JP2021123771A - Heat resistant alloy member, manufacturing method of the same, high temperature apparatus and manufacturing method of the same - Google Patents

Abstract

To provide a heat resistant alloy member and a manufacturing method of the same capable of obtaining an excellent high temperature oxidation resistance in addition to a diffusion barrier function and a peeling resistance of a top layer of a heat barrier layer when used under an atmosphere of a high temperature oxidative atmosphere with a heating/cooling cycle added even if a heat resistant alloy base material containing no Al or a low concentration Al is used, and further capable of improving a mechanical strength of the heat resistance alloy base material, capable of maintaining a high temperature property of the heat resistant alloy base material for a long period, and further capable of providing a heat resistance by providing a minimum necessary region with the top layer.SOLUTION: A heat resistant alloy member has a heat resistant alloy base material, a multipurpose alloy layer of a Re system, a W system, or a Cr system arranged in a region containing at least a region to be heat shielded on a surface, a bonding layer which is arranged in a region containing at least the region to be heat shielded thereon and is composed of Al-containing alloy, and a top layer which is composed of a heat shield ceramic and arranged only in the region to be heat shielded thereon.SELECTED DRAWING: Figure 1

Description

The present invention relates to a heat-resistant alloy member and a method for manufacturing the same, and a high-temperature device and the method for manufacturing the same. , Exhaust gas system members, etc. are suitable.

Thermal Barrier Coating (TBC) is applied to the heat-resistant alloy base material used in various combustion equipment, turbines, jet engines, and the like. As a typical TBC, for example, MCRAlY (M = Co, Ni) as a bond layer and a ceramic heat shield layer (for example, yttria (Y ₂ O ₃ ) stabilized zirconia (for example) as a top layer are used on the entire surface of the heat-resistant alloy base material. ZrO ₂ ) (Yttria Stabilized Zirconia: YSZ)) is constructed by thermal spraying, electron beam deposition, etc. _{A thermal oxide (TGO) mainly composed of Al 2} O ₃ is formed at the interface between the top layer and the bond layer to suppress the oxidation of the heat-resistant alloy base material. In addition, the top layer and the bond layer are sometimes called a heat shield layer (TBC).

However, in the heat-resistant alloy base material, the elements of the base material diffuse to the bond layer side and the Al of the bond layer diffuses to the base material side during use, so that the Al concentration of the bond layer decreases and a non-protective TGO is formed. -Since the top layer (YSZ) is peeled off at an early stage due to growth, a solution is required.

Conventionally, in a gas turbine blade for power generation, in order to suppress the mutual diffusion of the above-mentioned elements, Al is added by weight to 4.9 in addition to C, B, Hf, Cr, Mo, W, Re, Ta, Nb and Co. After forming a diffusion barrier layer containing Re and the like on the entire surface of a wing base material made of a Ni-based single crystal superalloy containing% or more and 5.2% or less and the balance being Ni, a bond layer and a bond layer and the entire surface thereof are formed. A technique for sequentially laminating top layers has been proposed (see Patent Documents 1 to 3). Details of the diffusion barrier layer are described in Patent Documents 4 to 7.

Japanese Patent No. 5905336 Japanese Patent No. 5905354 Japanese Patent No. 5905355 Patent No. 38576889 Japanese Patent No. 3857690 Patent No. 3910588 Japanese Patent No. 4735720

In the gas turbine blades for power generation described in Patent Documents 1 to 3, the diffusion barrier layer prevents the elements of the base material from diffusing to the bond layer side and the Al of the bond layer to the base material side during use. In addition to being able to prevent peeling of the top layer (YSZ) by being able to suppress the formation and growth of non-protective TGO, the wing base material contains Al by 4.9% or more by weight 5 Since it is made of a Ni-based single crystal superalloy containing .2% or less, protective Al ₂ O ₃ is formed on the surface of the blade base material during high-temperature oxidation, and oxidation resistance can be ensured. However, when a heat-resistant alloy base material that does not contain Al or that contains Al but has a low Al concentration is used, even if this technique is applied as it is, oxidation resistance is ensured and the top layer (YSZ) Peeling prevention cannot be achieved at the same time.

Therefore, the problem to be solved by the present invention is that even when a heat-resistant alloy base material containing no Al or having a low Al concentration is used, it is used in an environment in which a heating / cooling cycle is added in a high-temperature oxidizing atmosphere. In this case, in addition to the diffusion barrier function and the peeling resistance of the top layer of the heat shield layer, excellent high temperature oxidation resistance can be obtained, and further, the mechanical strength of the heat-resistant alloy base material can be improved. The high-temperature characteristics of the heat-resistant alloy base material can be maintained for a long period of time, and the heat-resistant alloy member and its manufacturing method, and such a heat-resistant alloy member, which are sufficient by providing the top layer in the minimum necessary area, are provided. It is to provide the high temperature apparatus including and the manufacturing method thereof.

In order to solve the above problems, the present invention
Heat resistant alloy base material and
A Re-based, W-based, or Cr-based multipurpose alloy layer provided in a region including at least a region for heat shielding on the surface of the heat-resistant alloy base material, and
A bond layer made of an Al-containing alloy provided in a region of the multipurpose alloy layer that includes at least a region to be heat-shielded, and a bond layer made of an Al-containing alloy.
A top layer made of heat-shielding ceramics provided only in the area on the bond layer to be heat-shielded, and
It is a heat-resistant alloy member having.

In the present invention, the Re-based, W-based or Cr-based Multi-Purpose Layer (MPL) has, in addition to the diffusion barrier ability, oxidation resistance, improvement of the mechanical properties of the heat-resistant alloy base material, and a top layer. It means an alloy layer that has multiple functions such as improved peeling resistance and can be used for multiple purposes. The Re-based, W-based or Cr-based multipurpose alloy layers contain Re, W and Cr, respectively.

For example, when the multipurpose alloy layer is Re-based or W-based, the multipurpose alloy layer, the bond layer, and the top layer are provided only in the region where heat shielding is to be performed on the surface of the heat-resistant alloy base material. In one typical example, the Re-based or W-based multipurpose alloy layer, bond layer, and top layer are provided only in the region where heat shielding should be performed on the surface of the heat-resistant alloy base material, and the region other than the region where heat shielding should be performed. An Al-containing alloy film is provided so as to cover the surface of the heat-resistant alloy base material of the portion. _{In this case, a protective Al 2} O ₃ film is formed by the oxidation of the Al-containing alloy film during the oxidation at a high temperature, and the high temperature oxidation resistance of the heat-resistant alloy base material can be ensured. The Al-containing alloy film is generally a Ni-based alloy having an Al concentration of 50 atomic% (at%) or less and 30% atoms or more, and an Al concentration is preferably 40 atomic% or less. The Al-containing alloy film typically comprises, but is not limited to, β-NiAl. The multipurpose alloy layer may be formed by laminating two different layers selected from a Re-based multipurpose alloy layer and a W-based multipurpose alloy layer. In another example, a Cr-based multipurpose alloy layer and an Al-containing alloy film on the multipurpose alloy layer are provided so as to cover the entire surface of the heat-resistant alloy base material, and the bond layer and the top layer are on the Al-containing alloy film. It is provided only in the area where heat insulation should be performed. Alternatively, the multipurpose alloy layer, the bond layer, and the top layer are provided only in the region where the heat shield should be performed on the surface of the heat resistant alloy base material, and cover the surface of the heat resistant alloy base material in the portion other than the region where the heat shield should be performed. A multipurpose alloy layer and an Al-containing alloy film on the multipurpose alloy layer are provided. Alternatively, a Cr-based multipurpose alloy layer and an Al-containing alloy film that also serves as a bond layer are provided on the multipurpose alloy layer so as to cover the entire surface of the heat-resistant alloy base material, and the top layer is on the Al-containing alloy film. It is provided only in the area where heat insulation should be performed.

The heat-resistant alloy base material is selected as needed, and may or may not be particularly limited. Unless otherwise limited, the heat-resistant alloy base material is made of a conventionally known alloy such as an Fe-based alloy, a Co-based alloy, or a Ni-based alloy having a Cr content of 20 atomic% or less. When a Cr-based multipurpose alloy layer is used, the heat-resistant alloy base material preferably contains 24.5 atoms in total of one or more metals selected from the group consisting of Cr, Mo, Nb and W. It is composed of a Ni-based alloy containing% or more. In this case, more preferably, the Ni-based alloy contains 18.7 atomic% or more of Cr, and 5.7 atomic% in total contains one or more metals selected from the group consisting of Mo, Nb and W. It contains 19.2 atomic% or less, and contains Fe and Nb in a total of 13.1 atomic% or less. When a Re-based multipurpose alloy layer is used, the heat-resistant alloy base material may be made of a Ni-based single crystal superalloy. The shape of the heat-resistant alloy base material is not particularly limited and is selected according to the intended use, and is, for example, flat plate-shaped, rod-shaped (square bar, round bar, etc.), tubular, box-shaped, and the like.

The Al-containing alloy constituting the bond layer is typically MCrAlY (M = Co, Ni), but is not limited to this, for example, β-NiAl, γ'-Ni ₃ Al, γ-. It may be Ni (Al, Cr) or the like.

The heat-shielding ceramics constituting the top layer are, for example, oxide ceramics containing zirconium, yttrium and oxygen (typically YSZ), oxide ceramics containing aluminum, yttrium and oxygen, and aluminum, lantern and oxygen. At least selected from the group consisting of oxide ceramics containing and, oxide ceramics containing aluminum, samarium and oxygen, oxide ceramics containing cerium and oxygen, and oxide ceramics containing thorium and oxygen. It consists of a kind.

The heat-resistant alloy member is not particularly limited, and specific examples thereof include a gas turbine member, a jet engine member, an exhaust gas system member, and the like.

Moreover, this invention
A step of forming a Re-based, W-based or Cr-based multipurpose alloy layer in a region including at least a region to be heat-shielded on the surface of the heat-resistant alloy base material, and a step of forming the Re-based, W-based or Cr-based multipurpose alloy layer.
A step of forming a bond layer made of an Al-containing alloy in a region of the multipurpose alloy layer including at least a region to be heat-shielded, and a step of forming the bond layer.
A step of forming a top layer made of heat-shielding ceramics only in the region on the bond layer to be heat-shielded, and
It is a method of manufacturing a heat-resistant alloy member having.

In the present invention, for example, the multipurpose alloy layer is formed only in the region where heat shielding is to be performed on the surface of the heat-resistant alloy base material, and then the bond layer and the top layer are sequentially formed on the multipurpose alloy layer. Thermal spraying, electron beam deposition, or the like can be used to form the bond layer and the top layer. Alternatively, a multipurpose alloy layer is formed only in the region where heat shielding should be performed on the surface of the heat-resistant alloy base material, and Al diffusion treatment is applied to cover the surface of the heat-resistant alloy base material in a portion other than the region where heat shielding should be performed. After forming an Al-containing alloy film on the surface, a bond layer and a top layer are sequentially formed on the multipurpose alloy layer. Here, when the heat-resistant alloy base material is made of a Ni-based alloy containing 24.5 atomic% or more in total of one or more kinds of metals selected from the group consisting of Cr, Mo, Nb and W, it is bonded. After forming the layers and the top layer in sequence, oxidation is performed at a high temperature to form a Cr-based multipurpose alloy layer between the heat-resistant alloy base material and the Al-containing alloy film by the reaction between the heat-resistant alloy base material and the Al-containing alloy film. Form. Alternatively, the heat-resistant alloy base material is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and is subjected to Al diffusion treatment. As a result, an Al-containing alloy film is formed on the entire surface of the heat-resistant alloy base material, and a bond layer and a top layer are sequentially formed only in the region to be heat-shielded, and then heat treatment is performed at a high temperature. By heating to a high temperature, a Cr-based multipurpose alloy layer is formed between the heat-resistant alloy base material and the Al-containing alloy film by the reaction between the heat-resistant alloy base material and the Al-containing alloy film. Furthermore, the heat-resistant alloy base material is made of a Ni-based alloy containing 24.5 atomic% or more in total of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and is subjected to Al diffusion treatment. By applying, an Al-containing alloy film that also serves as a bond layer is formed on the entire surface of the heat-resistant alloy base material, a top layer is formed only in the region on the Al-containing alloy film that should be heat-shielded, and then heat treatment at a high temperature is performed. I do. By heating to a high temperature, a Cr-based multipurpose alloy layer is formed between the heat-resistant alloy base material and the Al-containing alloy film by the reaction between the heat-resistant alloy base material and the Al-containing alloy film. For the formation of the bond layer and the top layer, for example, a thermal spraying method, an electron beam vapor deposition method, or the like can be used.

In the present invention, the matters other than the above are described in relation to the above invention of the heat-resistant alloy member as long as the properties are not contrary to the above.

Moreover, this invention
Heat resistant alloy base material and
A Re-based, W-based, or Cr-based multipurpose alloy layer provided in a region including at least a region for heat shielding on the surface of the heat-resistant alloy base material, and
A bond layer made of an Al-containing alloy provided in a region of the multipurpose alloy layer that includes at least a region to be heat-shielded, and a bond layer made of an Al-containing alloy.
It is a high temperature device having a heat-resistant alloy member having a top layer made of heat-shielding ceramics provided only in the region on the bond layer to be heat-shielded.

The high-temperature device may be various devices including the above-mentioned heat-resistant alloy member in part or all, and specifically, for example, a gas turbine, a jet engine, an exhaust gas device, or the like.

Moreover, this invention
A step of forming a Re-based, W-based or Cr-based multipurpose alloy layer in a region including at least a region to be heat-shielded on the surface of the heat-resistant alloy base material, and a step of forming the Re-based, W-based or Cr-based multipurpose alloy layer.
A step of forming a bond layer made of an Al-containing alloy in a region of the multipurpose alloy layer including at least a region to be heat-shielded, and a step of forming the bond layer.
This is a method for manufacturing a high temperature apparatus, which comprises a step of forming a top layer made of heat-shielding ceramics only in a region on the bond layer to be heat-shielded, and a step of manufacturing a heat-resistant alloy member by executing the steps.

In the invention of the high temperature device and the invention of the method of manufacturing the high temperature device, the matters other than the above are related to the invention of the heat resistant alloy member and the invention of the method of manufacturing the heat resistant alloy member, unless the properties are not particularly contrary to the above. The explanation is established.

According to the present invention, even when a heat-resistant alloy base material containing no Al or having a low Al concentration is used, the diffusion barrier is used in an environment where a heating / cooling cycle is added in a high-temperature oxidizing atmosphere. In addition to the function and the peeling resistance of the top layer of the heat shield layer, excellent high temperature oxidation resistance can be obtained, and the mechanical strength of the heat resistant alloy base material can be improved. The high temperature characteristics can be maintained for a long period of time, and it is sufficient to provide the top layer in the minimum necessary area.

It is sectional drawing which shows the heat-resistant alloy member by 1st Embodiment of this invention. It is sectional drawing which shows the heat-resistant alloy member by the 2nd Embodiment of this invention. It is sectional drawing which shows the heat-resistant alloy member by the 3rd Embodiment of this invention. It is sectional drawing which shows the heat-resistant alloy member by the 4th Embodiment of this invention. It is sectional drawing which shows the heat-resistant alloy member by the 5th Embodiment of this invention. It is sectional drawing which shows the heat-resistant alloy member by the 6th Embodiment of this invention. It is sectional drawing which shows the heat-resistant alloy member by 7th Embodiment of this invention. It is a perspective view which shows the test piece used for the high temperature cycle oxidation test. It is sectional drawing which shows the test piece used for a creep test. It is a perspective view which shows the test piece used for the high temperature cycle oxidation test. It is sectional drawing which shows the structure of the test piece of Example 1. FIG. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 1. FIG. It is sectional drawing which shows the structure of the test piece of Example 2. FIG. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 2. FIG. It is sectional drawing which shows the structure of the test piece of Example 3. FIG. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 3. FIG. It is sectional drawing which shows the structure of the test piece of Example 4. FIG. It is sectional drawing which shows the structure of the test piece of Example 5. FIG. It is sectional drawing which shows the structure of the test piece of Example 6. It is sectional drawing which shows the structure of the test piece of Example 7. FIG. It is sectional drawing which shows the structure of the test piece of Example 8. FIG. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 8. FIG. It is sectional drawing which shows the structure of the test piece of Example 9. FIG. It is sectional drawing which shows the structure of the test piece of Example 10. It is sectional drawing which shows the structure of the test piece of Example 11. FIG. It is sectional drawing which shows the structure of the test piece of Example 12. FIG. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 12. FIG. It is sectional drawing which shows the structure of the test piece of the comparative example 2. FIG. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Comparative Example 2. It is a schematic diagram which shows the cycle number dependence of the oxidation amount of the test piece of Examples 1-5, 8-10 and Comparative Example 1 which performed heating / cooling cycle oxidation. It is a drawing substitute photograph which shows the process which the YSZ layer of the top layer of the heat-resistant alloy member of Comparative Example 1 leads to peeling. It is a drawing substitute photograph which shows the process which the YSZ layer of the top layer of the heat-resistant alloy member of Example 1 leads to peeling. FIG. 5 is a schematic diagram showing the cycle number dependence of the Al concentration of the bond layer of the test pieces of Examples 1 to 5 and Comparative Example 1. It is a drawing-substituting photograph showing the cross-sectional structure of the test piece after Al diffusion of various Ni-based alloys shown in Table 1. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of various Ni-based alloys shown in Table 1 after four-cycle oxidation. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of various Ni-based alloys shown in Table 1 after 100 cycles of oxidation. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of various Ni-based alloys shown in Table 1 after 100 cycles of oxidation. It is a schematic diagram which shows the creep curve of the Ni-based alloy which formed various multipurpose alloy layers. It is a schematic diagram which shows the result of observing the surface and cross-sectional structure of the Ni-based alloy which formed various multipurpose alloy layers. It is a drawing substitute photograph showing the enlarged structure of the Re-based multipurpose alloy layer / β-NiAl film and the concentration distribution of each element in the cross-sectional structure shown in FIG. 39. It is a drawing substitute photograph and a schematic diagram which shows the creep behavior of the SUS310 base material which formed the Re system multipurpose alloy layer. It is a schematic diagram which shows the creep curve of the SUS310 base material which formed the Re system multipurpose alloy layer. It is a schematic diagram which shows the creep curve of the SUS310 base material which formed the Re system multipurpose alloy layer.

Hereinafter, embodiments for carrying out the invention (hereinafter, simply referred to as “embodiments”) will be described.

<First Embodiment>
[Heat-resistant alloy member]
FIG. 1 shows a heat-resistant alloy member according to the first embodiment. As shown in FIG. 1, in this heat-resistant alloy member, the Re-based multipurpose alloy layer 201, the bond layer 300, and the top layer 400 are sequentially laminated only in a specific region where heat shielding should be performed on the surface of the heat-resistant alloy base material 100. In other areas, the surface of the heat-resistant alloy base material 100 is exposed. The Re-based multipurpose alloy layer 201 is made of an alloy layer containing Re, and typically the upper part is made of a Ni—Cr alloy layer 201a. As the alloy layer containing Re, those described in Patent Document 4 and the like are used. The bond layer 300 is made of an Al-containing alloy such as MCrAlY (M = Ni, Co), β-NiAl, γ'-Ni ₃ Al, and γ-Ni (Al, Cr). The top layer 400 is made of heat-shielding ceramics such as YSZ. _{In this heat-resistant alloy member, a TGO-Al 2} O ₃ layer is formed between the bond layer 300 and the top layer 400 before or after the start of use. The thickness of this TGO-Al ₂ O ₃ layer is, for example, about several μm.

The heat-resistant alloy base material 100 is selected as necessary, and is selected from, for example, those already mentioned. Specifically, for example, a Ni-based alloy, an Fe-based alloy, a Co-based alloy, and in particular, Cr-containing among these. A Ni group containing 24.5 atomic% or more of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and those having an amount of 20 atomic% or more. Those made of alloys, those made of Ni-based single crystal superalloys, etc.

The thickness of the bond layer 300 is, for example, 50 μm or more and 150 μm or less. The thickness of the top layer 400 is, for example, 200 μm or more and 500 μm or less.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

Consider the case where the heat-resistant alloy base material 100 is made of a Ni-based alloy, an Fe-based alloy, a Co-based alloy, or the like. First, the surface of the heat-resistant alloy base material 100 is masked by covering a portion other than a specific region to be heat-shielded with insulating tape or forming an insulating coating film, and then plating is performed only on the specific region. To form a Re-containing layer. Specifically, for example, Ni plating → Re- (30 to 40) atomic% Ni plating → Ni plating → Cr plating or Ni plating → Re- (30 to 40) atomic% Ni plating → Ni (Co) plating. → Perform in the order of Cr plating. Next, the heat treatment is performed in a vacuum or in an inert gas atmosphere, preferably in an Ar + 3 vol% H ₂ atmosphere, at a temperature of, for example, 900 ° C. or higher and 1100 ° C. or lower for 1 to 10 hours. As a result, the Re-based multipurpose alloy layer 201 is formed by the reaction between the heat-resistant alloy base material 100 and the Re-containing layer. At this time, a Ni—Cr layer 201a is formed on the upper part of the Re-based multipurpose alloy layer 201. Next, the bond layer 300 and the top layer 400 are sequentially formed on the Re-based multipurpose alloy layer 201 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere, but if it is formed in advance, it may be formed. For example, after forming the bond layer 30, oxidation treatment is performed in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

As described above, according to the first embodiment, the bond layer 300 and the top layer 40 pass through the Re-based multipurpose alloy layer 201 only in a specific region where the surface of the heat-resistant alloy base material 100 should be shielded from heat. When this heat-resistant alloy member is used in an environment where heating and cooling are repeated in a high-temperature oxidizing atmosphere, the Re-based multipurpose alloy layer 201 is used to transfer the Al heat-resistant alloy base material 100 of the bond layer 300 to the Al heat-resistant alloy base material 100. It is possible to prevent the diffusion of the element of the heat-resistant alloy base material 100 into the bond layer 300, and the Al concentration of the bond layer 300 can be sufficiently high, for example, maintained at 13 atomic% or more, and the bond layer 300 can be maintained. _{The TGO-Al 2} O ₃ layer can be maintained between the top layer 400 and the top layer 400 for a long period of time, whereby not only excellent high temperature corrosion resistance can be obtained, but also the TGO-Al ₂ O ₃ layer can be maintained. By suppressing the formation of non-protective oxides other than the above, it is possible to effectively prevent the peeling of the top layer 400, thereby obtaining excellent peel resistance, and further, the heat-resistant alloy base material 100. The mechanical strength of the alloy can be improved. This heat-resistant alloy member sufficiently satisfies the required characteristics as a high-temperature member such as a gas turbine, a jet engine, an exhaust gas system member, etc., whose operating temperature tends to rise in recent years with the aim of increasing the output. be.

<Second Embodiment>
[Heat-resistant alloy member]
FIG. 2 shows a heat-resistant alloy member according to the second embodiment. As shown in FIG. 2, in this heat-resistant alloy member, the Re-based multipurpose alloy layer 201, the bond layer 300, and the top layer 400 are sequentially laminated only in a specific region where heat shielding should be performed on the surface of the heat-resistant alloy base material 100. ing. The Re-based multipurpose alloy layer 201 is the same as in the first embodiment. The portion of the surface of the heat-resistant alloy base material 100 other than the specific region to be heat-shielded is covered with the Al-containing alloy film 150. The Al-containing alloy film 150 typically comprises β-NiAl or Fe—Al. The heat-resistant alloy base material 100, the bond layer 300, and the top layer 400 are the same as those in the first embodiment.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

Consider the case where the heat-resistant alloy base material 100 is made of a Ni-based alloy, an Fe-based alloy, a Co-based alloy, or the like. First, the Re-based multipurpose alloy layer 201 is formed in a specific region where heat shielding should be performed on the surface of the heat-resistant alloy base material 100 in the same manner as in the first embodiment. Next, the Al-containing alloy film 150 is formed on the surface of the heat-resistant alloy base material 100 at a portion other than the Re-based multipurpose alloy layer 201 by performing the Al diffusion treatment. The Al diffusion treatment is carried out by burying the heat-resistant alloy base material 100 in (Al + NH ₄ Cl + Al ₂ O ₃ ), for example, and heating at a temperature of 700 to 800 ° C. for 30 minutes to 1.5 hours in an Ar atmosphere. Alternatively, the heat-resistant alloy base material 100 is _{embedded in (FeAl + NH 4} Cl + Al ₂ O ₃ ) or (Al + Ni + NH ₄ Cl + Al ₂ O ₃ ) and heated at a temperature of 900 to 1100 ° C. for 1 to 10 hours in an Ar + 3 vol% H _{2 atmosphere.} Do it by. Next, the bond layer 300 and the top layer 400 are sequentially formed on the Re-based multipurpose alloy layer 201 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere, but if it is formed in advance, it may be formed. For example, after forming the bond layer 300, oxidation treatment is performed in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

According to this second embodiment, the same advantages as those of the first embodiment can be obtained, and the surface of the heat-resistant alloy base material 100 other than the Re-based multipurpose alloy layer 201 is an Al-containing alloy film. Since it is coated with 150, a protective Al ₂ O ₃ film is formed and protected at the time of high temperature oxidation, so that it is possible to obtain an advantage that excellent high temperature oxidation resistance can be ensured.

<Third embodiment>
[Heat-resistant alloy member]
FIG. 3 shows a heat-resistant alloy member according to the third embodiment. As shown in FIG. 3, in this heat-resistant alloy member, the W-based multipurpose alloy layer 202, the bond layer 300, and the top layer 400 are sequentially laminated only in a specific region where heat shielding should be performed on the surface of the heat-resistant alloy base material 100. ing. The W-based multipurpose alloy layer 202 is composed of an alloy layer containing W, and typically has a Ni (Cr, Si) layer 202a at the upper portion. The portion of the surface of the heat-resistant alloy base material 100 other than the specific region to be heat-shielded is covered with the Al-containing alloy film 150. The Al-containing alloy film 150 typically comprises β-AlNi or Fe-Al. The heat-resistant alloy base material 100, the bond layer 300, and the top layer 400 are the same as those in the first embodiment.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

Consider the case where the heat-resistant alloy base material 100 is made of a Ni-based alloy, an Fe-based alloy, a Co-based alloy, or the like. First, a W-containing layer is formed by applying a slurry to a specific region on the surface of the heat-resistant alloy base material 100 to be heat-shielded. Specifically, for example, (25 to 50% by weight) W powder, (15 to 25% by weight) Cr powder, (15 to 30% by weight) Mo powder, and the balance Ni-based self-dissolving alloy (nominal composition (% by weight)). A slurry in which Ni-15Cr-3Si-2B-5Fe) is dissolved in a slurry solution is used. Next, the heat treatment is performed in a vacuum or in an inert gas atmosphere (for example, Ar + 3vol% H ₂ ) at a temperature of, for example, 1100 ° C. or higher and 1200 ° C. or lower for 1 to 10 hours. As a result, the W-based multipurpose alloy layer 202 is formed by the reaction between the heat-resistant alloy base material 100 and the W-containing layer. At this time, a Ni (Cr, Si) layer 202a is formed on the upper part of the W-based multipurpose alloy layer 202. Next, the Al-containing alloy film 150 is formed on the surface of the heat-resistant alloy base material 100 at a portion other than the W-based multipurpose alloy layer 202 by performing the Al diffusion treatment. The Al diffusion treatment is carried out by burying the heat-resistant alloy base material 10 in, for example, (Al + NH ₄ Cl + Al ₂ O ₃ ) and heating it in an Ar atmosphere at a temperature of 700 to 800 ° C. for 1 to 1.5 hours. Alternatively, it is carried out by burying it in (FeAl + NH ₄ Cl + Al ₂ O ₃ ) or (Al + Ni + NH ₄ Cl + Al ₂ O ₃ ) and heating it in an Ar + 3 vol% H ₂ atmosphere at a temperature of 900 to 1100 ° C. for 1 to 10 hours. Next, the bond layer 300 and the top layer 400 are sequentially formed on the W-based multipurpose alloy layer 202 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere, but if it is formed in advance, it may be formed. For example, after forming the bond layer 300, oxidation treatment is performed in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

According to this third embodiment, the same advantages as those of the first embodiment can be obtained, and the surface of the heat-resistant alloy base material 100 other than the W-based multipurpose alloy layer 202 is an Al-containing alloy film. Since it is coated with 150, a protective Al ₂ O ₃ film is formed and protected at the time of high temperature oxidation, so that it is possible to obtain an advantage that excellent high temperature oxidation resistance can be ensured.

<Fourth Embodiment>
[Heat-resistant alloy member]
FIG. 4 shows a heat-resistant alloy member according to the fourth embodiment. As shown in FIG. 4, in this heat-resistant alloy member, the Re-based multipurpose alloy layer 201, the bond layer 300, and the top layer 400 are sequentially laminated only in a specific region where heat shielding should be performed on the surface of the heat-resistant alloy base material 105. Has been done. The heat-resistant alloy base material 100 is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W. The portion of the surface of the heat-resistant alloy base material 100 other than the specific region to be heat-shielded is covered with the Cr-based multipurpose alloy layer 203 and the Al-containing alloy film 150 on the Cr-based multipurpose alloy layer 203. The Cr-based multipurpose alloy layer 203 is composed of an alloy layer containing α-Cr, and is typically one or more selected from the group consisting of constituent elements of the heat-resistant alloy base material 100, for example, Mo, Nb, and W. Contains metal. The Al-containing alloy film 150 is typically made of β-AlNi. The bond layer 300 and the top layer 400 are the same as in the first embodiment.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

As shown in FIG. 4, first, the Re-based multipurpose alloy layer 201 is formed in a specific region on the surface of the heat-resistant alloy base material 105 to be heat-shielded in the same manner as in the first embodiment. Next, the Al-containing alloy film 150 is formed on the surface of the heat-resistant alloy base material 105 at a portion other than the Re-based multipurpose alloy layer 201 by performing the Al diffusion treatment. At this time, the Cr-based multipurpose alloy layer 203 is formed between the heat-resistant alloy base material 105 and the Al-containing alloy film 150. Next, the bond layer 300 and the top layer 400 are sequentially formed on the Re-based multipurpose alloy layer 201 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere, but if it is formed in advance, it may be formed. For example, after forming the bond layer 300, oxidation treatment is performed in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

According to this fourth embodiment, the same advantages as those of the third embodiment can be obtained.

<Fifth Embodiment>
[Heat-resistant alloy member]
FIG. 5 shows a heat-resistant alloy member according to the fifth embodiment. As shown in FIG. 5, in this heat-resistant alloy member, the W-based multipurpose alloy layer 202, the bond layer 300, and the top layer 400 are sequentially laminated only in a specific region where heat shielding should be performed on the surface of the heat-resistant alloy base material 105. Has been done. The heat-resistant alloy base material 105 is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W. The portion of the surface of the heat-resistant alloy base material 105 other than the specific region to be heat-shielded is covered with the Cr-based multipurpose alloy layer 203 and the Al-containing alloy film 150 on the Cr-based multipurpose alloy layer 203. The Cr-based multipurpose alloy layer 203 is the same as that of the fourth embodiment. The Al-containing alloy film 150 is typically made of β-NiAl. The bond layer 300 and the top layer 400 are the same as in the first embodiment.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

First, the W-based multipurpose alloy layer 202 is formed in a specific region on the surface of the heat-resistant alloy base material 105 in the same manner as in the second embodiment. Next, as in the third embodiment, the Cr-based multipurpose alloy layer 203 and the Al-containing alloy film 150 are applied to the surface of the heat-resistant alloy base material 105 at a portion other than the W-based multipurpose alloy layer 202 by performing the Al diffusion treatment. To form. Next, the bond layer 300 and the top layer 400 are sequentially formed on the W-based diffusion barrier layer 202 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere, but if it is formed in advance, it may be formed. For example, after forming the bond layer 300, oxidation treatment is performed in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

According to this fifth embodiment, the same advantages as those of the fourth embodiment can be obtained.

<Sixth Embodiment>
[Heat-resistant alloy member]
FIG. 6 shows a heat-resistant alloy member according to the sixth embodiment. As shown in FIG. 6, in this heat-resistant alloy member, a Cr-based multipurpose alloy layer 203 and an Al-containing alloy film 150 on the Cr-based multipurpose alloy layer 203 are provided on the entire surface of the heat-resistant alloy base material 105. The heat-resistant alloy base material 105 is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W. The Al-containing alloy film 150 is typically made of β-NiAl. The Cr-based multipurpose alloy layer 203 is the same as that of the fourth embodiment. The bond layer 300 and the top layer 400 are sequentially laminated on the Al-containing alloy film 150 of the heat-resistant alloy base material 105 only in a specific region to be heat-shielded. The Al-containing alloy film 150 in the specific region to be heat-shielded constitutes a part of the bond layer 300. The top layer 400 is the same as in the first embodiment.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

First, as in the fourth embodiment, the Cr-based multipurpose alloy layer 203 and the Al-containing alloy film 150 are formed on the entire surface of the heat-resistant alloy base material 105 by performing the Al diffusion treatment. Next, the bond layer 300 and the top layer 400 are sequentially formed on the Al-containing alloy film 150 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere, but if it is formed in advance, it may be formed. For example, after forming the bond layer 300, oxidation treatment is performed in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

According to this sixth embodiment, the same advantages as those of the fourth embodiment can be obtained.

<Seventh Embodiment>
FIG. 7 shows a heat-resistant alloy member according to the seventh embodiment. As shown in FIG. 7, in this heat-resistant alloy member, a Cr-based multipurpose alloy layer 203 and an Al-containing alloy film 150 on the Cr-based multipurpose alloy layer 203 are provided on the entire surface of the heat-resistant alloy base material 105. The heat-resistant alloy base material 105 is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W. The Al-containing alloy film 150 is typically made of β-NiAl. The Cr-based multipurpose alloy layer 203 is the same as that of the sixth embodiment. The top layer 400 is laminated on the Al-containing alloy film 150 only in a specific region where the heat-resistant alloy base material 105 should be heat-shielded. The Al-containing alloy film 150 in the specific region to be heat-shielded also serves as the bond layer 300. The top layer 400 is the same as in the first embodiment.

[Manufacturing method of heat-resistant alloy members]
A method for manufacturing this heat-resistant alloy member will be described.

First, as in the sixth embodiment, the Cr-based multipurpose alloy layer 203 and the Al-containing alloy film 150 are formed on the entire surface of the heat-resistant alloy base material 105 by performing the Al diffusion treatment. Next, the top layer 400 is formed on the Al-containing alloy film 150 by thermal spraying, electron beam deposition, or the like. _{The TGO-Al 2} O ₃ layer between the Al-containing alloy film 150 that also serves as the bond layer 300 and the top layer 400 is generally formed when the heat-resistant alloy member is used in a high-temperature oxidizing atmosphere. When it is formed in advance, for example, after forming the Al-containing alloy film 150, it is oxidized in a low oxygen partial pressure atmosphere.

From the above, the target heat-resistant alloy member is manufactured.

According to this seventh embodiment, the same advantages as those of the sixth embodiment can be obtained.

Examples will be described.

The following (1) to (3) were used as the heat-resistant alloy base material 100.
(1) Base material made of Ni-based heat-resistant alloy shown in Table 1 (extracted from the catalog of Osaka Stainless Co., Ltd.)

In Table 1, Alloy 201 corresponds to Ni (industrial). Other alloys can be said to be Ni-based alloys.

(2) SUS310 base material (composition (% by weight) is Cr: 25, Ni: 20, Fe: balance)
(3) Ni-based single crystal superalloy (composition (% by weight) is Al: 4.9 to 5.3, Co: 0.8 to 1.2, Cr: 6.9 to 7.3, Mo: 0. 7 to 1.0, W: 7.0 to 9.0, Re: 1.2 to 1.6, Ta: 8.5 to 9.5, Nb: 0.6 to 1.0, Ni: balance)

As the bond layer 300 of the heat-shielding coating film, one composed of CoNiCrAlY (nominal composition (wt%); Ni-25Cr-10Al-0.5Y) was used. The CoNiCrAlY layer was formed by a thermal spraying process (high-speed frame thermal spraying method) of HVOF (High Velocity Oxy-Fuel). The thickness of the CoNiCrAlY layer was 100 μm. The top layer 400 YSZ (nominal composition _{(mol%); 8Y 2 O} 3 -92ZrO 2) was used made of. The YSZ layer was formed by an atmospheric plasma (APS) spraying process. The thickness of the YSZ layer was set to 300 μm.

The shapes and sizes of the test piece for the cycle oxidation test and the test piece for the creep test when (1) is used as the heat-resistant alloy base material 100 and (2) is used as the heat-resistant alloy base material 100 are shown in FIGS. 8 and 9, respectively. show. As shown in FIG. 8, the test piece has a multipurpose alloy layer, a bond layer and a top layer (the multipurpose alloy layer is MPL, and the bond layer and the top layer are TBC) on the upper end surface of a columnar base material having a diameter of 20 mm and a height of 10 mm. (Indicated) is formed, and the circumferential surface of the base material may be left as it is or an Al-containing alloy film may be formed. FIG. 10 shows a test piece for a cycle oxidation test when (3) is used as the heat-resistant alloy base material 100. As shown in FIG. 10, the test piece has a multipurpose alloy layer, a bond layer, and a top layer formed on the upper end surface of a columnar base material having a diameter of 25.4 mm and a height of 3 mm, and is a circumferential surface of the base material. As it is. In these test pieces, for convenience, the upper end surface of the base material is designated as a specific region to be heat-shielded.

(Example 1)
The first embodiment corresponds to the sixth embodiment.

The Ni-based alloy base material shown in Table 1 was used as the heat-resistant alloy base material 105. The entire surface (upper surface, lower surface, circumferential surface) of the Ni-based alloy base material was subjected to Al diffusion treatment. That is, the Ni-based alloy base material _{was embedded in a mixed powder of Al: Ni: NH 4} Cl: Al ₂ O ₃ = 3: 2.5: 2: 60 (weight ratio), and 1000 ° C. in _{an Ar + 3 vol% H 2 atmosphere.} Al diffusion treatment was performed by heating in. Next, heat treatment was performed by heating at 1000 ° C. for 4 hours in an Ar + 3 vol% H _{2 atmosphere.} As a result, as shown in FIG. 11, a Cr-based multipurpose alloy layer 203 and an Al-containing alloy film 150 (β-NiAl film) were formed on the surface of the heat-resistant alloy base material 105.

Next, as shown in FIG. 11, a CoNiCrAlY layer was formed as a bond layer 300 by HVOF thermal spraying on the upper end surface of the test piece, and then a YSZ layer was formed as a top layer 400 by APS thermal spraying on the CoNiCrAlY layer. At the time of formation, a TGO-Al ₂ O ₃ layer was formed between the CoNiCrAlY layer and the YSZ layer. In this way, a test piece was prepared.

A part of the base material 105 / Cr-based multipurpose alloy layer 203 / bond layer 300 / top layer 400 construction surface of the test piece is cut, and the cross-sectional structure observation and the measurement of the concentration distribution of each element are performed by an SEM-EDX device (scanning). It was performed with a scanning electron microscope-energy dispersive spectroscope). FIG. 12 shows a cross-sectional SEM photograph.

(Example 2)
The second embodiment corresponds to the seventh embodiment.

First, in the same manner as in Example 1, as shown in FIG. 13, a Cr-based multipurpose alloy layer 203 and an Al-containing alloy film 150 (β-NiAl film) were formed on the entire surface of the heat-resistant alloy base material 105.

Next, a YSZ layer was formed as the top layer 400 on the upper end surface of the test piece by APS spraying, and a TGO-Al ₂ O ₃ layer was formed between the β-NiAl film and the YSZ layer when the YSZ layer was formed. A test piece was prepared.

Base material 105 of test piece / Cr-based multipurpose alloy layer 203 / Al-containing alloy film 150 (β-NiAl film) / Top layer 400 A part of the construction surface is cut, and the cross-sectional structure is observed and the concentration distribution of each element is measured. And were performed with the SEM-EDX apparatus. FIG. 14 shows a cross-sectional SEM photograph.

(Example 3)
The third embodiment corresponds to the first embodiment.

A SUS310 base material was used as the heat-resistant alloy base material 100. First, the surface of the test piece was smoothed and degreased. Next, the lower end surface and the circumferential surface of the test piece were covered with insulating tape and masked. Next, (Ni strike plating 1 μm) → (Ni watt plating 1 μm) → (Re-Ni alloy plating 8 μm) → (Ni watt plating 15 μm) → (Cr plating 7 μm) are performed in this order, and the total thickness of the plating layer is 32 μm. Was formed. Next, heat treatment was performed at 1000 ° C. for 5 hours in vacuum. As a result, as shown in FIG. 15, the Re-based multipurpose alloy layer 201 was formed on the upper end surface of the test piece. A Ni—Cr layer 201a was formed on the upper part of the Re-based multipurpose alloy layer 201.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as a bond layer 300 on the Re-based multipurpose alloy layer 201, and then a YSZ layer was formed as a top layer 400 by APS thermal spraying on the CoNiCrAlY layer. At the time of formation, a TGO-Al ₂ O ₃ layer was formed between the CoNiCrAlY layer and the YSZ layer to prepare a test piece.

Part of the base material 100 / Re-based multipurpose alloy layer 201 / bond layer 300 / top layer 400 construction surface of the test piece is cut, and the cross-sectional structure is observed and the concentration distribution of each element is measured by the SEM-EDX device. rice field. FIG. 16 shows a cross-sectional SEM photograph.

(Example 4)
The fourth embodiment corresponds to the second embodiment.

The Re-based multipurpose alloy layer 201 is formed on the upper end surface of the test piece through the same treatment as in Example 3, and then the Al diffusion treatment is performed to form the Al-containing alloy film 150 on the lower end surface and the circumferential surface of the test piece. bottom. A Ni—Cr layer was formed on the upper part of the Re-based multipurpose alloy layer.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as a bond layer 300 on the Re-based multipurpose alloy layer 201, and then a YSZ layer was formed as a top layer 400 by APS thermal spraying on the CoNiCrAlY layer. At the time of formation, a TGO-Al ₂ O ₃ layer was formed between the CoNiCrAlY layer and the YSZ layer to prepare a test piece. The test piece thus produced is shown in FIG.

Part of the base material 100 / Re-based multipurpose alloy layer 201 / bond layer 300 / top layer 400 construction surface of the test piece is cut, and the cross-sectional structure is observed and the concentration distribution of each element is measured by the SEM-EDX device. As a result, it was the same as in Example 3.

(Example 5)
The fifth embodiment corresponds to the case where the Cr-based multipurpose alloy layer 203 is provided between the Re-based multipurpose alloy layer 201 and the bond layer 300 in the second embodiment.

The Re-based multipurpose alloy layer 201 was formed on the upper end surface of the test piece through the same treatment as in Example 3, and then the Cr-based multipurpose alloy layer 203 was formed in the same manner as in Example 1. Next, the Al-containing alloy film 150 was formed on the lower end surface and the circumferential surface of the test piece by performing the Al diffusion treatment in the same manner as in Example 4.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the Cr-based multipurpose alloy layer 203 to prepare test pieces. The test piece thus produced is shown in FIG.

Base material 100 / Re-based multipurpose alloy layer 201 / Cr-based multipurpose alloy layer 203 / bond layer 300 / top layer 400 of the test piece A part of the construction surface was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Was carried out with the SEM-EDX apparatus, and was the same as in Example 3.

(Example 6)
The sixth embodiment corresponds to the fourth embodiment.

The Ni-based alloy base material shown in Table 1 was used as the heat-resistant alloy base material 105. First, the surface of the test piece was smoothed and degreased. Next, the upper end surface of the test piece was covered with insulating tape and masked. Next, the Cr-based multipurpose alloy layer 203 and the Al-containing alloy film 150 were formed on the lower end surface and the circumferential surface of the test piece in the same manner as in Example 1. Next, the lower end surface and the circumferential surface of the test piece were covered with insulating tape and masked. Next, the Re-based multipurpose alloy layer 201 was formed on the upper end surface of the test piece in the same manner as in Example 4. Next, an Al-containing alloy film 150 was formed on the circumferential surface of the Re-based multipurpose alloy layer 201.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the Re-based multipurpose alloy layer 201 to prepare test pieces. The test piece thus produced is shown in FIG.

(Example 7)
The seventh embodiment corresponds to the case where the Cr-based multipurpose alloy layer 203 is provided between the Re-based multipurpose alloy layer 201 and the bond layer 300 in the fourth embodiment.

The Ni-based alloy base material shown in Table 1 was used as the heat-resistant alloy base material 105. First, the surface of the test piece was smoothed and degreased. Next, after the Re-based multipurpose alloy layer 201 is formed on the upper end surface of the test piece through the same treatment as in Example 3, the upper end surface and lower end surface of the test piece are subjected to the same Al diffusion treatment as in Example 1. A Cr-based multipurpose alloy layer 203 and an Al-containing alloy film 150 were formed on the circumferential surface.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the Cr-based multipurpose alloy layer 203 on the upper end surface of the test piece to prepare a test piece. The test piece thus produced is shown in FIG.

(Example 8)
The eighth embodiment corresponds to the one in which the W-based multipurpose alloy layer 202 is used instead of the Re-based multipurpose alloy layer 201 in the first embodiment.

A SUS310 base material was used as the heat-resistant alloy base material 100. A slurry was prepared by adding 25% by weight W powder, 25% by weight Cr powder and 25% by weight Mo powder to a Ni-based self-melting alloy (nominal composition (wt%); Ni-15Cr-3Si-2B-5Fe), and heat-treated. After being applied to the surface of the alloy base material 100, it was heat-treated at 1150 ° C. for 6 hours in _{an Ar + 3 vol% H 2 atmosphere.} As a result, the W-based multipurpose alloy layer 202 was formed on the surface of the heat-resistant alloy base material 100.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the W-based multipurpose alloy layer 202 on the upper end surface of the test piece to prepare a test piece. The test piece thus produced is shown in FIG.

Part of the base material 100 / W-based multipurpose alloy layer 202 / bond layer 300 / top layer 400 construction surface of the test piece is cut, and the cross-sectional structure is observed and the concentration distribution of each element is measured by the SEM-EDX device. rice field. FIG. 22 shows a cross-sectional SEM photograph.

(Example 9)
The ninth embodiment corresponds to the third embodiment.

A SUS310 base material was used as the heat-resistant alloy base material 100. After forming the W-based multipurpose alloy layer 202 on the surface of the heat-resistant alloy base material 100 in the same manner as in Example 8, the Al-containing alloy film 150 was formed on the lower end surface and the circumferential surface of the test piece.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the W-based multipurpose alloy layer 202 on the upper end surface of the test piece to prepare a test piece. The test piece thus produced is shown in FIG.

Part of the base material 100 / Re-based multipurpose alloy layer 201 / bond layer 300 / top layer 400 construction surface of the test piece is cut, and the cross-sectional structure is observed and the concentration distribution of each element is measured by the SEM-EDX device. As a result, it was the same as in Example 8.

(Example 10)
The tenth embodiment corresponds to the case where the Cr-based multipurpose alloy layer 203 is provided between the W-based multipurpose alloy layer 202 and the bond layer 300 in the fifth embodiment.

The Ni-based alloy base material shown in Table 1 was used as the heat-resistant alloy base material 105. After forming the W-based multipurpose alloy layer 202 on the upper end surface of the test piece in the same manner as in Example 8, the Cr-based multipurpose alloy layer 203 is formed on the entire surface of the test piece in the same manner as in Example 7, and the test piece is formed. An Al-containing alloy film 150 was formed on the lower end surface and the circumferential surface.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the Cr-based multipurpose alloy layer 203 to prepare test pieces. The test piece thus produced is shown in FIG.

Part of the base material 105 / W-based multipurpose alloy layer 202 / bond layer 300 / top layer 400 construction surface of the test piece is cut, and the cross-sectional structure is observed and the concentration distribution of each element is measured by the SEM-EDX device. As a result, it was the same as in Example 8.

(Example 11)
The eleventh embodiment corresponds to the first embodiment.

A Ni-based single crystal superalloy base material was used as the heat-resistant alloy base material 109. The Re-based multipurpose alloy layer 201 was formed on the upper end surface of the test piece in the same manner as in Example 4.

Next, in the same manner as in Example 1, a CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 on the Re-based multipurpose alloy layer 201 to prepare test pieces. The test piece thus produced is shown in FIG.

(Comparative Example 1)
A SUS310 base material was used as the heat-resistant alloy base material 100. A CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 directly on the heat-resistant alloy base material 100 to prepare test pieces. The test piece thus produced is shown in FIG.

A part of the base material 100 / bond layer 300 / top layer 400 construction surface of the test piece was cut, and the cross-sectional structure of the test piece was observed and the concentration distribution of each element was measured by an SEM-EDX apparatus. FIG. 27 shows a cross-sectional SEM photograph.

(Comparative Example 2)
A Ni-based single crystal superalloy base material was used as the heat-resistant alloy base material 109. A CoNiCrAlY layer was formed as the bond layer 300 and a YSZ layer was formed as the top layer 400 directly on the heat-resistant alloy base material 109 to prepare test pieces. The test piece thus produced is shown in FIG.
A part of the base material 109 / bond layer 300 / top layer 400 construction surface of the test piece was cut, and the cross-sectional structure of the test piece was observed and the concentration distribution of each element was measured by an SEM-EDX apparatus. FIG. 29 shows a cross-sectional SEM photograph.

[High temperature oxidation test]
The high temperature oxidation test was carried out in the air under the conditions of repeated heating and cooling. Specifically, a test piece is placed on a horizontally movable sample table (alumina rod), inserted into an electric furnace controlled at 1100 ° C., cooled in the air for 15 minutes after 45 minutes, and then returned to the electric furnace. It is a so-called cycle oxidation test to insert.

FIG. 30 summarizes the cycle number dependence of the oxidation amount of the test pieces of Examples 1 to 5, 8 to 10 and Comparative Example 1 and the number of cycles in which YSZ peeling of the top layer occurs (the number of peeling cycles).

After the lapse of a predetermined number of cycles, the weight change of the test piece was measured at room temperature, but the oxidation behavior was different between the MPL / TBC construction surface and other surfaces. In this case, the amount of oxidation was measured as the value divided by the area of the entire test piece, and as a result, the amount of oxidation obtained strongly reflected the results of the other surface (TBC unconstructed surface).

FIG. 30 shows the cycle number dependence of the oxidation amount of the alloy base material Alloy-X for comparison. The amount of oxidation starts to decrease from around 200 cycles, and then decreases in proportion to the number of cycles.

In Comparative Example 1, the amount of oxidation started to decrease from around 200 cycles, which is similar to the number of cycles dependence of the amount of oxidation of the alloy base material Alloy-X. The heat shield layer YSZ was peeled off after 600 to 700 cycles.

In Examples 3 and 8, the amount of oxidation decreased according to the cycle number dependence similar to that of Comparative Example 1, and the heat shield layer YSZ was peeled off in 1600 to 1800 cycles.

From these results, as compared with the conventional base material / TBC (Comparative Example 1), in Examples 3 to 7 using the Re-based multipurpose alloy layer and Examples 8 to 10 using the W-based multipurpose alloy layer, YSZ It can be seen that the peel resistance is more than doubled.

In Examples 3 and 8, the oxidation of Alloy-X progresses in the portion where MPL / TBC has not been applied, and a decrease in the amount of oxidation is observed in proportion to the number of cycles. This is due to the oxidative evaporation (CrO ₃ (g)) and oxide of _{Cr 2} O ₃ formed on the alloy Alloy-X under the oxidation conditions of this experiment (1100 ° C; 45 minutes ⇔ room temperature; 15 minutes, in the air). This is due to the overlapping of peeling of the film.

In Examples 1, 2, 4, 5, 9, and 10, an Al-containing alloy film 150 was formed on the base material Alloy-X, and then MPL / DBC was formed in a specific region thereof. _{In cycle oxidation, since Al 2} O ₃ is formed as a protective film on the surface of the base material on which TBC is not applied, the decrease in the amount of oxidation due to the number of cycles is small. The peeling of the heat shield layer YSZ is 1600 to 1800 cycles, which is almost the same as the number of peeling observed in Examples 3 and 8.

From the above results, in the base material / MPL / TBC proposed in the present invention, the peel resistance of the top layer 400 is obtained in any of the Re-based multipurpose alloy layer 201, the W-based multipurpose alloy layer 202, and the Cr-based multipurpose alloy layer 203. Is improved, and high temperature oxidation resistance can also be improved at the same time by forming a protective oxide film by the Al-containing alloy film 150 formed on the surface of the heat-resistant alloy base material 100 or the heat-resistant alloy base material 105. It was revealed.

[In-situ observation of cracks and peeling of YSZ layer]
The surface of the test piece when it was taken out from the electric furnace and cooled was observed by photography. As a result, it is observed that the destruction of the YSZ layer starts as delamination from the peripheral corners of the test piece and progresses toward the center (the delaminated portion is darkened earlier. Can be identified by.

The result of Comparative Example 1 is shown in FIG. As shown in FIG. 31, the part that looks dark in the photograph is because the YSZ layer was delaminated during the cooling process and a groove was formed between the YSZ layer and the bond layer 300. It can be seen that it originates from the periphery of the piece and progresses toward the center with the number of cycles. In Comparative Example 1, the YSZ layer was completely peeled off in the cooling process after 593 cycles.

The result of Example 1 is shown in FIG. As shown in FIG. 32, in the base material / Cr-based MPL (Al diffusion) / TBC, when the number of cycles exceeds 1000 cycles, the partial peeling of the YSZ layer starts from the periphery and progresses toward the center with the number of cycles. There is. After the end of the 1850 cycle, the YSZ layer was completely peeled off while being kept at room temperature.

Similar results were observed in Examples 2-5, 8-10.

That is, by inserting the Re-based multipurpose alloy layer 201, the W-based multipurpose alloy layer 202, or the Cr-based multipurpose alloy layer 203 between the heat-resistant alloy base material 100 or the heat-resistant alloy base material 105 and the TBC, the YSZ layer can be peeled off. It can be seen that it is suppressed.

The base material / TBC (Comparative Example 1) and the base material / MPL / TBC (Examples 3, 4, 8 and 9) were cut after the end of a predetermined cycle, and the cross-sectional structure was observed and the concentration distribution of each element was measured. FIG. 33 shows the cycle number dependence of the Al concentration (atomic%) of the bond layer 300. From FIG. 33, in the base material / TBC of Comparative Example 1, the Al concentration of the bond layer 300 decreased from about 18 atomic% at the initial stage to several atomic% after 200 cycles, and then gradually decreased to 1 atomic% or less. , The YSZ layer was peeled off in about 600 cycles. On the other hand, in the base material / MPL / TBC, the Al concentration gradually decreased, decreased to 1 atomic% or less around 1600 to 1800 cycles, and the YSZ layer was peeled off.

When the Al concentration of the bond layer 300 is several atomic% or less (broken line in FIG. 33), oxides of _{Cr 2} O ₃ and Ni _{Al 2} O ₄ are observed in addition to _{Al 2} O _{3 in the thermal oxide TGO.} When these oxides are formed from the periphery and propagate to the center side of the bond layer 300 and are formed on the entire TGO, the YSZ layer is peeled off over the entire surface.

In the substrate / MPL / TBC, high Al concentration of the bond layer 300 by MPL layer, Al ₂ O ₃ principal TGO is formed and maintained, from about 1000 _{cycles, Cr 2 O 3, NiAl 2} O 4 and the like around The exfoliation of the YSZ layer started from the periphery and propagated to the center side, and the entire surface was exfoliated in 1850 cycles.

For the Ni-based alloys shown in Table 1, the formation of the Cr-based multipurpose alloy layer 203 by Al diffusion treatment was examined in the same manner as in Alloy-X. Subsequently, 4-cycle and 100-cycle oxidation tests were performed, and the cross-sectional structure of the test piece was observed and the concentration distribution of each element was measured. The results obtained are shown below.

The cross-sectional structure of each test piece after Al diffusion treatment is summarized in FIG. 34. From FIG. 34, after the Al diffusion treatment, no layer corresponding to the Cr-based multipurpose alloy layer 203 is observed in any of the alloys.

The structure of the cross section of the above Al diffusion-treated Ni-based alloy after being oxidized for 4 cycles is shown in FIG. 35. The microstructure photograph shows the elements (Cr + Mo + Nb + W) contained in the alloy in the order of the sum (atomic%).

The structure of the cross section of the above Al diffusion-treated Ni-based alloy after being oxidized for 100 cycles is shown in FIG. 36. The microstructure photograph shows the elements (Cr + Mo + Nb + W) contained in the alloy in the order of the sum (atomic%).

With the above Ni-based heat-resistant alloy, after Al diffusion treatment, concentration analysis of each element after 4-cycle and 100-cycle oxidation in the air was carried out. Table 2 summarizes the elements and concentrations constituting the inner layer of the Cr-based multipurpose alloy layer 203.

From the results of the above structure observation and the analysis result of the concentration distribution of each element, the following relationship with the concentration of each element in the alloy can be obtained for the formation of the Cr-based multipurpose alloy layer 203.

Table 3 shows the relationship between the total concentration of Cr + Mo + Nb + W elements and the Cr-based multipurpose alloy layer. It is summarized as follows.

(1) After the Al diffusion treatment, the formation of the Cr-based multipurpose alloy layer is not clearly observed.
(2) After 4-cycle oxidation, the Cr-based multipurpose alloy layer is clearly observed with the following alloys.
Alloy-22, Alloy-625, Alloy-C276,
Alloy-X, Alloy-718, Alloy-825, Alloy-20
The total concentration of Cr + Mo + Nb + W is 23.4 atomic% or more.
(Alloy B2 has high Mo and low Cr content)
(3) After 4-cycle oxidation, the formation of the Cr-based multipurpose alloy layer cannot be confirmed with the following alloys.
Alloy-601, Alloy-800HT
The total concentration of Cr + Mo + Nb + W is 24.5 atomic% or less.
(4) After 100 cycles of oxidation, the alloys forming the continuous layer of the Cr-based multipurpose alloy layer are as follows.
Alloy-22, Alloy-625, Alloy-C276
These have a total concentration of Cr + Mo + Nb + W of 30.5 atomic% or more.
The alloys in which the Cr-based multipurpose alloy layer is formed discontinuously are as follows.
Alloy-X, Alloy-718, Alloy825, Alloy-20
These have a total concentration of Cr + Mo + Nb + W of 23.4 atomic% or more and 30.1 atomic% or less.
The alloys on which the Cr-based multipurpose alloy layer is not formed are as follows.
Alloy601, Alloy800HT
These have a total concentration of Cr + Mo + Nb + W of 24.5 atomic% or less.

From the above results, Cr, Mo, Nb, and W in the alloy base material are effective for forming the Cr-based multipurpose alloy layer. However, as seen in the results of Alloy-B2, a large amount of Mo makes the Cr-based multipurpose alloy layer brittle, and from the viewpoint of oxidation resistance, the combined addition of Cr and Mo is effective.

The effect of Fe (+ Nb) contained in the heat-resistant alloy base material 105 (after 100 cycles) is shown in FIG. 37. From FIG. 37, the higher the concentration of Fe (+ Nb), the less the formation of the Cr-based multipurpose alloy layer 203 is observed. Therefore, the concentration of Fe (+ Nb) is preferably 29.9 atomic% or less for the formation and maintenance of the Cr-based multipurpose alloy layer 203.

Tables 4 and 5 show the elements and concentrations (atomic%) of the Re-based multipurpose alloy layer 201 formed on the heat-resistant alloy base material 105 made of a Ni-based alloy.

The results shown in Tables 4 and 5 are summarized as follows.

The Re-based multipurpose alloy layer 201 is observed in all alloys after 4 cycles, 25 cycles of oxidation, and 100 cycles of oxidation after Al diffusion treatment. The total concentration of Re, Cr, Nb, and Mo contained in the Re-based multipurpose alloy layer 201 is 51.8 atomic% to 73.5 atomic%. However, after 100 cycles, the Re-based multipurpose alloy layer 201 disappears in Alloy B2 and Alloy 201. This is because Alloy 201 is industrial purity Ni and the Cr concentration of Alloy B2 is as low as 0.2 atomic%.

[Creep strength]
The creep behavior of a Ni-based alloy (Alloy-X) forming three types of multipurpose alloy layers (Re-based, W-based, Cr-based) was investigated at 970 ° C; in the atmosphere at a stress of 20 to 50 MPa. The resulting Larson Miller Parameter plot is shown in FIG. Larson Miller parameter is defined by _{P = T (C + logt r} ). However, T is the absolute temperature, _tr is the breaking time (h), and C is the material constant.

From FIG. 38, the fracture time of Alloy-X on which the Cr-based multipurpose alloy layer 203 is formed is the same as that of the base alloy, and the fracture time of Alloy-X on which the Re-based multipurpose alloy layer 201 and the W-based multipurpose alloy layer 202 are applied. Is located on the long side. That is, in Alloy-X in which three types of multipurpose alloy layers (Re type, W type, Cr type) are formed, no decrease in strength is observed, and conversely, in the Re type multipurpose alloy layer 201 and the W type multipurpose alloy layer 202. It was clarified that it contributed to high strength.

FIG. 39 shows the creep curves (970 ° C.; stresses of 22.5 MPa, 27.5 MPa, 40 MPa in the atmosphere) of the Ni-based heat-resistant alloy (Alloy-X) forming the Re-based multipurpose alloy layer 201. From FIG. 39, when compared at a stress of 27.5 MPa, the breaking time of Alloy-X is 220 hours, whereas that of the base material / Re-based multipurpose alloy layer 201 is 380 hours. It was revealed that the steady-state creep rate was lower in the base material / Re-based multipurpose alloy layer 201 than in the base material (Alloy-X).

In the creep test shown in FIG. 39, the creep test at a stress of 22.5 MPa was interrupted at a strain of 3.5% for 190 hours, and the results of observing the surface and cross-sectional structure of the test piece are shown in FIG. From FIG. 40, θAl ₂ O ₃ is formed on the surface of the test piece, and vertical cracks (perpendicular to the stress axis) and partial peeling are observed. From the cross-sectional observation of the test piece, the Re-based multipurpose alloy layer 201 / β-NiAl film remains continuously, and no cracks or peeling are observed. That is, it can be seen that the Re-based multipurpose alloy layer 201 / β-NiAl film is creep-deformed together with the base material.

FIG. 41 shows the enlarged structure of the Re-based multipurpose alloy layer 201 / β-NiAl film and the concentration distribution of each element in the cross-sectional structure shown in FIG. 40. From FIG. 41, the composition (atomic%) of the Re-based multipurpose alloy layer 201 is 25 atomic% Re-35 atomic% Cr-16 atomic% Ni-10 atomic% Fe-10 atomic% Mo. _{Although a part of θAl 2} O ₃ formed on the surface of the test piece is peeled off, no defects such as cracks are observed in the Re-based multipurpose alloy layer 201 and the β-NiAl film. Al in the β-NiAl film did not diffuse and permeate into the substrate side, and the Re-based multipurpose alloy layer 201 functions as an Al diffusion barrier despite creep deformation.

FIG. 42 shows the results of investigating the creep behavior of the SUS310 base material on which the Re-based multipurpose alloy layer 201 was formed at 900 ° C. and a stress of 22.5 MPa in the atmosphere. FIG. 42 also shows the results of investigating the creep behavior of the SUS310 base material for comparison. From FIG. 42, for example, when the strain (%) at a creep time of 200 hours is compared, the SUS310 base material is 21%, whereas the SUS310 forming the Re-based multipurpose alloy layer 201 having a thickness of 10 μm and 20 μm is formed. The base material is 11% and 8.5%. It can be seen that the creep resistance of the SUS310 base material is improved by forming the Re-based multipurpose alloy layer 201.

FIG. 43 shows the cross-sectional structure of the test piece after rupture in the creep test shown in FIG. 42. From FIG. 43, a large number of fine grain boundary cracks are observed in the SUS310 base material, whereas the frequency of grain boundary fracture is low in the base material / Re-based multipurpose alloy layer 201.

A Cr (Mo) -based multipurpose alloy layer 203 and a Re-based multipurpose alloy layer 201 were formed on the alloy base material (Alloy-X), and their fatigue resistance characteristics were investigated under the conditions shown in Table 6.

Table 6 Fatigue test conditions
Test waveform triangular wave
Test Standard ASTM E606 / E606M-12
Temperature 760 ° C
Strain range 0.4%
Strain rate 0.4% / sec

As a result, the number of fatigue fracture cycles is 1.16 to 1.24 for the base material / Cr-based multipurpose alloy layer 203 and 2.59 to 2 for the base material / Re-based multipurpose alloy layer 201 as relative values with respect to the alloy base material. It was .75.

From the above results, it can be seen that the fatigue resistance characteristics of the base material / Cr-based multipurpose alloy layer 203 are almost the same as those of the base material, and that the base material / Re-based multipurpose alloy layer 201 is improved more than twice.

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present invention. Is possible.

100, 105, 109 ... Heat-resistant alloy base material, 150 ... Al-containing alloy film, 201 ... Re-based multipurpose alloy layer, 202 ... W-based multipurpose alloy layer, 203 ... Cr-based multipurpose alloy layer, 300 ... Bond layer, 400 ... Top layer

Claims (21)

Heat resistant alloy base material and
A Re-based, W-based, or Cr-based multipurpose alloy layer provided in a region including at least a region for heat shielding on the surface of the heat-resistant alloy base material, and
A bond layer made of an Al-containing alloy provided in a region of the multipurpose alloy layer that includes at least a region to be heat-shielded, and a bond layer made of an Al-containing alloy.
A top layer made of heat-shielding ceramics provided only in the area on the bond layer to be heat-shielded, and
Heat resistant alloy member with. The heat-resistant alloy member according to claim 1, wherein the Re-based or W-based multipurpose alloy layer, the bond layer, and the top layer are provided only in the region of the surface of the heat-resistant alloy base material to be heat-shielded. The multipurpose alloy layer, the bond layer, and the top layer are provided only in the region where heat shielding should be performed on the surface of the heat-resistant alloy base material, and the surface of the heat-resistant alloy base material in a portion other than the region where heat shielding should be performed. The heat-resistant alloy member according to claim 1, wherein an Al-containing alloy film is provided so as to cover the heat-resistant alloy member. The heat-resistant alloy member according to claim 1, wherein the multipurpose alloy layer is formed by laminating two different layers selected from a Re-based multipurpose alloy layer, a W-based multipurpose alloy layer, and a Cr-based multipurpose alloy layer. The Cr-based multipurpose alloy layer and the Al-containing alloy film on the multipurpose alloy layer are provided so as to cover the entire surface of the heat-resistant alloy base material, and the bond layer and the top layer are the above on the Al-containing alloy film. The heat-resistant alloy member according to claim 1, which is provided only in the area where heat shielding should be performed. The multipurpose alloy layer, the bond layer, and the top layer are provided only in the region where heat shielding should be performed on the surface of the heat-resistant alloy base material, and the surface of the heat-resistant alloy base material in a portion other than the region where heat shielding should be performed. The heat-resistant alloy member according to claim 3, wherein the multipurpose alloy layer and an Al-containing alloy film on the multipurpose alloy layer are provided so as to cover the above-mentioned multipurpose alloy layer. An Al-containing alloy film that also serves as the bond layer is provided on the Cr-based multipurpose alloy layer and the multipurpose alloy layer so as to cover the entire surface of the heat-resistant alloy base material, and the top layer is the Al-containing alloy film. The heat-resistant alloy member according to claim 3, which is provided only in the above-mentioned area where heat shielding should be performed. The heat-resistant alloy base material is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and the multipurpose alloy layer is Cr. The heat-resistant alloy member according to claim 1, which is a system. The Ni-based alloy contains 18.7 atomic% or more of Cr, and contains 5.7 atomic% or more and 19.2 atomic% or less in total of one or more metals selected from the group consisting of Mo, Nb and W. The heat-resistant alloy member according to claim 8, which contains Fe and Nb in a total amount of 13.1 atomic% or less. The heat-resistant alloy member according to claim 1, wherein the heat-resistant alloy base material is made of a Ni-based single crystal superalloy, and the multipurpose alloy layer is a Re system. The Al-containing alloy constituting the bond layer is any one of claims 1 to 10 composed of MCrAlY (M = Co, Ni), β-NiAl, γ'-Ni ₃ Al or γ-Ni (Al, Cr). The heat-resistant alloy member described in the item. The heat-shielding ceramics constituting the top layer are oxide ceramics containing zirconium, yttrium and oxygen, oxide ceramics containing aluminum, yttrium and oxygen, and oxide ceramics containing aluminum, lantern and oxygen. Claims 1 to be composed of at least one selected from the group consisting of oxide ceramics containing aluminum, samarium and oxygen, oxide ceramics containing cerium and oxygen, and oxide ceramics containing thorium and oxygen. The heat-resistant alloy member according to any one of 11. The heat-resistant alloy member according to claim 3, 5, 6 or 7, wherein the Al-containing alloy film is made of β-NiAl. A step of forming a Re-based, W-based or Cr-based multipurpose alloy layer in a region including at least a region to be heat-shielded on the surface of the heat-resistant alloy base material, and a step of forming the Re-based, W-based or Cr-based multipurpose alloy layer.
A step of forming a bond layer made of an Al-containing alloy in a region of the multipurpose alloy layer including at least a region to be heat-shielded, and a step of forming the bond layer.
A step of forming a top layer made of heat-shielding ceramics only in the region on the bond layer to be heat-shielded, and
A method for manufacturing a heat-resistant alloy member having. The heat-resistant alloy according to claim 14, wherein the multipurpose alloy layer is formed only in the region of the surface of the heat-resistant alloy base material to be heat-shielded, and then the bond layer and the top layer are sequentially formed on the multipurpose alloy layer. Manufacturing method of parts. The multipurpose alloy layer is formed only in the region of the surface of the heat-resistant alloy base material to be heat-shielded, and the surface of the heat-resistant alloy base material is formed in a portion other than the region to be heat-shielded by performing Al diffusion treatment. The method for producing a heat-resistant alloy member according to claim 14, wherein the bond layer and the top layer are sequentially formed on the multipurpose alloy layer after forming an Al-containing alloy film so as to cover the above. The heat-resistant alloy base material is composed of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and the bond layer and the top. The Cr-based multipurpose alloy is formed between the heat-resistant alloy base material and the Al-containing alloy film by the reaction between the heat-resistant alloy base material and the Al-containing alloy film by sequentially forming the layers and then oxidizing the layers at a high temperature. The method for manufacturing a heat-resistant alloy member according to claim 16, wherein the layer is formed. The heat-resistant alloy base material is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and is subjected to Al diffusion treatment. An Al-containing alloy film is formed on the entire surface of the heat-resistant alloy base material, and the bond layer and the top layer are sequentially formed only in the region where heat shielding should be performed, and then the heat-resistant alloy is oxidized at a high temperature. The method for producing a heat-resistant alloy member according to claim 16, wherein a Cr-based multipurpose alloy layer is formed between the heat-resistant alloy base material and the Al-containing alloy film by the reaction between the base material and the Al-containing alloy film. The heat-resistant alloy base material is made of a Ni-based alloy containing at least 24.5 atomic% of one or more metals selected from the group consisting of Cr, Mo, Nb and W, and is subjected to Al diffusion treatment. An Al-containing alloy film that also serves as the bond layer is formed on the entire surface of the heat-resistant alloy base material, and the top layer is formed only in the region on the Al-containing alloy film that should be heat-shielded, and then at a high temperature. 16. The 16th aspect of claim 16, wherein a Cr-based multipurpose alloy layer is formed between the heat-resistant alloy base material and the Al-containing alloy film by reacting the heat-resistant alloy base material with the Al-containing alloy film by performing oxidation. A method for manufacturing a heat-resistant alloy member. Heat resistant alloy base material and
A Re-based, W-based, or Cr-based multipurpose alloy layer provided in a region including at least a region for heat shielding on the surface of the heat-resistant alloy base material, and
A bond layer made of an Al-containing alloy provided in a region of the multipurpose alloy layer that includes at least a region to be heat-shielded, and a bond layer made of an Al-containing alloy.
A high-temperature device having a heat-resistant alloy member having a top layer made of heat-shielding ceramics provided only in a region on the bond layer to be heat-shielded. A step of forming a Re-based, W-based or Cr-based multipurpose alloy layer in a region including at least a region to be heat-shielded on the surface of the heat-resistant alloy base material, and a step of forming the Re-based, W-based or Cr-based multipurpose alloy layer.
A step of forming a bond layer made of an Al-containing alloy in a region of the multipurpose alloy layer including at least a region to be heat-shielded, and a step of forming the bond layer.
A method for manufacturing a high-temperature device, which comprises a step of forming a top layer made of heat-shielding ceramics only in a region on the bond layer to be heat-shielded, and a step of manufacturing a heat-resistant alloy member by executing the steps.

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