different compositions.   The outer layer of at least one layer contains 0.1 atomic% to 50 atomic% of Cr, 0.1 atomic% to 22 atomic% of Al, and 51 atomic% to 99 atomic% of Ni (Cr, Al and Ni Or 0.1 to 10 atomic percent of Cr, 23 to 29 atomic percent of Al, and 70 to 75 atomic percent of Ni (Cr and 100 atomic% in total of Al and Ni), or 0.1 atomic% to 14 atomic% in Cr, 30 to 55 atomic% in total in Al and Si, and Ni, Co and Fe in total Or 45 atomic% to 65 atomic% (total of Cr, Al, Si, Ni, Co and Fe is 100 atomic%), or Cr is 0.1 atomic% to 20 atomic% and Al is 58%. Atomic% to 63 atomic%, Ni is 3 From atomic% to 41 atomic% (total of Cr, Al, and Ni is 100 atomic%), or Cr is from 56 atomic% to 99 atomic%, Al is from 0.1 atomic% to 43 atomic%, Contains 0.1 atomic percent or more and 25 atomic percent or less of Ni (100 atomic percent in total of Cr, Al, and Ni), or contains 0.1 atomic percent or more and 15 atomic percent or less of Cr, and 0.1 atom of Al % Or more and 10 atomic% or less, Fe is contained in 86 atomic% or more and 99 atomic% or less (total of Cr, Al and Fe is 100 atomic%), or Cr is 0.1 atomic% or more and 99 atomic% or less, Al 0.1 atomic% or more and 50 atomic% or less, Fe 0.1 atomic% or more and 99 atomic% or less (total of Cr, Al, and Fe is 100 atomic%), or Cr is 0.1 atomic% 50 atomic% or less, Al 55 atomic% or more and 65 atomic% or less, F In an amount of 0.1 atomic% to 44 atomic% (total of Cr, Al, and Fe is 100 atomic%), or Al is 25 atomic% to 50 atomic%, and Cr is 0.1 atomic% to 10 atomic%. Atomic% or less, Co 0.1 atomic% to 10 atomic%, Si 0.1 atomic% to 10 atomic%, Ni 19.9 atomic% to 74 atomic% (Al, Cr and Co) The heat-resistant alloy member according to any one of claims 1 to 4, wherein the sum of Si and Ni is 100 atomic%.   The heat-resistant alloy member according to any one of claims 1 to 5, wherein the alloy film includes at least two outer layers having different compositions.   At least one of the inner layers has a total of 25 at least one element selected from the group consisting of Fe, Co, and Ni, W at 10 atomic% to 21 atomic%, Cr 23 atomic% to 53 atomic%. Containing at least atomic percent and not more than 66 atomic percent (total of W, Cr, Fe, Co, and Ni is 100 atomic percent), or W is not less than 30 atomic percent and not more than 45 atomic percent, and Cr is not less than 10 atomic percent and not more than 40 atomic percent Hereinafter, at least one element selected from the group consisting of Fe, Co, and Ni is contained in a total of 30 atomic% to 59 atomic% (the total of W, Cr, Fe, Co, and Ni is 100 atomic%). Or, W is 35 atomic% to 45 atomic%, Cr is 0.1 atomic% to 50 atomic%, and at least one element selected from the group consisting of Fe and Co and Ni is 15 atomic% in total. Less than 64 atomic percent or less (100 atomic percent in total of W, Cr, Fe, Co and Ni), or W 0.1 atomic percent to 20 atomic percent, Cr 70 atomic percent to 99 atomic percent Containing at least one element selected from the group consisting of Fe, Co and Ni in a total of 0.1 atomic% to 29 atomic% (total of W, Cr, Fe, Co and Ni is 100 atomic%) Or, W is 77 atomic% or more and 99 atomic% or less, Cr is 0.1 atomic% or more and 20 atomic% or less, and at least one element selected from the group consisting of Fe and Co and Ni is 0. 1 atom% or more and 2 atom% or less (100 atom% in total of W, Cr, Fe, Co and Ni), or W 0.1 atom% or more and 3 atom% or less, Cr 52 atom% or more 65 atomic% or less, consisting of Co, Fe and Ni Contains at least one element selected from the group by 30 to 54 atomic% in total (100 atomic% in total of W, Cr, Co, Fe and Ni), or W at 3 atomic% or more 25 atomic% or less, Cr 30 atomic% or more and 65 atomic% or less, and a total of 25 atomic% or more and 55 atomic% or less of at least one element selected from the group consisting of Co and Fe and Ni (W and Cr) The total of Co, Fe, and Ni is selected from the group consisting of Co, Fe, and Ni, or W is 25 atomic% to 35 atomic%, Cr is 20 atomic% to 40 atomic%. In addition, at least one element is contained in a total of 30 atomic% to 50 atomic% (the total of W, Cr, Co, Fe, and Ni is 100 atomic%), or W is 30 atomic% to 55 atomic%. , Cr 0.1 Containing at least one element selected from the group consisting of Co, Fe, and Ni in a total of 20 atomic% or more and 60 atomic% or less (total of W, Cr, Co, Fe, and Ni) Or at least one element selected from the group consisting of Co, Fe, and Ni, W is 0.1 atomic% to 25 atomic%, Cr is 65 atomic% to 99 atomic% Is contained in a total of 0.1 atomic% to 25 atomic% (the total of W, Cr, Co, Fe and Ni is 100 atomic%), or W is 75 atomic% to 99 atomic% and Cr is 0%. 1 atom% or more and 25 atom% or less, and a total of at least one element selected from the group consisting of Co, Fe, and Ni is 0.1 atom% or more and 3 atom% or less (W, Cr, Co, Fe and 100 atoms in total with Ni Or a total of at least one element selected from the group consisting of Ni, Fe and Co, with W at 2 atomic% to 20 atomic%, Cr at 40 atomic% to 65 atomic% in total More than 40 atom% (W, Cr, Ni, Fe, Co total 100 atom%), or W 0.1 atomic% or more and 20 atom% or less, Cr 70 atom% or more 99 atom% Hereinafter, at least one element selected from the group consisting of Ni, Fe and Co is contained in a total amount of 0.1 atomic% to 30 atomic% (the total of W, Cr, Ni, Fe and Co is 100 atomic%) Or W is 80 atomic% to 99 atomic%, Cr is 0.1 atomic% to 20 atomic%, and at least one element selected from the group consisting of Ni, Fe, and Co is 0 in total. .1 atom% or more 3 atoms The following contains (W, Cr and 100 atomic percent total of Ni, Fe and Co) to claim 1 or 2, heat-resistant alloy member according.   At least one outer layer includes at least one element selected from the group consisting of Cr, 0.1 atomic% to 50 atomic%, Al 0.1 atomic% to 22 atomic%, Ni, Fe, and Co. In a total of 51 atomic% to 99 atomic% (total of Cr, Al, Ni, Fe and Co is 100 atomic%), or Cr is 0.1 atomic% to 10 atomic% and Al is 23 Containing at least one element selected from the group consisting of Ni, Fe, and Co in a total amount of 70 atomic% to 75 atomic% (total of Cr, Al, Ni, Fe, and Co) Or at least one element selected from the group consisting of Ni, Fe, and Co, and Cr is 0.1 atomic% or more and 20 atomic% or less, Al is 58 atomic% or more and 63 atomic% or less The total 36 atomic% or more and 41 atomic% or less (total of Cr, Al, Ni, Fe and Co is 100 atomic%), or Cr is 56 atomic% or more and 99 atomic% or less, and Al is 0.1 atomic%. Not less than 43 atomic% and containing at least one element selected from the group consisting of Ni, Fe and Co in a total amount of not less than 0.1 atomic% and not more than 25 atomic% (sum of Cr, Al, Ni, Fe and Co) Or at least one selected from the group consisting of 0.1 atomic% and 15 atomic%, Al 0.1 atomic% and 10 atomic%, and Fe, Co and Ni. Element is contained in a total of 86 atomic% to 99 atomic% (total of Cr, Al, Fe, Co and Ni is 100 atomic%), or Cr is 0.1 atomic% to 99 atomic%, Al 0.1 atom% to 50 atoms Hereinafter, a total of at least one element selected from the group consisting of Fe, Co, and Ni is 0.1 atomic percent or more and 99 atomic percent or less (total of Cr, Al, Fe, Co, and Ni is 100 atomic percent) Or a total of at least one element selected from the group consisting of Fe, Co, and Ni, and 0.1% to 50% by atom of Cr, 55% to 65% by atom of Al The heat-resistant alloy member according to claim 1 or 2, which is contained in an amount of 1 atomic% to 44 atomic% (100 atomic% in total of Cr, Al, Fe, Co, and Ni).   The inner layer of at least one layer includes W and at least one element selected from the group consisting of Mo and Ta in total from 10 atomic% to 21 atomic%, Cr from 23 atomic% to 53 atomic%, and Fe from 25 Containing at least one atomic element selected from the group consisting of W, Mo, and Ta, or at least one element selected from the group consisting of W, Mo, Ta, Cr, and Fe. 30 atomic% to 45 atomic%, Cr 10 atomic% to 40 atomic%, Fe 30 atomic% to 59 atomic% (total of W, Mo, Ta, Cr and Fe is 100 atomic%) Or, W and at least one element selected from the group consisting of Mo and Ta in total 35 atomic% to 45 atomic%, Cr 0.1 atomic% to 50 atomic%, Fe, Co and N At least one element selected from the group consisting of 15 to 64 atomic% in total (100 atomic% in total of W, Mo, Ta, Cr, Fe, Co and Ni), or W And at least one element selected from the group consisting of Mo and Ta in total from 0.1 atomic% to 20 atomic%, Cr from 70 atomic% to 99 atomic%, Fe, Co and Ni Contains at least one selected element in a total amount of 0.1 atomic% to 29 atomic% (total of W, Mo, Ta, Cr, Fe, Co, and Ni is 100 atomic%), or W and Mo And at least one element selected from the group consisting of Ta and 77 atomic% to 99 atomic% in total, Cr being selected from the group consisting of 0.1 atomic% and 20 atomic%, Fe, Co and Ni Containing at least one element in a total amount of 0.1 atomic% to 2 atomic% (total of W, Mo, Ta, Cr, Fe, Co, and Ni is 100 atomic%), or from W, Mo, and Ta At least one element selected from the group consisting of at least one element selected from the group consisting of 0.1 atom% to 3 atom%, Cr 52 atom% to 65 atom%, Fe, Co and Ni In a total of 30 atomic percent to 54 atomic percent (total of W, Mo, Ta, Cr, Fe, Co, and Ni is 100 atomic percent), or selected from the group consisting of W, Mo, and Ta At least one element selected from the group consisting of 3 atomic% to 25 atomic%, Cr 30 atomic% to 65 atomic%, Fe, Co and Ni in total 25 At least one element selected from the group consisting of W, Mo, Ta, and 55 atom% (total of W, Mo, Ta, Cr, Fe, Co, and Ni is 100 atom%) or W, Mo, and Ta And a total of at least one element selected from the group consisting of Fe, Co and Ni, and a total of 30 atomic% to 50 atomic%. The following content (100 atom% in total of W, Mo, Ta, Cr, Fe, Co and Ni) or at least one element selected from the group consisting of W, Mo and Ta in total 30 atoms % And 55 atom% or less, Cr 0.1 atom% or more and 50 atom% or less, and a total of at least one element selected from the group consisting of Fe, Co and Ni is 20 atom% or more and 60 atom% or less W, Mo, Ta, Cr, Fe, Co and Ni in total 100 atom%), or at least one element selected from the group consisting of W, Mo and Ta in total 0.1 atomic% 25 atomic% or less, Cr 65 atomic% or more and 99 atomic% or less, and a total of at least one element selected from the group consisting of Fe, Co, and Ni is 0.1 atomic% or more and 25 atomic% or less (W and Or a total of at least one element selected from the group consisting of W, Mo, and Ta is 75 atomic% or more and 99 atomic% in total. In the following, Cr is contained in an amount of 0.1 atomic% to 25 atomic% and at least one element selected from the group consisting of Fe, Co, and Ni is added in a total amount of 0.1 atomic% to 3 atomic% (W, Mo and Ta and Cr e, Co, and Ni in total 100 atom%), or W and at least one element selected from the group consisting of Mo and Ta in total 2 atomic% to 20 atomic%, and Cr 40 atoms % Or more and 65 atom% or less, and a total of at least one element selected from the group consisting of Fe, Co, and Ni is 30 atom% or more and 40 atom% or less (W, Mo, Ta, Cr, Fe, Co, and Ni Or a total of at least one element selected from the group consisting of W and Mo and Ta, and a total of 0.1 atomic% to 20 atomic%, and Cr is 70 atomic% to 99 atoms. %, Containing at least one element selected from the group consisting of Fe, Co, and Ni in a total of 0.1 atomic% to 30 atomic% (the total of W, Mo, Ta, Cr, Fe, Co, and Ni) 10 0 atom%) or at least one element selected from the group consisting of W and Mo and Ta in a total of 80 atom% or more and 90 atom% or less, Cr is 0.1 atom% or more and 20 atom% or less, The heat-resistant alloy member according to claim 1 or 2, wherein Ni is contained in an amount of 0.1 atomic% to 3 atomic% (100 atomic% in total of W, Mo, Ta, Cr and Ni).   The outer layer of at least one layer includes Cr of 0.1 atomic% to 50 atomic%, Al of 0.1 atomic% to 22 atomic%, Ni of 51 atomic% to 99 atomic%, Y, Hf, Cs, Containing at least one element selected from the group consisting of Mg and Ti in a total amount of 0.01 atomic% to 2 atomic% (total of 100 atoms in total of Cr, Al, Ni, Y, Hf, Cs, Mg and Ti Or Cr is 0.1 atomic% to 10 atomic%, Al is 23 atomic% to 29 atomic%, Ni is 70 atomic% to 75 atomic%, Y, Hf, Cs, Mg and Ti Containing at least one element selected from the group consisting of 0.01 to 2 atomic% in total (100 atomic% in total of Cr, Al, Ni, Y, Hf, Cs, Mg and Ti) Or Cr at 0.1 atomic% or less 14 atomic% or less, Al and Si in total 30 to 55 atomic%, Ni, Co and Fe in total 45 to 65 atomic%, Y, Hf, Cs, Mg and Ti Contains at least one selected element in a total amount of 0.01 atomic% to 2 atomic% in total (100 atomic% in total of Cr, Al, Si, Ni, Co, Fe, Y, Hf, Cs, Mg and Ti Or Cr from 0.1 atomic% to 20 atomic%, Al from 58 atomic% to 63 atomic%, Ni from 36 atomic% to 41 atomic%, Y, Hf, Cs, Mg and Ti Containing at least one element selected from the group consisting of 0.01 to 2 atomic% in total (100 atomic% in total of Cr, Al, Ni, Y, Hf, Cs, Mg and Ti), Or 56 atoms of Cr 99 atomic% or less, Al 0.1 atomic% or more and 43 atomic% or less, Ni 0.1 atomic% or more and 25 atomic% or less, and at least one selected from the group consisting of Y, Hf, Cs, Mg and Ti In a total of 0.01 atomic percent or more and 2 atomic percent or less (total of Cr, Al, Ni, Y, Hf, Cs, Mg, and Ti is 100 atomic percent), or Cr is 0.1 atomic percent % Of atomic% to 15 atomic%, Al of 0.1 atomic% to 10 atomic%, Fe of 86 atomic% to 99 atomic%, and at least one selected from the group consisting of Y, Hf, Cs, Mg and Ti Contains 0.01 atomic percent or more and 2 atomic percent or less of total elements (total of 100 atomic% of Cr, Al, Fe, Y, Hf, Cs, Mg, and Ti) or 0.1 atomic% of Cr 99 atomic% or less, Al 0.1 atomic% or more 5 0 atomic% or less, Fe 0.1 atomic% or more and 99 atomic% or less, and at least one element selected from the group consisting of Y, Hf, Cs, Mg and Ti in total 0.01 atomic% or more and 2 atomic% Or less (Cr, Al, Fe, Y, Hf, Cs, Mg, and Ti in a total of 100 atomic%), or Cr is 0.1 atomic% to 50 atomic% and Al is 55 atomic% to 65 Atomic% or less, Fe 0.1 atomic% or more and 44 atomic% or less, and at least one element selected from the group consisting of Y, Hf, Cs, Mg, and Ti in total 0.01 atomic% or more and 2 atomic% or less Contained (total of Cr, Al, Fe, Y, Hf, Cs, Mg and Ti is 100 atomic%), or Al is 25 atomic% to 50 atomic% and Cr is 0.1 atomic% to 10 atomic% % Or less, Co 0.1 atomic% or more and 10 atomic% Lower, Si is 0.1 atomic% to 10 atomic%, Ni is 19.9 atomic% to 74 atomic%, and at least one element selected from the group consisting of Y, Hf, Cs, Mg and Ti is summed 0.01 atomic percent or more and 2 atomic percent or less (100 atomic percent in total of Al, Cr, Co, Si, Ni, Y, Hf, Cs, Mg, and Ti), or 0.1 atomic percent of Cr % To 50 atomic%, Al to 0.1 atomic% to 22 atomic%, Ni and at least one element selected from the group consisting of Fe and Co in total 51 atomic% to 99 atomic%, Y Containing at least one element selected from the group consisting of Hf, Cs, Mg, and Ti in a total amount of 0.01 atomic% to 2 atomic% (Cr, Al, Ni, Fe, Co, Y, Hf, and Cs 100 raw materials for the sum of Mg and Ti Or a total of at least one element selected from the group consisting of Ni, Fe, and Co, Cr 0.1 atomic% or more and 10 atomic% or less, Al 23 atomic% or more and 29 atomic% or less 70 atomic% or more and 75 atomic% or less, and a total of at least one element selected from the group consisting of Y, Hf, Cs, Mg and Ti is 0.01 atomic% or more and 2 atomic% or less (Cr, Al, Ni and Fe, Co, Y, Hf, Cs, Mg and Ti in total 100 atom%), or Cr 0.1 atomic% to 20 atomic%, Al 58 atomic% to 63 atomic%, Ni And at least one element selected from the group consisting of Fe and Co in a sum total of at least one element selected from the group consisting of 36 atom% to 41 atom%, Y, Hf, Cs, Mg and Ti 0 0.01 atomic% or more and 2 atomic% or less (Cr, Al, Ni, Fe, Co, Y, Hf, Cs, Mg, and Ti are combined at 100 atomic%), or Cr is 56 atomic% or more and 99 atoms %, Al is 0.1 atomic% or more and 43 atomic% or less, and at least one element selected from the group consisting of Ni and Fe and Co is combined in a total of 0.1 atomic% and 25 atomic%, Y, Hf Containing at least one element selected from the group consisting of Cs, Mg and Ti in a total amount of 0.01 atomic percent to 2 atomic percent (Cr, Al, Ni, Fe, Co, Y, Hf, Cs and Mg 100 atomic% in total with Ti), or selected from the group consisting of Cr 0.1 atomic% to 15 atomic%, Al 0.1 atomic% to 10 atomic%, Fe, Co, and Ni A sum of at least one element 6 atomic% or more and 99 atomic% or less, and a total of at least one element selected from the group consisting of Y, Hf, Cs, Mg and Ti is 0.01 atomic% or more and 2 atomic% or less (Cr, Al, Fe and Co, Ni, Y, Hf, Cs, Mg and Ti in total 100 atom%) or Cr 0.1 atomic% to 99 atomic% and Al 0.1 atomic% to 50 atomic% Fe and at least one element selected from the group consisting of Co and Ni are at least one selected from the group consisting of 0.1 atomic% to 99 atomic% in total, Y, Hf, Cs, Mg and Ti In a total of 0.01 atomic percent or more and 2 atomic percent or less (100 atomic percent in total of Cr, Al, Fe, Co, Ni, Y, Hf, Cs, Mg, and Ti), or Cr 0.1 atomic% to 50 atomic% , Al is 55 atomic% or more and 65 atomic% or less, and Fe and Co and at least one element selected from the group consisting of Co and Ni in total is 0.1 atomic% or more and 44 atomic% or less, Y, Hf, Cs, Mg And a total of at least one element selected from the group consisting of Ti and 0.01 atomic% to 2 atomic% (total of Cr, Al, Fe, Co, Ni, Y, Hf, Cs, Mg and Ti The heat-resistant alloy member according to claim 1, which is 100 atomic%). On the surface of an alloy substrate containing at least 10 atomic% or more of Cr in the surface layer portion, it is composed of at least one element selected from the group consisting of Fe, Co and Ni, W and Cr (Fe, Co and Ni and W and Cr in total of 100 atomic%), or at least one element selected from the group consisting of Fe, Co and Ni and at least one element selected from the group consisting of W, Cr, Mo and Ta Forming a first layer comprising (100 atomic% in total of Fe, Co, Ni, W, Cr, Mo and Ta),
By heating the alloy substrate on which the first layer is formed to a temperature of 800 ° C. or more and 1300 ° C. or less, from at least one element selected from the group consisting of Fe, Co and Ni, and W and Cr Or at least one element selected from the group consisting of Fe, Co and Ni, and a group consisting of W, Cr, Mo and Ta. Forming an inner layer comprising at least one selected element (total of Fe, Co, Ni, W, Cr, Mo and Ta at 100 atomic%) ;
Forming a second layer containing at least one element selected from the group consisting of Fe, Co, and Ni and Al and Cr, but not containing Re, on the inner layer;
By heating the alloy substrate on which the second layer is formed to a temperature of 800 ° C. or higher and 1300 ° C. or lower, at least one element selected from the group consisting of Fe, Co and Ni, and Al and Cr A method for producing a heat-resistant alloy member, comprising the step of forming an outer layer that contains but does not contain Re.   The heat-resistant alloy member according to claim 11, wherein the first layer and the second layer are formed by at least one method selected from the group consisting of a slurry method, a spray method, a plating method, a thermal spraying method, and an electron beam evaporation method. Manufacturing method. Having at least one inner layer and at least one outer layer formed on the surface of an alloy substrate containing at least a surface layer of 10 atomic% or more of Cr,
At least one of the inner layers is composed of at least one element selected from the group consisting of Fe, Co, and Ni and W and Cr (total of Fe, Co, Ni, W, and Cr is 100 atomic%), or And at least one element selected from the group consisting of Fe, Co and Ni, and at least one element selected from the group consisting of W, Cr, Mo and Ta (Fe, Co, Ni, W, Cr and The total of Mo and Ta is 100 atomic%),
An alloy film in which at least one outer layer contains at least one element selected from the group consisting of Fe, Co, and Ni, and Al and Cr, but does not contain Re. On the surface of an alloy substrate containing at least 10 atomic% or more of Cr in the surface layer portion, it is composed of at least one element selected from the group consisting of Fe, Co and Ni, W and Cr (Fe, Co and Ni and W and Cr in total of 100 atomic%), or at least one element selected from the group consisting of Fe, Co and Ni and at least one element selected from the group consisting of W, Cr, Mo and Ta Forming a first layer comprising (100 atomic% in total of Fe, Co, Ni, W, Cr, Mo and Ta) ,
By heating the alloy substrate on which the first layer is formed to a temperature of 800 ° C. or more and 1300 ° C. or less, from at least one element selected from the group consisting of Fe, Co and Ni, and W and Cr Or at least one element selected from the group consisting of Fe, Co and Ni, and a group consisting of W, Cr, Mo and Ta. Forming an inner layer comprising at least one selected element (total of Fe, Co, Ni, W, Cr, Mo and Ta at 100 atomic%) ;
Forming a second layer containing at least one element selected from the group consisting of Fe, Co, and Ni and Al and Cr, but not containing Re, on the inner layer;
By heating the alloy substrate on which the second layer is formed to a temperature of 800 ° C. or higher and 1300 ° C. or lower, at least one element selected from the group consisting of Fe, Co and Ni, and Al and Cr A method for producing an alloy film comprising: forming an outer layer that contains but does not contain Re.