JP2024005333A - Heat resistant metal member, method for manufacturing the same, high temperature device and plating solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistant metal member capable of: using various kinds of metal bases; continuously obtaining a diffusion barrier function in a high temperature oxidizing atmosphere or high temperature corrosive atmosphere; continuously maintaining a protective oxide film on the outermost surface over a long period, thereby; and replacing even a process required for manufacturing with a simple process, such as electroplating method, and a method for manufacturing the same.

SOLUTION: A heat resistant metal member includes: a boundary layer (200) including Co on a metal base (100); a diffusion barrier layer (300) including a Re containing Co-based alloy as a main component; and an Al containing alloy layer (500) in this order. A method for manufacturing the heat resistant metal member comprises: forming a Co film, a Re (Ni) film and a Co film or a Ni film in this order on the metal base by an electroplating method; burying and heating the metal base into a powder mixture including Cr powder and Al₂O₃ powder to form the diffusion barrier layer; and subjecting the diffusion barrier layer to Al diffusion to form an Al containing alloy layer on the diffusion barrier layer.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a heat-resistant metal member, a method for manufacturing the same, a high-temperature device, and a plating solution, and particularly relates to incinerators, exhaust gas system members, boilers, internal combustion engines, gas turbines, etc. used in high-temperature oxidizing or high-temperature corrosive atmospheres It is suitable for application to jet engines, satellite thruster engines, fuel cells, etc.

High-temperature oxidation-resistant coatings are applied to heat-resistant alloy base materials used in various combustion equipment, internal combustion engines, boilers, incinerators, exhaust gas system components, turbines, jet engines, fuel cells, etc. Typical coatings include Al-containing alloy coatings that form protective alumina (Al ₂ O ₃ ) [(Ni-Al alloy coating (β-NiAl), γ'-(Ni, Pt) ₃ Al (or Pt-added γ Cr-containing alloy coatings [γ _- Ni(Cr), Fe-Cr, etc.] forming protective chromia (Cr ₂ O ₃ ) are used. ing.

However, in the above-mentioned Al-containing alloy film, the Al concentration decreases during use at high temperatures, and the high-temperature oxidation resistance ability is lost at an early stage (see Non-Patent Document 1).

In order to suppress the decrease in Al concentration of the Al-containing alloy film, the present inventors formed a Re-Cr-Ni-based σ-phase diffusion barrier layer (referred to as σ-Re-based barrier) on the base material. , a technique has been proposed in which an Al-containing Ni-based alloy layer is laminated on the surface thereof. Diffusion Barrier Coating (DBC), which includes the σ-Re barrier and the Al-containing Ni-based alloy layer, and the base material, the diffusion barrier, the Al-containing Ni-based alloy layer, and the protective alumina coating are collectively referred to as diffusion barrier coatings (DBC). They are called barrier coating systems. Details of the diffusion barrier layer are described in Patent Documents 1 to 4.

In the σ-Re based barriers of Patent Documents 1 to 4, the Re-Cr-Ni σ-phase is composed of a continuous/single layer, and after a long period of time at high temperature, the Ni-based single crystal superalloy and the σ-Re Since voids may be formed in the boundary layer existing between the diffusion barrier layer and the diffusion barrier layer, and at the same time, cracks may occur within the diffusion barrier layer, Patent Documents 5 to 7 disclose that the diffusion barrier layer is a Re-Cr-Ni-based diffusion barrier layer. The diffusion barrier layer has a multi-phase structure of a σ-phase and a Ni-Cr based γ-phase, and the σ-phase is precipitated within the matrix of the γ-phase, which is a so-called discontinuous σ-Re layer. A three-layer structure is proposed.

The phenomenon in which voids form and grow in the boundary layer between the base material and the σ-Re barrier layer during the process of heating at high temperatures and for long periods of time is caused by the formation and growth of voids in the boundary layer between the base material and the σ-Re barrier layer. It is also seen in the σ-Re based barrier coating formed on -10Mo alloy (mass%). Regarding this problem, Patent Document 8 proposes that the formation of voids can be suppressed by increasing the thickness of the Ni layer inserted between the base material and the σ-Re barrier layer to 60 μm or more.

Since the γ-Ni (Cr) phase constituting the diffusion barrier layer described in Patent Documents 5 to 7 serves as a diffusion path for Al in the Al-containing alloy layer and elements contained in the base material, the σ phase described in Patent Documents 1 to 4 - Inferior to diffusion barrier ability compared to Re-based barriers. The increase in the thickness of the Ni layer described in Patent Document 8 causes the Cr and Re of the σ-Re based barrier to dissolve in the Ni layer and promote the decomposition and disappearance of the σ-Re based barrier, resulting in loss of diffusion barrier ability. It turns out.

In Patent Documents 1 to 8, high and low heat treatment temperatures are respectively used to form a diffusion barrier layer. That is, since the σ-Re-based barriers of Patent Documents 1 to 4 and 8 are formed at a relatively high temperature (1200° C. or higher), there is a possibility that the structure of the base material changes and the crystal grains become coarser. On the other hand, the diffusion barrier layers in which the σ-phase is precipitated within the γ-phase described in Patent Documents 5 to 7 can be formed by heat treatment at a relatively low temperature (below 1120°C), so that structural changes and coarsening of crystal grains can be suppressed. However, even if a three-layer structure is adopted, the diffusion barrier ability is inferior.

On the other hand, the following problems have been pointed out with Cr-containing alloy films [(Fe-Cr, γ-Ni(Cr)]. Namely, as Cr-containing alloys, stainless steels (Fe-Cr, Fe-Cr- Ni) is used and forms Cr ₂ O ₃ as a protective film, but according to Non-Patent Document 2, oxidation (O ₂ , H ₂ O, etc.) and carburization at high temperatures (above 1000°C) It is known that it loses its properties early in harsh corrosive environments such as (CH ₄ etc.).Therefore, as a coating, Cr pack treatment, which is heat treated in a (Cr + NH ₄ Cl + Al ₂ O ₃ ) mixed powder, is used. However, depending on the shape of the component, a high Cr (α-Cr phase) layer may be formed at the corners, which can cause cracking and peeling. The problem is inducing it.

Patent No. 3857689 Patent No. 3857690 Patent No. 3910588 Patent No. 4753720 Patent No. 5905336 specification Patent No. 5905354 specification Patent No. 5905355 specification

“Heat-resistant coating for jet engines” Issei Otera, Yoshihiro Tsuda, Takato Araki, Nobuyoshi Mori, Akihiro Sato; Surface Technology, Vol.63, No.1, pp.19-23, (2012) Supervised by Masaharu Nakamori High-temperature corrosion cases caused by boiler combustion gas and countermeasures, ISBN978-4-924728-66-OC 3050

As mentioned above, the formation of the σ-Re-based barriers of Patent Documents 1 to 4 and 8 requires heat treatment at a high temperature of 1200°C or higher, which can cause changes in the structure of the base material and coarsening of crystal grains. Due to the nature of the It was difficult to use the base material. Further, in Patent Documents 5 to 7, although the temperature of the heat treatment required to form the diffusion barrier layer was low, the diffusion barrier ability was low. Furthermore, regarding the Cr-containing alloy film, it is impossible to avoid the formation of a high-Cr α-Cr phase that induces cracking and peeling in the Cr-containing Ni-based alloy film formed by the Cr pack treatment method.

Therefore, the problem to be solved by this invention is that various metal substrates including general-purpose substrates can be used, and when used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere, the diffusion barrier function can be improved. By being able to continuously obtain the protective oxide film, it is possible to maintain the protective oxide film on the outermost surface for a long period of time, and in particular, when using a Cr-containing alloy layer, the protective oxide film can be prevented from cracking or peeling. Heat-resistant metal parts and manufacturing methods thereof that can reduce the amount of heat resistant and require simple processes such as plating and pack processing, as well as high-temperature equipment including such heat-resistant metal parts and manufacturing of heat-resistant metal parts. An object of the present invention is to provide a plating solution suitable for use in a method.

In order to solve the above problems, this invention
a metal base material;
a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the metal base material;
a boundary layer containing at least Co between the metal base material and the diffusion barrier layer;
an Al-containing alloy layer or a Cr-containing alloy layer on the diffusion barrier layer;
It is a heat-resistant metal member having.

The Re concentration of the diffusion barrier layer is typically 1 atomic % or more. The diffusion barrier layer preferably consists of an α-Co(Re) continuous layer containing 10 atomic % of Re, and the α-Co(Re) continuous layer contains ε-Re(Co) phase precipitates. . Here, Co(Re) means Co containing Re, and is synonymous with Co--Re alloy. The same applies to Re(Co) and Re(Ni), which will be described later. The thickness of the diffusion barrier layer is selected as necessary, but is typically 10 μm or more and 100 μm or less. In addition to Re and Co, the diffusion barrier layer may contain one or more elements contained in the metal base material and the Al-containing alloy layer or the Cr-containing alloy layer. In this case, when the ε-Re(Co) phase contains Ni in addition to Co, it is described as an ε-Re(Co, Ni) phase, but the ε-Re(Co) phase is , Ni) phase. The same applies when the ε-Re(Co) phase contains other elements in addition to Co and Ni.

When having an Al-containing alloy layer on the diffusion barrier layer, this Al-containing alloy layer may also contain Pt. In this case, the Pt concentration in the Al-containing alloy layer is typically 1.5 at.% or more. Since the Al-containing alloy layer contains Pt in this manner, the Al concentration of the Al-containing alloy layer can be maintained high during use of the heat-resistant metal member. By containing Co in the boundary layer, it is possible to suppress the formation of voids in the boundary layer when the heat-resistant metal member is used. Also, in this case, the boundary layer typically contains Al. The Al concentration of this boundary layer is typically 1 atomic % or more, but preferably 3 atomic % or more and 25 atomic % or less. When the boundary layer contains Al in this way, the decomposition of the Al-containing alloy layer is delayed when the heat-resistant metal member is used, so that a decrease in the Al concentration can be prevented. Further, since the solubility of Re in the Al-containing alloy layer is low, Al contained in the boundary layer suppresses decomposition of the diffusion barrier layer, so that the diffusion barrier layer can be stably maintained. The thickness of the boundary layer is not particularly limited, but is typically 5 μm or more and 200 μm or less, preferably 10 μm or more and 100 μm or less.

The Al-containing alloy layer forms protective alumina (Al ₂ O ₃ ) on the outermost surface of the heat-resistant metal member when the heat-resistant metal member is used, and makes the entire heat-resistant metal member, including the metal base material, boundary layer, and diffusion barrier layer, susceptible to high-temperature oxidation. It has the function of protecting from atmosphere and high temperature corrosive atmosphere. The Al-containing alloy layer is not particularly limited, but is made of, for example, β-NiAl, γ'-Ni ₃ Al, CoAl, FeAl, etc. Typically, the elements other than Al are mainly Co and Ni. . The Al-containing alloy layer may inevitably contain elements contained in the metal substrate, boundary layer, and diffusion barrier layer. Although the Al concentration of the Al-containing alloy layer is not particularly limited, it is typically 10 atomic % or more and 60 atomic % or less. The thickness of the Al-containing alloy layer is selected as required, but is typically 20 μm or more and 100 μm or less. The Cr-containing alloy layer forms protective chromia (Cr ₂ O ₃ ) on the outermost surface of the heat-resistant metal member when the heat-resistant metal member is used, making the entire heat-resistant metal member including the metal base material, boundary layer, and diffusion barrier layer susceptible to high-temperature oxidation. It has the function of protecting from atmosphere and high temperature corrosive atmosphere. The Cr-containing alloy layer is typically made of NiCrAl, FeCrAl, or a Ni--Al alloy containing Cr particles, and typically mainly contains Co and Ni as elements other than Cr. The Cr-containing alloy layer may inevitably contain elements contained in the metal substrate, boundary layer and diffusion barrier layer. The Cr concentration of the Cr-containing alloy layer is not particularly limited, but is typically 10 atomic % or more and 50 atomic % or less. The thickness of the Cr-containing alloy layer is selected as required, but is generally 20 μm or more and 100 μm or less.

The refractory metal component may further include a transition layer between the diffusion barrier layer and the Al-containing alloy layer or the Cr-containing alloy layer. This transition layer typically has a Re concentration of less than 1 atomic % and an Al or Cr concentration of 10 atomic % or less, but is not limited thereto.

The metal base material is selected as necessary and various materials can be used, and examples thereof include Fe-based alloys, Co-based alloys, Ni-based alloys, Ni-based single crystal superalloys, etc. . Among these, Fe-based alloys include, for example, SUS304, SUS310, etc.; Co-based alloys include, for example, alloys containing Co as a main component and Cr, W, etc.; Ni-based alloys such as alloys containing Fe and the like include, for example, Hastelloy-X, Inconel, and the like. The shape of the metal base material is not particularly limited and is selected depending on the intended use, and examples thereof include a flat plate, a rod (square rod, round rod, etc.), a tube, a box, and the like.

Heat-resistant metal members are not particularly limited, but specific examples include incinerators, boilers, gas turbine members, jet engine members, exhaust gas system members, and the like.

Moreover, this invention
a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, and the second Co film or the Ni film are formed is embedded in a mixed powder containing Cr powder and Al ₂ O ₃ powder. A step of forming a boundary layer containing at least Co and a diffusion barrier layer on the boundary layer containing at least a Co-based alloy containing Re as a main component by performing heat treatment;
forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal base material on which the boundary layer and the diffusion barrier layer are formed;
A method of manufacturing a heat-resistant metal member having the following steps.

Plating method means electroplating method. The temperature and time of heat treatment of the metal substrate on which the first Co film, Re(Ni) film, and second Co film or Ni film are formed are selected as necessary, but the temperature is, for example, 1050°C or more and 1150°C or less. The time is, for example, 1 hour or more and 20 hours or less, typically 2 hours or more and 12 hours or less. This heat treatment is preferably performed in an inert gas atmosphere. The inert gas atmosphere is not particularly limited, but is preferably a mixed gas of Ar (argon) and He (helium) or a mixed gas of Ar and H ₂ (hydrogen), especially Ar and 3 vol% H ₂ A mixed gas with The temperature and time of the Al diffusion treatment are selected as necessary, but the temperature is, for example, 950° C. or more and 1100° C. or less, typically 1000° C. or more and 1050° C. or less, and the time is, for example, 1 hour or more and 20 hours or less. This Al diffusion treatment is also preferably performed in the same inert gas atmosphere as above.

In this invention, with respect to matters other than the above, the same as described in connection with the invention of the above-mentioned heat-resistant metal member applies unless it is contrary to the nature thereof.

Moreover, this invention
a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film and the second Co film or the Ni film are formed is a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder. A boundary layer containing at least Co, a diffusion barrier layer on the boundary layer whose main component is at least a Co-based alloy containing Re, and an Al-containing layer on the diffusion barrier layer are buried in the interior and subjected to heat treatment. a step of simultaneously forming an alloy layer;
A method of manufacturing a heat-resistant metal member having the following steps.

In this invention, by immersing the metal base material in a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder and performing heat treatment, Al and Al are formed by the reaction between Ti and Al ₂ O ₃ . By generating TiO or Al and MgO through a reaction between Mg and Al ₂ O ₃ , Al diffusion is enabled and an Al-containing alloy layer is formed. If necessary, powder of an Al source such as FeAl or NiAl may be mixed with the mixed powder.

The temperature, time, and atmosphere for the heat treatment of the metal base material on which the first Co film, Re(Ni) film, and second Co film or Ni film are formed are the same as in the invention of the method for manufacturing a heat-resistant metal member described above.

When the Al-containing alloy layer contains Pt, for example, a Pt film is formed on the second Co film by a plating method, or Pt powder (for example, particle size of about 1 μm) is applied by a slurry method. In this way, an Al-containing alloy layer containing Pt can be formed by performing heat treatment.

In this invention, with respect to matters other than the above, the explanations in connection with the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed contains Ni powder, NiAl powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. By embedding it in the mixed powder and performing heat treatment, a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer containing at least a Co-based alloy containing Re, and a diffusion barrier layer on the diffusion barrier layer are formed. simultaneously forming an Al-containing alloy layer;
A method of manufacturing a heat-resistant metal member having the following steps.

The temperature, time, and atmosphere for the heat treatment of the metal base material on which the first Co film, Re(Ni) film, and second Co film or Ni film are formed are the same as in the invention of the method for manufacturing a heat-resistant metal member described above.

In this invention, the explanations regarding the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
forming at least a Co--Re alloy film containing Ni on the metal substrate by a plating method using a plating solution containing a mixture of a Co plating solution and a Re(Ni) plating solution;
By immersing the metal base material on which the Co(Re) alloy film is formed in a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder and performing heat treatment, a boundary containing at least Co is formed. simultaneously forming a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the boundary layer, and an Al-containing alloy layer on the diffusion barrier layer;
A method of manufacturing a heat-resistant metal member having the following steps.

The mixing ratio (vol%) of the Co plating solution (electrolytic solution containing Co ions) and the Re(Ni) plating solution (electrolytic solution containing Re ions and Ni ions) in the plating solution is selected as necessary. Typically, the range is 10 vol% Co plating solution, 90 vol% Re(Ni) plating solution to 60 vol% Co plating solution, 40 vol% Re(Ni) plating solution, preferably 20 vol% Co plating solution, 90 vol% Re(Ni) plating solution. The range is from 80 vol% Ni) plating solution to 50 vol% Co plating solution and 50 vol% Re(Ni) plating solution. By performing plating using such a plating solution, Co--Re alloy films containing Ni can be formed with various compositions.

The heat treatment carried out by embedding it in a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder is as explained in connection with the above invention.

In this invention, with respect to matters other than the above, the explanations in connection with the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
forming at least a Co(Re) alloy film containing Ni on the metal substrate by a plating method using a plating solution containing a mixture of a Co plating solution and a Re(Ni) plating solution;
forming a Co film on the Co-Re alloy film by plating;
By immersing the metal base material on which the Co--Re alloy film and the Co film are formed in a mixed powder containing Cr powder and Al ₂ O ₃ powder and performing heat treatment, a boundary layer containing at least Co and a simultaneously forming a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the boundary layer;
forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal base material on which the boundary layer and the diffusion barrier layer are formed;
A method of manufacturing a heat-resistant metal member having the following steps.

The temperature, time, and atmosphere of the heat treatment are as explained in connection with the above invention.

In this invention, with respect to matters other than the above, the explanations in connection with the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
a step of sequentially forming at least a first Co film, a Re(Ni) film, a second Co film, and a Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, the second Co film, and the Ni film are formed is treated with Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. A boundary layer containing at least Co, a diffusion barrier layer on the boundary layer containing at least a Co-based alloy containing Re, and a diffusion barrier layer on the diffusion barrier layer are embedded in a mixed powder containing Co and subjected to heat treatment. simultaneously forming a Cr-containing alloy layer;
forming an Al-containing alloy layer on the Cr-containing alloy layer by performing an Al diffusion treatment on the metal base material on which the boundary layer, the diffusion barrier layer, and the Cr-containing alloy layer are formed;
A method of manufacturing a heat-resistant metal member having the following steps.

In this invention, the explanations regarding the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, and the second Co film are formed is placed in a mixed powder containing Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. A boundary layer containing at least Co, a diffusion barrier layer on the boundary layer whose main component is at least a Co-based alloy containing Re, and a Cr-containing alloy on the diffusion barrier layer. forming layers simultaneously;
A method of manufacturing a heat-resistant metal member having the following steps.

In this invention, the explanations regarding the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
After applying a slurry containing a mixed powder containing at least Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder on the second Co film, the metal substrate coated with the slurry is coated with Cr. A boundary layer containing at least Co is formed by immersing it in a mixed powder containing powder and Al ₂ O ₃ powder and performing heat treatment, and a Co-based alloy containing Re is the main component on the boundary layer. simultaneously forming a diffusion barrier layer and a Cr-containing alloy layer on the diffusion barrier layer;
A method of manufacturing a heat-resistant metal member having the following steps.

In this invention, the explanations regarding the invention of the heat-resistant metal member and the invention of the method of manufacturing the heat-resistant metal member described above hold true unless contrary to the nature thereof.

Moreover, this invention
a metal base material;
a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the metal base material;
a boundary layer containing at least Co between the metal base material and the diffusion barrier layer;
an Al-containing alloy layer or a Cr-containing alloy layer on the diffusion barrier layer;
This is a high-temperature device having a heat-resistant metal member.

The high-temperature device may be any type of device that partially or entirely includes the above-mentioned heat-resistant metal members, and specifically includes, for example, a gas turbine, a jet engine, an exhaust gas device, a boiler, a heat treatment furnace, an incinerator, etc. It is.

In the invention of this high-temperature device, the explanations regarding the above-described invention of the heat-resistant metal member hold true unless it is contrary to its nature.

Moreover, this invention
This is a plating solution that is a mixture of Co plating solution and Re(Ni) plating solution.

In this invention, what has been described in connection with the invention of the method for manufacturing a heat-resistant metal member described above using this plating solution holds true.

According to this invention, the heat-resistant metal member includes a boundary layer containing at least Co on a metal base material, a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component, and an Al-containing alloy layer or a Cr-containing alloy layer. By having this, it is possible to continuously obtain a diffusion barrier function, so that when used in a high temperature oxidizing atmosphere or a high temperature corrosive atmosphere, a protective oxide film can be maintained on the outermost surface for a long period of time. In particular, when a Cr-containing alloy layer is used, cracking and peeling of the protective oxide film can be suppressed, and furthermore, heat-resistant metal parts can be processed at temperatures below 1100°C, including the formation of a diffusion barrier layer. By being able to manufacture various metal substrates, including general-purpose substrates made of Fe-based alloys, Co-based alloys, Ni-based alloys, etc., the processes required for manufacturing include plating methods and pack processing methods. , etc., the manufacturing cost of heat-resistant metal members can be kept low.

FIG. 1 is a sectional view showing a heat-resistant metal member according to a first embodiment of the present invention. FIG. 1 is a sectional view showing a heat-resistant metal member according to a first embodiment of the present invention. 1 is a cross-sectional view showing a first example of a method for manufacturing a heat-resistant metal member according to a first embodiment of the present invention. 1 is a cross-sectional view showing a first example of a method for manufacturing a heat-resistant metal member according to a first embodiment of the present invention. FIG. 7 is a cross-sectional view showing a fifth example of the method for manufacturing a heat-resistant metal member according to the first embodiment of the present invention. FIG. 7 is a cross-sectional view showing a seventh example of the method for manufacturing a heat-resistant metal member according to the first embodiment of the present invention. FIG. 7 is a cross-sectional view showing an eighth example of the method for manufacturing a heat-resistant metal member according to the first embodiment of the present invention. FIG. 3 is a sectional view showing a heat-resistant metal member according to a second embodiment of the invention. FIG. 3 is a sectional view showing a heat-resistant metal member according to a second embodiment of the invention. 2 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 1 after plating and heat treatment. 10A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 10A. FIG. 10A is a photograph substituted for a drawing showing an enlarged part of the metal base material shown in FIG. 10A. 11A is a schematic diagram showing the measurement results of the concentration distribution of Re in the cross section of the metal base material shown in FIG. 11A. FIG. FIG. 2 is a schematic diagram showing a phase diagram of a Co--Re binary system. 10A is a photograph substituted for a drawing showing a cross-sectional structure after an Al diffusion treatment performed after forming an additional Ni film on the metal base material shown in FIG. 10A. 13A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 13A. FIG. 3 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 2 after plating, heat treatment, additional Ni plating, and Al diffusion treatment. 14A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 14A. FIG. 3 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 3 after plating and heat treatment. 15A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 15A. FIG. 15A is a photograph substituted for a drawing showing a cross-sectional structure after an Al diffusion treatment performed after forming an additional Ni film on the metal base material shown in FIG. 15A. 16A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 16A. FIG. 16A is a photograph substituted for a drawing showing an enlarged part of the metal base material shown in FIG. 16A. FIG. 17A is a schematic diagram showing the measurement results of the concentration distribution of Re in the cross section of the metal base material shown in FIG. 17A. 3 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 4 after plating and Ti treatment. 18A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 18A. FIG. 3 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 5 after plating and Ti treatment. 18A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 18A. FIG. It is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 6 after plating and (Ti+Mg) treatment. 20A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 20A. FIG. It is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 7 after plating and (Ti+FeAl) treatment. 21A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 21A. FIG. It is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 8 after plating and (Ti+NiAl) treatment. 22A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 22A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 9 after plating and (Ti+NiAl) treatment. 23A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 23A. FIG. 3 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 10 after plating and (Ti+NiAl) treatment. 24A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 24A. FIG. 3 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 11 after plating and (Ti+NiAl) treatment. 25A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 25A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 12 after plating and (Ti+NiAl) treatment. 26A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 26A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 13 after plating and (Ti+NiAl) treatment. 27A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 27A. FIG. 3 is a schematic diagram showing the dependence of the concentrations of Al, Ni, and Co in the Al-containing alloy layer on the Pt concentration added to the Al-containing alloy layer, which was determined from the results of Examples 9 to 13. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 14 after plating and (Ni+NiAl) treatment. 29A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 29A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 15 after plating and (Cr+Ni) treatment. 30A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 30A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 15 after FeAl treatment. 31A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 31A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 16 after plating and (Cr+Ni) treatment. 32A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 32A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 16 after FeAl treatment. 33A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 33A. FIG. 3 is a photograph substituted for a drawing showing a cross-sectional structure of a metal base material after plating using plating solution (1) in Example 17. 34A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 34A. FIG. 3 is a photograph substituted for a drawing showing a cross-sectional structure of a metal base material after plating using plating solution (1) in Example 17. 35A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 35A. FIG. 11 is a photograph substituted for a drawing showing a cross-sectional structure of a metal base material after plating using plating solution (2) in Example 17. 36A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 36A. FIG. 11 is a photograph substituted for a drawing showing a cross-sectional structure of a metal base material after plating using plating solution (2) in Example 17. 37A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 37A. FIG. 11 is a photograph substituted for a drawing showing a cross-sectional structure of a metal base material after plating using plating solution (3) in Example 17. 38A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 38A. FIG. FIG. 7 is a schematic diagram showing the relationship between the volume ratio of Co plating solution in the plating solution and the concentrations of Co, Re, and Ni in the plating film, which were determined from the results of Example 17. 34A is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material shown in FIG. 34A in Example 18 after Ti treatment. 40A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 40A. FIG. 35A is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material shown in FIG. 35A in Example 19 after Ti treatment. 40A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 40A. FIG. 37A is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material shown in FIG. 37A in Example 20 after Ti treatment. 40A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 40A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 21 after plating and heat treatment. 43A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 43A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 22 after plating and heat treatment. 44A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 44A. FIG. 12 is a photograph substituted for a drawing showing the cross-sectional structure of the metal base material of Example 23 after plating and heat treatment. 45A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross section of the metal base material shown in FIG. 45A. FIG.

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

<First embodiment>
[Heat-resistant metal parts]
FIG. 1 shows a heat-resistant metal member according to a first embodiment. As shown in FIG. 1, in this heat-resistant metal member, a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500 are laminated in this order on the surface of a metal base material 100. A transition layer 400 may exist between the diffusion barrier layer 300 and the Al-containing alloy layer 500, and the stacked structure in that case is shown in FIG.

The metal base material 100 is selected as necessary, for example, from among those already listed, but specifically, for example, Fe-based alloy, Co-based alloy, Ni-based alloy, Ni-based single crystal superalloy, etc. The boundary layer 200 contains at least Co, and in addition, one or more elements constituting the metal base material 100, one or more elements constituting the diffusion barrier layer 300, and optionally an Al-containing alloy. This is a layer containing one or more elements constituting the layer 500. The boundary layer 200 may or may not contain Al. When the boundary layer 200 contains Al, if the Al concentration of the boundary layer 200 exceeds 25 at%, voids are likely to be formed between the boundary layer 200 and the diffusion barrier layer 300 when the heat-resistant metal member is used. The Al concentration is typically selected to be 25 atomic % or less, preferably 15 atomic % or less. The presence of Al in the boundary layer 200 can suppress the decomposition of the diffusion barrier layer 300 due to the diffusion of Re and the decomposition of the Al-containing alloy layer 500 due to the diffusion of Al. The diffusion barrier layer 300 is made of a Co-based alloy containing Re, and contains one or more elements constituting the metal base 100 and one or more elements constituting the Al-containing alloy layer 500, Typically, it has a structure in which an ε-Re(Co) phase is precipitated within a continuous layer of an α-Co(Re) phase containing 10 at % of Re. The diffusion barrier layer 300 makes it possible to maintain the Al concentration in the Al-containing alloy layer 500 when the heat-resistant metal member is used, as well as form and maintain protective Al ₂ O ₃ and improve regeneration performance. Are better. Typically, the Al-containing alloy layer 500 is mainly composed of Co and Ni other than Al, and includes one or more elements constituting the metal base material 100 and one or more elements constituting the diffusion barrier layer 300. Contains. The Al concentration of the Al-containing alloy layer 500 is not particularly limited, but is typically 10 atomic % or more and 60 atomic % or less. The Al-containing alloy layer 500 may contain, for example, 1.5 atomic % or more of Pt. Pt in the Al-containing alloy layer 500 has a function of maintaining a high Al concentration and can ensure oxidation resistance. The transition layer 400 is a layer containing one or more elements forming the diffusion barrier layer 300 and one or more elements forming the Al-containing alloy layer 500. The thickness of the boundary layer 200 is not particularly limited, but is typically 5 μm or more and 200 μm or less, more typically 10 μm or more and 100 μm or less. The thickness of the diffusion barrier layer 300 is selected as necessary, but is preferably 10 μm or more and 100 μm or less. The thickness of transition layer 400 is not particularly limited. The thickness of the Al-containing alloy layer 500 is selected as necessary, but is typically 20 μm or more and 100 μm or less.

[Method for manufacturing heat-resistant metal parts]
A method of manufacturing this heat-resistant metal member will be explained. Here, first to seventh examples of manufacturing methods (manufacturing methods 1 to 7) will be described.

(1) Manufacturing method 1
As shown in FIG. 3, first, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on a metal base material 100 by a plating method. do. The Ni strike film is formed for the purpose of improving the adhesion of the plating film to the metal base material 100, and the plating is performed at a current density of 0.5 A/cm ² for 1 minute, for example. Plating of the first Co film 110 and the second Co film 130 is typically performed at a current density of 0.03 A/cm ² for 10 to 25 minutes. Plating of the Re(Ni) film 120 is typically performed at a current density of 0.04 A/cm ² for 10 to 60 minutes. A Ni film may be formed instead of the second Co film 130.

Next, the metal base material 100 on which the first Co film 110, the Re(Ni) film 120, and the second Co film 130 have been formed is treated with a mixed powder containing Cr powder and Al ₂ O ₃ powder (for example, (10 ~15) By embedding in mass % Cr powder + (90 to 85 mass % Al ₂ O ₃ powder) and performing heat treatment, a boundary layer 200 and a diffusion barrier layer 300 are formed as shown in FIG. . The temperature of the heat treatment is, for example, 1050° C. or more and 1150° C. or less (for example, 1100° C.), and the time is, for example, 2 hours or more and 12 hours or less. The atmosphere for the heat treatment is an inert gas atmosphere, preferably an Ar+3vol% _H2 atmosphere, for example.

Next, by performing an Al diffusion treatment on the metal base material 100 on which the boundary layer 200 and the diffusion barrier layer 300 have been formed, an Al-containing alloy layer 500 is formed on the diffusion barrier layer 300, as shown in FIG. do. In the Al diffusion treatment, the metal base material 100 on which the boundary layer 200 and the diffusion barrier layer 300 have been formed is treated with a mixed powder (for example, (10 to 15)) containing FeAl powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. Mass % FeAl powder + (1 to 2) mass % NH ₄ Cl powder + (89 to 83) mass % Al ₂ O ₃ powder) and immersed in an inert gas atmosphere, preferably Ar + 3 vol % H ₂ atmosphere. This is carried out by heating at a temperature of 1000°C or more and 1050°C or less, preferably 1000°C or more and 1050°C or less, for 1 hour or more and 10 hours or less. In this Al diffusion treatment, it is possible to form an Al-containing alloy layer 500 having an Al concentration of, for example, 50 atomic % or more and 60 atomic % or less. At the stage of forming the Al-containing alloy layer 500, a transition layer 400 in which the diffusion barrier layer 300 and the Al-containing alloy layer 500 are mixed may be formed between the diffusion barrier layer 300 and the Al-containing alloy layer 500.

Through the above steps, the intended heat-resistant metal member shown in FIG. 1 is manufactured.

(2) Manufacturing method 2
First, similarly to manufacturing method 1, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on a metal base material 100 by a plating method. do.

Next, the metal base material 100 on which the first Co film 110, Re(Ni) film 120, and second Co film 130 are formed is placed in a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder. As shown in FIG. 1, a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500 are simultaneously formed by embedding the layer in the substrate and performing heat treatment. When the mixed powder contains Ti powder and Al ₂ O ₃ powder, it is, for example, (10-22) mass % Ti powder + (90-78) mass % Al ₂ O ₃ powder. In this case, for example, an Al-containing alloy layer 500 having an Al concentration of 10 atomic % or more and 30 atomic % or less can be formed. When the mixed powder contains Ti powder, Mg powder, and Al ₂ O ₃ powder, for example, (10 to 20) mass% Ti powder + (0 to 2) mass% Mg powder + (90 to 78) mass% It is Al ₂ O ₃ powder. In this case, for example, an Al-containing alloy layer 500 having an Al concentration of 10 atomic % or more and 55 atomic % or less can be formed. When the mixed powder contains Mg powder and Al ₂ O ₃ powder, it is, for example, (10 to 22) weight % Mg powder + (90 to 78) weight % Al ₂ O ₃ powder. The temperature of the heat treatment is, for example, 1050° C. or more and 1150° C. or less (for example, 1100° C.), and the time is, for example, 2 hours or more and 12 hours or less. The atmosphere for the heat treatment is an inert gas atmosphere, preferably an Ar+3vol% _H2 atmosphere, for example. The Al concentration of the boundary layer 200 thus formed is typically 25 atomic % or less, preferably 15 atomic % or less. If necessary, a powder of FeAl, NiAl, etc., which serves as an Al source, may be mixed with the mixed powder.

Through the above steps, the intended heat-resistant metal member shown in FIG. 1 is manufactured.

(3) Manufacturing method 3
Manufacturing method 3 includes sequentially forming a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 on the metal base material 100 by plating. Furthermore, unlike manufacturing method 2, a Pt film (not shown) is formed on the second Co film 130 by the same plating method, or a Pt powder (not shown) is applied by a slurry method. The rest is the same as manufacturing method 2. Plating of the Pt film is performed, for example, at a current density of 0.02 A/cm ² for 1 to 10 minutes. The metal base material 100 on which the first Co film 110, Re(Ni) film 120, second Co film 130, and Pt film or Pt powder layer were formed in this way is mixed with Ti powder and/or Mg powder and Al ₂ O ₃ powder. The boundary layer 200, the diffusion barrier layer 300, and the Al-containing alloy layer 500 are simultaneously formed by embedding the powder in a mixed powder containing Pt, and the Al-containing alloy layer 500 is made to contain Pt. The Al concentration of the Al-containing alloy layer 500 to which Pt is added is, for example, 30 atomic % or more and 40 atomic % or less.

Through the above steps, the intended heat-resistant metal member shown in FIG. 1 is manufactured.

(4) Manufacturing method 4
First, similarly to manufacturing method 1, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on a metal base material 100 by a plating method. do.

Next, the metal base material 100 on which the first Co film 110, the Re(Ni) film 120, and the second Co film 130 have been formed is made of a material containing Ni powder, NiAl powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. By immersing it in the mixed powder and performing heat treatment, a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500 are simultaneously formed as shown in FIG. The mixed powder is, for example, (1-5) mass% Ni powder + (25-29) mass% NiAl powder + (1-2) mass% NH ₄ Cl powder + (73-64) mass% Al ₂ O ₃ powder. It is. In this case, for example, an Al-containing alloy layer 500 having an Al concentration of 40 atomic % or more and 55 atomic % or less can be formed. The temperature of the heat treatment is, for example, 950° C. or more and 1100° C. or less, typically 1000° C. or more and 1050° C. or less (for example, 1100° C.), and the time is, for example, 2 hours or more and 12 hours or less. The atmosphere for the heat treatment is an inert gas atmosphere, preferably an Ar+3vol% _H2 atmosphere, for example.

Through the above steps, the intended heat-resistant metal member shown in FIG. 1 is manufactured.

(5) Manufacturing method 5
As shown in FIG. 5, in manufacturing method 4, after forming a Ni strike film (not shown) on the metal base material 100, a plating solution containing a Co plating solution and a Re(Ni) plating solution was used. A Co(Re) alloy film 600 containing Ni is formed by a plating method. The mixing ratio (vol%) of the Co plating solution and the Re(Ni) plating solution in this plating solution is typically 10 vol% for the Co plating solution, 90 vol% for the Re(Ni) plating solution, 60 vol% for the Co plating solution, The range is 40 vol% of the Re(Ni) plating solution, preferably 20 vol% of the Co plating solution, and 80 vol% of the Re(Ni) plating solution to 50 vol% of the Co plating solution and 50 vol% of the Re(Ni) plating solution. If necessary, a Ni film (not shown) is further formed on the Co(Re) alloy film 600 by plating. The conditions for plating the Ni film are the same as in manufacturing method 1.

Next, similarly to manufacturing method 2, the Co(Re) alloy film 600 containing Ni or the metal base material 100 further formed with the Ni film is mixed with Ti powder and/or Mg powder and Al ₂ O ₃ powder. The boundary layer 200, the diffusion barrier layer 300, and the Al-containing alloy layer 500 are simultaneously formed by immersing it in powder and performing heat treatment.

Through the above steps, the intended heat-resistant metal member shown in FIG. 1 is manufactured.

(6) Manufacturing method 6
In manufacturing method 6, similarly to manufacturing method 5, a Ni strike film (not shown) is formed on the metal base material 100, and plating is performed using a plating solution that is a mixture of a Co plating solution and a Re(Ni) plating solution. A Co(Re) alloy film 600 containing Ni is formed by a method. If necessary, a Co film (not shown) is further formed on the Co(Re) alloy film 600 by plating. Co film plating is typically performed at a current density of 0.03 A/cm ² for 20 to 60 minutes.

Next, similarly to manufacturing method 1, the Co(Re) alloy film 700 containing Ni or the metal base material 100 on which a Co film is further formed is embedded in a mixed powder containing Cr powder and Al ₂ O ₃ powder. The boundary layer 200 and the diffusion barrier layer ₃₀₀ are heat-treated at 1050° C. or more and 1150° C. or less (for example, 1100° C.) for 2 hours or more and 12 hours or less in an inert gas atmosphere, such as an Ar + 3 vol% H 2 atmosphere. form at the same time.

Next, similarly to manufacturing method 1, an Al-containing alloy layer 500 is formed on the diffusion barrier layer 300 by performing an Al diffusion treatment on the metal base material 100 on which the boundary layer 200 and the diffusion barrier layer 300 are formed. do.

Through the above steps, the intended heat-resistant metal member shown in FIG. 1 is manufactured.

(7) Manufacturing method 7
In manufacturing method 7, similarly to manufacturing method 1, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are formed on the metal base material 100 using a plating method. After forming the second Co film 130 in this order, a Ni film (not shown) is formed on the second Co film 130 by the same plating method.

Next, the metal base material 100 on which the first Co film 110, the Re(Ni) film 120, the second Co film 130, and the Ni film are formed is mixed with Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O _{3 .} As shown in FIG. 6, a boundary layer 200, a diffusion barrier layer 300 containing Re and Cr, and a Cr-containing alloy layer 700 are buried in a mixed powder containing Re and Cr and subjected to heat treatment (Cr diffusion treatment). are formed at the same time. The mixed powder is, for example, (15-25) mass% Ni powder + (10-15) mass% Cr powder + (1-2) mass% NH ₄ Cl powder + (74-58) mass% Al ₂ O ₃ powder. It is. The temperature of the heat treatment is, for example, 1050° C. or more and 1150° C. or less (for example, 1100° C.), and the time is, for example, 2 hours or more and 12 hours or less. The atmosphere for the heat treatment is an inert gas atmosphere, preferably an Ar+3vol% _H2 atmosphere, for example. The Cr concentration of the Cr-containing alloy layer 700 thus formed is, for example, 10 atomic % or more and 50 atomic % or less. Cr-containing alloy layer 700 is typically a γ-Co (Cr, Ni) layer and does not contain a high Cr phase (eg, α-Cr phase).

Next, in the same manner as in manufacturing method 1, the metal base material 100 on which the boundary layer 200, the diffusion barrier layer 300, and the Cr-containing alloy layer 700 have been formed is subjected to an Al diffusion treatment, thereby producing a structure as shown in FIG. , converting the Cr-containing alloy layer 700 into an Al-containing alloy layer 500. At this time, a transition layer 400 containing Cr from the Cr-containing alloy layer 700 is formed between the diffusion barrier layer 300 and the Al-containing alloy layer 500.

Through the above steps, the desired heat-resistant metal member is manufactured.

As described above, according to the first embodiment, the heat-resistant metal member has a laminated structure consisting of the boundary layer 200, the diffusion barrier layer 300, and the Al-containing alloy layer 500 on the metal base material 100, so that the Fe-based Various metal substrates 100 can be used, including general-purpose substrates made of alloys, Co-based alloys, Ni-based alloys, etc., and the diffusion barrier function can be continuously obtained by the diffusion barrier layer 300. When the component is used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere, the Al concentration of the Al-containing alloy layer 500 can be maintained at a high level, thereby providing a protective Al ₂ O ₃ on the outermost surface for a long period of time. Not only can excellent high-temperature oxidation resistance or high-temperature corrosion resistance be obtained by maintaining the film, but also the ability to suppress the formation of voids in the boundary layer 200 increases the length of the heat-resistant metal member. It is possible to extend the service life. In addition, the process required to manufacture the heat-resistant metal member is simple, such as plating, pack processing, etc., so manufacturing costs can be kept low.

<Second embodiment>
[Heat-resistant metal parts]
FIG. 8 shows a heat-resistant metal member according to a second embodiment. As shown in FIG. 8, in this heat-resistant metal member, a boundary layer 200, a diffusion barrier layer 300, and a Cr-containing alloy layer 700 are laminated in this order on the surface of a metal base material 100. A transition layer 400 may exist between the diffusion barrier layer 300 and the Cr-containing alloy layer 700, and the stacked structure in that case is shown in FIG.

The metal base material 100 is the same as that in the first embodiment. The boundary layer 200 contains at least Co, and in addition, one or more elements constituting the metal base material 100, one or more elements constituting the diffusion barrier layer 300, and optionally a Cr-containing alloy. This is a layer containing one or more elements constituting the layer 700. The boundary layer 200 may or may not contain Al, and when the boundary layer 200 contains Al, the Al concentration and the effects obtained are the same as in the first embodiment. The diffusion barrier layer 300 is made of a Co-based alloy containing Re, and contains one or more elements constituting the metal base 100 and one or more elements constituting the Cr-containing alloy layer 700. Typically, it has a structure in which an ε-Re(Co) phase is precipitated within a continuous layer of an α-Co(Re) phase containing 10 at % of Re. The diffusion barrier layer 300 makes it possible to maintain the Cr concentration in the Cr-containing alloy layer 600 when the heat-resistant metal member is used, and also to form and maintain protective Cr ₂ O ₃ , which also improves regeneration ability. Are better. The transition layer 400 is a layer containing one or more elements forming the diffusion barrier layer 300 and one or more elements forming the Cr-containing alloy layer 700. The Cr concentration of the Cr-containing alloy layer 700 is not particularly limited, but is typically 10 atomic % or more and 50 atomic % or less, and other than Cr is mainly composed of Co and Ni. The thicknesses of the boundary layer 200, diffusion barrier layer 300, and transition layer 400 are the same as in the first embodiment. The thickness of the Cr-containing alloy layer 700 is the same as that of the Al-containing alloy layer 500.

[Method for manufacturing heat-resistant metal parts]
A method of manufacturing this heat-resistant metal member will be explained. Here, eighth to ninth examples of manufacturing methods (manufacturing methods 8 to 9) will be described.

(1) Manufacturing method 8
First, in the same manner as in manufacturing method 6, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on a metal base material 100 by plating. After the formation, the first Co film 110, the Re(Ni) film 120, the second Co film 130, and the metal base material 100 on which the Ni film has been formed are mixed with Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O. As shown in FIG. ₈ , a boundary layer 200, a diffusion barrier layer 300, and a Cr-containing alloy layer 700 are formed at the same time by embedding the layer in a mixed powder containing three powders and performing heat treatment.

Through the above steps, the intended heat-resistant metal member shown in FIG. 8 is manufactured.

(2) Manufacturing method 9
First, in the same manner as manufacturing method 6, a first Co film 110, a Re-Ni film 120, and a second Co film 130 are sequentially formed on a metal base material 100 by plating.

Next, a slurry containing a mixed powder containing Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder (composition is, for example, 20 mass % Ni powder + 10 mass % Cr powder) is applied on the second Co film 130. powder + 2% by mass NH ₄ Cl powder + 68% by mass Al ₂ O ₃ powder) is applied and dried, and then the metal substrate 100 coated with the slurry is placed in a mixed powder containing Cr powder and Al ₂ O ₃ powder. The boundary layer 200, the diffusion barrier layer 300, and the Cr-containing alloy layer 600 are formed at the same time by embedding the layer in the substrate and performing heat treatment.

Through the above steps, the intended heat-resistant metal member shown in FIG. 8 is manufactured.

As described above, according to the second embodiment, the heat-resistant metal member has a laminated structure consisting of the boundary layer 200, the diffusion barrier layer 300, and the Cr-containing alloy layer 700 on the metal base material 100. Various metal substrates 100 can be used, including general-purpose substrates made of base alloys, Co-based alloys, Ni-based alloys, and the like. Furthermore, since the diffusion barrier function can be continuously obtained by the diffusion barrier layer 300, when the heat-resistant metal member is used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere, the Cr concentration of the Cr-containing alloy layer 700 can be increased. By being able to maintain the protective Cr ₂ O ₃ film on the outermost surface for a long period of time, it is possible to not only obtain excellent high temperature oxidation resistance or high temperature corrosion resistance. By suppressing the formation of voids in the boundary layer 200, it is possible to extend the life of the heat-resistant metal member, and furthermore, it is possible to prevent the Cr-containing alloy layer 700 from containing the α-Cr phase. By doing so, cracking and peeling of the protective Cr ₂ O ₃ film can be suppressed. In addition, the process required to manufacture the heat-resistant metal member is simple, such as plating, pack processing, etc., so manufacturing costs can be kept low.

An example will be explained.

In Examples 1 to 23 below, the following four types of base materials were used as the metal base material 100.

(1) SCH-2 base material (Fe-based alloy base material)
(2) SUS310 base material (Fe-based alloy base material)
(3) Hastelloy-X base material (Ni-based alloy base material)
(4) CMSX-4 base material (Ni-based single crystal superalloy base material)

The composition (mass%) of each base material is as follows.

Composition of contained elements (mass%)
Fe Co Ni Cr Al Mn Mo W Ta Re
SCH-2 base material 73 27
SUS310 base material 53 20 25 1.5
Hastelloy -X base material 19 1.5 47 22 0.5 9
CMSX-4 base material 9.6 60 6.6 5.6 0.6 6.4 6.5 3.0

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

A heat-resistant metal member was manufactured by manufacturing method 1 using a SUS310 base material as the metal base material 100.

First, the surface of the SUS310 base material was smoothed and degreased, and then a Ni strike film, a Co film, a Re(Ni) film, and a Ni film were sequentially formed on the surface by plating. The Ni strike film was plated at a current density of 0.5 A/cm ² for 1 minute. Co film plating was performed at a current density of 0.03 A/cm ² for 10 minutes, and Re(Ni) film and Ni film plating was performed at a current density of 0.04 A/cm ² for 10 minutes. The Ni strike film had a thickness of about 2 μm, the Co film had a thickness of about 10 μm, the Re(Ni) film had a thickness of about 4.5 μm, and the Ni film had a thickness of about 7.5 μm. Next, the SUS310 base material on which the plating film was formed was immersed in a mixed powder of Cr powder and Al ₂ O ₃ powder (10 mass % Cr powder + 90 mass % Al ₂ O ₃ powder) and mixed with Ar + 3 vol% H ₂ Heat treatment was performed at 1100° C. for 7 hours in an atmosphere.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured using a SEM-EDX device (scanning electron microscope-energy dispersive spectrometer). 10A and 10B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 10A) measured using a cross-sectional SEM photograph and EDX, respectively. From FIG. 10A and FIG. 10B, it is clear that the structure contains Re, consisting of a continuous layer of α-Co(Re) phase with about 10 atomic % of Re as a solid solution, and an ε-Re (Co, Ni, Cr, Fe) phase precipitated therein. A diffusion barrier layer 300 made of a Co-based alloy layer is observed. 11A and 11B show a cross-sectional SEM photograph showing an enlarged view of the vicinity of the diffusion barrier layer 300 in FIG. 10A and measurement results of the concentration distribution of Re (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 11A). 11A and 11B, the Re-containing Co-based alloy layer constituting the diffusion barrier layer 300 contains ε-Re( It can be seen that the structure has a precipitated phase (Co, Ni, Cr, Fe). The ε-Re (Co, Ni, Cr, Fe) phase is simply expressed as ε-Re (Co) in FIG. 11B. The phase relationship between the α-Co(Re) phase and the ε-Re(Co) phase of the diffusion barrier layer 300 can be explained using the Co-Re binary system phase diagram shown in FIG. Furthermore, from FIGS. 10A and 10B, a transition layer 400 made of a Ni--Co alloy containing several atomic percent of Fe is observed above the diffusion barrier layer 300. Further, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300.

After forming an additional Ni film on the surface of the SUS310 base material shown in FIG. 10A by plating, an Al diffusion treatment was performed. In the Al diffusion treatment, the SUS310 base material shown in FIG. 10A is mixed with a mixed powder of FeAl powder, NH ₄ Cl powder, and Al ₂ O ₃ powder (10 mass % FeAl powder + 1 mass % NH ₄ Cl powder + 89 mass % Al ₂ O ₃ The test was carried out by immersing the sample in powder) and heating it at 1000° C. for 4 hours in an Ar+3 vol% H ₂ atmosphere. A part of the SUS310 base material/coating surface after Al diffusion treatment was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 13A and 13B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG3 in the photograph shown in FIG. 13A). 13A and 13B, an Al-containing alloy layer 500 containing Ni and Co as main constituents other than Al is observed in the upper layer of the transition layer 400. The structures of boundary layer 200, diffusion barrier layer 300 and transition layer 400 are maintained. The concentration of Al contained in the diffusion barrier layer 300 is very small, and no diffusion of Al into the boundary layer 200 and the SUS310 base material side is observed.

(Example 2)
Example 2 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and the steps were performed in the same manner as in Example 1, including Al diffusion treatment, to produce a heat-resistant metal member.

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 14A and 14B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 14A). 14A and 14B, similarly to Example 1, a boundary layer 200, a diffusion barrier layer 300, a transition layer 400, and an Al-containing alloy layer 500 are observed.

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

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured by Manufacturing Method 1.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, a Re(Ni) film, and a Ni film were sequentially formed by plating. did. The thickness of these films and the plating conditions are the same as in Example 1.

Next, in the same manner as in Example 1, the Hastelloy-X substrate on which the plating film was formed was embedded in a mixed powder of Cr powder and Al ₂ O ₃ powder, and heated at 1100°C in an Ar + 3 vol% H ₂ atmosphere. Heat treatment was performed for 7 hours.

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 15A and 15B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 15A). 15A and 15B, the diffusion barrier layer 300 is made of a Co-based alloy layer containing Re, which has a structure in which multiple layers of ε-Re(Co) phase are precipitated on a continuous layer of α-Co(Re) phase. be observed. A transition layer 400 made of a Ni--Co alloy is observed above the diffusion barrier layer 300. Similarly, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the Hastelloy-X substrate and the diffusion barrier layer 300.

Al diffusion treatment was performed on the Hastelloy-X substrate shown in FIG. 15A. The Al diffusion treatment was performed under the same conditions as in Example 1.

A part of the Hastelloy-X base material/coating surface after Al diffusion treatment was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 16A and 16B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG in the photograph shown in FIG. 16A). It can be seen from FIGS. 16A and 16B that the structures of the boundary layer 200 and diffusion barrier layer 300 shown in FIG. 15A are maintained. Although the Al concentration of the Al-containing alloy layer 500 is as high as 36.4 atomic % to 57.1 atomic %, no diffusion of Al into the boundary layer 200 and the metal base material 100 side is observed.

17A and 17B show a cross-sectional SEM photograph showing an enlarged view of the vicinity of the diffusion barrier layer 300 in FIG. 16A and measurement results of the concentration distribution of Re (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 17A). 17A and 17B, the Re-containing Co-based alloy layer constituting the diffusion barrier layer 300 contains ε-Re( It can be seen that the sample has a multi-phase structure in which the Co) phase precipitates.

(Example 4)
Example 4 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured by manufacturing method 2.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, and a Co film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the Hastelloy -X base material on which the plating film was formed was immersed in a mixed powder of Ti powder and Al ₂ O ₃ powder (20 mass% Ti powder + 80 mass% Al ₂ O ₃ powder), and Ar+3vol% Heat treatment was performed at 1100° C. for 7 hours in an H ₂ atmosphere (Ti treatment).

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 18A and 18B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 18A). From FIG. 18A and FIG. 18B, a Co-based alloy layer containing Re consists of a structure in which an ε-Re(Co) phase is precipitated in a thick continuous layer of an α-Co(Re) phase containing about 10 atomic % Re as a solid solution. A diffusion barrier layer 300 consisting of is observed. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 14.0 atomic % to 14.9 atomic % (Max 35.0 atomic %). A boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X base material and the diffusion barrier layer 300. Al is Hastelloy
-X also diffuses into the base material and boundary layer 200 side. No transition layer 400 is observed.

(Example 5)
Example 5 corresponds to the first embodiment.

A heat-resistant metal member was manufactured by manufacturing method 2 using a CMSX-4 base material as the metal base material 100.

First, the surface of the CMSX-4 base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the same Ti treatment as in Example 4 was performed on the CMSX-4 base material on which the plating film was formed. However, the Ti treatment was carried out for 12 hours.

A part of the CMSX-4 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 19A and 19B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line of the photograph shown in FIG. 19A). From FIG. 19A and FIG. 19B, it can be seen that from a Co-based alloy layer containing Re, which has a structure in which an ε-Re(Co) phase is precipitated in a continuous layer of an α-Co(Re) phase containing about 10 atomic percent of Re as a solid solution. A diffusion barrier layer 300 is observed. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 13.2 atomic % to 14.7 atomic % (Max 36.3 atomic %). A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the CMSX-4 base material and the diffusion barrier layer 300. Although the Al concentration in the boundary layer 200 is about 9 atomic %, no Al is detected in the diffusion barrier layer 300. Al existing in the boundary layer 200 is considered to have diffused into the boundary layer 500 from both the CMSX-4 base material and the Al-containing alloy layer 500, but Al from the CMSX-4 base material is predominant, and as a result, the Re boundary It can be seen that diffusion toward the layer 200 side is prevented.

(Example 6)
Example 6 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured by manufacturing method 2.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the Hastelloy-X base material on which the plating film was formed was mixed with a mixed powder of Ti powder, Mg powder, and Al ₂ O ₃ powder (20 mass % Ti powder + 2 mass % Mg powder + 78 mass % Al ₂ O ₃ powder). The sample was buried in a heat treatment at 1100° C. for 2 hours in an Ar+3 vol% H ₂ atmosphere ((Ti+Mg) treatment).

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 20A and 20B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 20A). From FIGS. 20A and 20B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X base material and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is as high as 36.3 atomic % to 49.0 atomic %, and diffusion of Al is observed on the boundary layer 200 side. No transition layer 400 is observed.

(Example 7)
Example 7 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured by manufacturing method 2.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the Hastelloy-X base material on which the plating film was formed was mixed with a mixed powder of Ti powder, FeAl powder, and Al ₂ O ₃ powder (20 mass % Ti powder + 2 mass % FeAl powder + 78 mass % Al ₂ O ₃ powder). The substrate was buried in a heat treatment at 1100° C. for 2 hours in an Ar+3 vol% H ₂ atmosphere ((Ti+FeAl) treatment).

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 21A and 21B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG4 in the photograph shown in FIG. 21A). From FIGS. 21A and 21B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X base material and the diffusion barrier layer 300. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 13.6 atomic % to 18.8 atomic % (Max 37.3 atomic %), and diffusion of Al toward the boundary layer 200 side is suppressed.

(Example 8)
Example 8 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured by manufacturing method 2.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the Hastelloy-X base material on which the plating film was formed was mixed with a mixed powder of Ti powder, NiAl powder, and Al ₂ O ₃ powder (20 mass % Ti powder + 2 mass % NiAl powder + 78 mass % Al ₂ O ₃ powder). The substrate was buried in a heat treatment at 1100° C. for 2 hours in an Ar+3 vol% H ₂ atmosphere ((Ti+NiAl) treatment).

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 22A and 22B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG4 in the photograph shown in FIG. 22A). From FIGS. 22A and 22B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. Although not shown, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X base material and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 was 36.3 atomic % to 49.0 atomic %, and diffusion of Al toward the boundary layer 200 side was observed.

(Example 9)
Example 9 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured according to manufacturing method 3.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Pt film were sequentially formed by plating. The thickness of the Pt film was approximately 3 μm. The Pt film was plated at a current density of 0.02 A/cm ² for 10 minutes. The thickness of the films other than the Pt film and the plating conditions are the same as in Example 1.

Next, the Hastelloy-X base material on which the plating film was formed was subjected to Ti treatment in the same manner as in Example 4.

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 23A and 23B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 23A). From FIGS. 23A and 23B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X base material and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 31.4 atomic % to 32.7 atomic %, and diffusion of Al toward the boundary layer 200 side is observed.

(Example 10)
Example 10 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured according to manufacturing method 3.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Pt film were sequentially formed by plating. The thickness of the Pt film and the plating conditions are the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions are the same as in Example 1.

Next, the Hastelloy-X base material on which the plating film was formed was subjected to Ti treatment in the same manner as in Example 4.

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 24A and 24B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line of the photograph shown in FIG. 24A). A diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed from FIGS. 24A and 24B. A boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X base material and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 31.8 atomic % to 35.5 atomic %. Diffusion of Al toward the boundary layer 200 side is observed.

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

A heat-resistant metal member was produced by manufacturing method 3 using a SUS310 base material as the metal base material 100.

First, the surface of the SUS310 base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Pt film were sequentially formed by plating. The thickness of the Pt film and the plating conditions are the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions are the same as in Example 1.

Next, the SUS310 base material on which the plating film was formed was subjected to Ti treatment in the same manner as in Example 4.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 25A and 25B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line of the photograph shown in FIG. 25A). From FIGS. 25A and 25B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 29.1 atomic % to 33.9 atomic %.

(Example 12)
Example 12 corresponds to the first embodiment.

A heat-resistant metal member was produced by manufacturing method 3 using a SUS310 base material as the metal base material 100.

First, the surface of the SUS310 base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Pt film were sequentially formed by plating. The thickness of the Pt film and the plating conditions are the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions are the same as in Example 1.

Next, the SUS310 base material on which the plating film was formed was subjected to Ti treatment in the same manner as in Example 4.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 26A and 26B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 26A). From FIGS. 26A and 26B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 32.9 atomic % to 37.6 atomic %, and diffusion of Al toward the boundary layer 200 side is observed.

(Example 13)
Example 13 corresponds to the first embodiment.

A heat-resistant metal member was produced by manufacturing method 3 using a SUS310 base material as the metal base material 100.

First, the surface of the SUS310 base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Pt film were sequentially formed by plating. The thickness of the Pt film and the plating conditions are the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions are the same as in Example 1.

Next, the SUS310 base material on which the plating film was formed was subjected to Ti treatment in the same manner as in Example 4.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 27A and 27B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG7 in the photograph shown in FIG. 27A). From FIGS. 27A and 27B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 34.8 atomic % to 41.3 atomic %, and Al diffusion toward the boundary layer 200 side is observed.

FIG. 28 shows the Pt concentration dependence of the Al, Ni, and Co concentrations in the Al-containing alloy layer 500 obtained from the results shown in Examples 9 to 13. From FIG. 28, when the Pt concentration was about 1.5 atomic % or more, the Co concentration decreased, the Ni concentration increased, and the Al concentration increased from 30 atomic % to 42 atomic %.

(Example 14)
Example 14 corresponds to the first embodiment.

A SUS310 base material was used as the metal base material 100, and a heat-resistant metal member was produced using manufacturing method 4.

First, the surface of the SUS310 base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, and a Co film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the SUS310 base material on which the plating film was formed was mixed with a mixed powder of Ni powder, NiAl powder, NH ₄ Cl powder, and Al ₂ O ₃ powder (3 mass % Ni powder + 10 mass % NiAl powder + 1.5 mass % NH ₄ Cl powder + 16 mass % Al ₂ O ₃ powder) and heat treated at 1100° C. for 2 hours in an Ar + 3 vol % H ₂ atmosphere ((Ni+NiAl) treatment).

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 29A and 29B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line of the photograph shown in FIG. 29A). 29A and 29B, a boundary layer 200, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re, a transition layer 400, and an Al-containing alloy layer with an Al concentration of 37.5 to 44.6 at.% are formed. I can see that Al diffuses into the boundary layer 200 by about 20 μm.

(Example 15)
Example 15 corresponds to the first embodiment.

A SUS310 base material was used as the metal base material 100, and a heat-resistant metal member was produced using manufacturing method 7.

First, the surface of the SUS310 base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the SUS310 base material on which the plating film was formed was mixed with a mixed powder of Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder (20 mass % Ni powder + 10 mass % Cr powder + 1.5 mass % NH ₄ Cl powder + 68% by mass Al ₂ O ₃ powder) and heat treated at 1100° C. for 8 hours in an Ar + 3vol% H ₂ atmosphere ((Cr+Ni) treatment).

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 30A and 30B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 30A). It can be seen from FIGS. 30A and 30B that a boundary layer 200, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re, and a transition layer 400 are formed. Diffusion barrier layer 300 contains Cr and Fe. The transition layer 400 consists of a γ-Ni (Co, Cr) layer which is a Cr-containing alloy layer, and no α-Cr phase was detected.

Next, an Al diffusion treatment was performed on the SUS310 base material shown in FIG. 30A. The Al diffusion treatment was performed at 1050° C. for 5 hours using the same mixed powder and atmosphere as in Example 1.

A part of the SUS310 base material/coating surface after Al diffusion treatment was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 31A and 31B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 31A). From FIGS. 31A and 31B, the structure of the boundary layer 200 and diffusion barrier layer 300 shown in FIG. 30A is maintained. Although the Al concentration of the Al-containing alloy layer 500 is as high as 48.1 atomic % to 60.6 atomic %, no diffusion of Al into the boundary layer 200 and the metal base material 100 side is observed. That is, it can be seen that the diffusion barrier layer 300 formed by Cr diffusion processing functions as an Al diffusion barrier. Furthermore, enrichment of Cr is observed in the transition layer 400. This is because when Al diffuses into the Ni(Cr) alloy layer, Cr is concentrated on the diffusion barrier layer 300 side because the solubility of Cr in γ'-Ni ₃ Al and β-NiAl is low. It is.

(Example 16)
Example 16 corresponds to the first embodiment.

A Hastelloy-X base material was used as the metal base material 100, and a heat-resistant metal member was manufactured according to manufacturing method 7.

First, the surface of the Hastelloy-X base material was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions are the same as in Example 1.

Next, the Hastelloy-X base material on which the plating film was formed was subjected to the same (Cr+Ni) treatment as in Example 15.

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 32A and 32B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 32A). It can be seen from FIGS. 32A and 32B that a boundary layer 200 made of a Co-containing alloy layer, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re, and a transition layer 400 are formed. Diffusion barrier layer 300 contains Cr and Fe. The transition layer 400 consists of a γ-Ni (Co, Cr) layer which is a Cr-containing alloy layer, and no α-Cr phase was detected.

Next, Al diffusion treatment was performed on the Hastelloy-X base material shown in FIG. 32A. The Al diffusion treatment was performed under the same conditions as in Example 15.

A part of the Hastelloy-X base material/coating surface after Al diffusion treatment was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 33A and 33B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG3 in the photograph shown in FIG. 33A). From FIGS. 33A and 33B, the structure of the boundary layer 200 and diffusion barrier layer 300 shown in FIG. 32A is maintained. Boundary layer 200 is a Co-containing alloy layer. An Al-containing alloy layer 500 made of a β-NiAl layer is observed on the diffusion barrier layer 300. Although the Al concentration of the Al-containing alloy layer 500 is as high as 45.4 atomic % to 60.17 atomic %, no diffusion of Al into the boundary layer 200 is observed. Concentration of Cr is seen in the transition layer 400.

(Example 17)
Example 17 describes a case where a Co(Re) alloy film containing Ni is formed by a plating method using a plating solution prepared by mixing a Co plating solution and a Re(Ni) plating solution at various ratios. do.

That is, plating solutions having three types of mixing ratios were prepared as shown below.
Co plating solution Re(Ni) plating solution Plating solution (1) 50vol% 50vol%
Plating solution (2) 25vol% 75vol%
Plating solution (3) 20vol% 80vol%

The surface of the SUS310 base material was treated in the same manner as in Example 1 to form a Ni strike film, and then a Co(Re) alloy film containing Ni was formed by plating using plating solution (1). A Ni film was formed thereon by plating. The Co(Re) alloy film containing Ni was plated at a current density of 0.03 A/cm ² for 20 minutes. Plating of the Ni film was performed under the same conditions as in Example 1.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 34A and 34B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 34A).

The surface of the SUS310 base material was treated in the same manner as in Example 1 to form a Ni strike film, a Co film was formed by plating, and then Co (containing Ni) was formed by plating using plating solution (1). A Re) alloy film was formed, and a Co film was further formed thereon by plating. The Co(Re) alloy film containing Ni was plated at a current density of 0.03 A/cm ² for 20 minutes. Plating of the Ni film and Co film was performed under the same conditions as in Example 1. A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 35A and 35B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG3 in the photograph shown in FIG. 35A).

After treating the surface of the SUS310 base material in the same manner as in Example 1, a Ni strike film was formed, and a Co(Re) alloy film containing Ni was formed by plating using plating solution (2). A Ni film was formed thereon by plating. The Co(Re) alloy film containing Ni was plated at a current density of 0.03 A/cm ² for 20 minutes. Plating of the Ni film was performed under the same conditions as in Example 1. A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 36A and 36B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 36A).

After treating the surface of the SUS310 base material in the same manner as in Example 1, a Ni strike film was formed, a Ni film was formed thereon by plating, and then Ni was deposited by plating using plating solution (2). A Co(Re) alloy film was formed, and a Ni film was further formed thereon by plating. The Co(Re) alloy film containing Ni was plated at a current density of 0.03 A/cm ² for 20 minutes. Plating of the Ni film was performed under the same conditions as in Example 1. A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 37A and 37B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along analysis line LG4 in the photograph shown in FIG. 37A).

After treating the surface of the SUS310 base material in the same manner as in Example 1, a Ni strike film was formed, and a Co(Re) alloy film containing Ni was formed by plating using plating solution (3). A Ni film was formed thereon by plating. The Co(Re) alloy film containing Ni was plated at a current density of 0.03 A/cm ² for 20 minutes. Plating of the Ni film was performed under the same conditions as in Example 1. A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 38A and 38B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG5 in the photograph shown in FIG. 38A).

From the results of forming a Co(Re) alloy film containing Ni using plating solution (1), plating solution (2), and plating solution (3) as described above, the volume ratio of Co plating solution in the plating solution is FIG. 39 shows the changes in the concentration of each element (Co, Re, Ni) in the Co(Re) alloy film containing Ni when the values were changed. Note that the concentrations of Re and Ni in the Re(Ni) alloy film formed using the Re(Ni) plating solution are 40 to 75 atomic % for Re and 60 to 25 atomic % for Ni.

From FIG. 39, as the volume ratio of the Co plating solution in the plating solution decreases, the Re concentration in the Co(Re) alloy film increases, and the Co concentration decreases from 100 to 0 atomic %. Note that the Ni concentration in the Co(Re) alloy film gradually increases toward the value of the Re(Ni) alloy.

These results show that a Co(Re) alloy film with an arbitrary Co concentration or Ni concentration can be formed by selecting the composition of the plating solution.

(Example 18)
Example 18 corresponds to the first embodiment.

In Example 17, a plating film was formed on the SUS310 base material as shown in FIG. 35A using the plating solution (1), and then Ti treatment was performed on the SUS310 base material on which the plating film was formed to form a heat-resistant metal member. Created. The Ti treatment was performed in the same manner as in Example 4.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 40A and 40B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 40A).

From FIG. 40A and FIG. 40B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. In the diffusion barrier layer 300, Re is dissolved throughout the Co-based alloy layer. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 6.8 atomic % to 12.8 atomic %. No diffusion of Al toward the boundary layer 200 side is observed.

(Example 19)
Example 19 corresponds to the first embodiment.

In Example 17, a plating film was formed on the SUS310 base material as shown in FIG. 36A using the plating solution (2), and then Ti treatment was performed on the SUS310 base material on which the plating film was formed to form a heat-resistant metal member. Created. The Ti treatment was performed in the same manner as in Example 4.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 41A and 41B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG3 in the photograph shown in FIG. 41A). From FIGS. 41A and 41B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. In the diffusion barrier layer 300, a Re enriched layer (20 atomic %) exists in a Co(Re) solid solution. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 4.3 atomic % to 6.6 atomic %, and no diffusion of Al toward the boundary layer 200 is observed.

(Example 20)
Example 20 corresponds to the first embodiment.

In Example 17, a plating film was formed on the SUS310 base material as shown in FIG. 38A using the plating solution (3), and then Ti treatment was performed on the SUS310 base material on which the plating film was formed to form a heat-resistant metal member. Created. The Ti treatment was performed in the same manner as in Example 4.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 42A and 42B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG4 in the photograph shown in FIG. 42A). From FIGS. 42A and 42B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. In the diffusion barrier layer 300, a Re enriched layer (20 to 25 atomic %) exists in a Co(Re) solid solution. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 10 atomic % to 40.2 atomic %, and Al diffusion toward the boundary layer 200 side is observed.

(Example 21)
Example 21 corresponds to the first embodiment.

After treating the surface of the SUS310 base material in the same manner as in Example 1, a Ni strike film was formed, and a Co(Re) alloy film containing Ni was formed by plating using plating solution (2). A Co film was formed thereon by plating. Next, the SUS310 base material on which the plating film was formed was immersed in a mixed powder of Cr powder and Al ₂ O ₃ powder (10 mass % Cr powder + 90 mass % Al ₂ O ₃ powder) and mixed with Ar + 3 vol% H ₂ Heating was performed at 1100° C. for 2 hours in an atmosphere.

A part of the SUS310 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 43A and 43B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG3 in the photograph shown in FIG. 43A). From FIGS. 43A and 43B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. Furthermore, a transition layer 400 made of a Ni--Co alloy containing Fe is observed above the diffusion barrier layer 300. Further, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300.

Although not shown, an Al-containing alloy layer 500 was then formed on the uppermost layer by performing an Al diffusion treatment in the same manner as in Example 1.

(Example 22)
Example 22 corresponds to the first embodiment.

After treating the surface of the SCH-2 base material in the same manner as in Example 1, a Ni strike film was formed, and a Co(Re) alloy film containing Ni was formed by a plating method using plating solution (2). Further, a Co film was formed thereon by plating. Next, the SCH-2 base material on which the plating film was formed was subjected to the same heat treatment as in Example 21.

A part of the SCH-2 base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 44A and 44B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 44A). From FIGS. 44A and 44B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. Furthermore, a transition layer 400 made of a Ni--Co alloy containing Fe is observed above the diffusion barrier layer 300. Further, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300.

Although not shown, an Al-containing alloy layer 500 was then formed on the uppermost layer by performing an Al diffusion treatment in the same manner as in Example 1.

(Example 23)
Example 23 corresponds to the first embodiment.

After treating the surface of the Hastelloy-X base material in the same manner as in Example 1, a Ni strike film was formed, and a Co(Re) alloy film containing Ni was formed by plating using plating solution (2). Further, a Co film was formed thereon by plating. Next, the Hastelloy-X base material on which the plating film was formed was subjected to the same heat treatment as in Example 21.

A part of the Hastelloy-X base material/coating surface was cut, and its cross-sectional structure was observed and the concentration distribution of each element was measured. 45A and 45B respectively show a cross-sectional SEM photograph and measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 45A). From FIGS. 45A and 45B, a diffusion barrier layer 300 made of a Co-based alloy layer containing Re is observed. Furthermore, a transition layer 400 made of a Ni--Co alloy containing Fe is observed above the diffusion barrier layer 300. Further, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 base material and the diffusion barrier layer 300.

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

In the invention of the method for manufacturing a heat-resistant metal member described in this specification, multiple layers of various metal films are sequentially formed on a metal base material by a plating method, but in the broadest sense, The metal film formed by the plating method can be expressed as a metal film containing Co, Re, and Ni as a whole. This metal film may be a single layer or multiple layers. For example, in the invention of a method for manufacturing a heat-resistant metal member in which at least a first Co film, a Re(Ni) film, and a second Co film or Ni film are sequentially formed on a metal base material, the first Co film, Re(Ni) film, Instead of the Ni) film and the second Co film or Ni film, a single-layer or multi-layer metal film containing Co, Re, and Ni as a whole may be formed. The first Co film, Re(Ni) film, and second Co film or Ni film are examples of such metal films.

DESCRIPTION OF SYMBOLS 100... Metal base material, 200... Boundary layer, 300... Diffusion barrier layer, 400... Transition layer, 500... Al-containing alloy layer, 700... Cr-containing alloy layer

Claims (23)

a metal base material;
a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the metal base material;
a boundary layer containing at least Co between the metal base material and the diffusion barrier layer;
an Al-containing alloy layer or a Cr-containing alloy layer on the diffusion barrier layer;
A heat-resistant metal member having 2. The diffusion barrier layer comprises an α-Co(Re) continuous layer containing 10 atomic % of Re, and the α-Co(Re) continuous layer contains ε-Re(Co) phase precipitates. heat-resistant metal parts. The heat-resistant metal member according to claim 1, comprising the Al-containing alloy layer on the diffusion barrier layer, and the Al-containing alloy layer contains Pt. The heat-resistant metal member according to claim 1, comprising the Al-containing alloy layer on the diffusion barrier layer, and wherein the boundary layer contains Al. 5. The heat-resistant metal member according to claim 4, wherein the boundary layer has an Al concentration of 1 atomic % or more and 25 atomic % or less. 2. The heat-resistant metal member according to claim 1, comprising the Al-containing alloy layer on the diffusion barrier layer, the Al-containing alloy layer mainly consisting of Co and Ni other than Al. 2. The heat-resistant metal member according to claim 1, comprising the Cr-containing alloy layer on the diffusion barrier layer, the Cr-containing alloy layer mainly consisting of Co and Ni other than Cr. The heat-resistant metal member according to claim 1, further comprising a transition layer between the diffusion barrier layer and the Al-containing alloy layer or the Cr-containing alloy layer. 9. The heat-resistant metal member according to claim 8, wherein the transition layer has a Re concentration of less than 1 atomic % and an Al concentration of 10 atomic % or less. 2. The heat-resistant metal member according to claim 1, wherein the metal base material is made of an Fe-based alloy, a Co-based alloy, a Ni-based alloy, or a Ni-based single crystal superalloy. a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed is immersed in a mixed powder containing Cr powder and Al ₂ O ₃ powder and heat treated. forming a boundary layer containing at least Co and a diffusion barrier layer on the boundary layer containing at least a Co-based alloy containing Re as a main component;
forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal base material on which the boundary layer and the diffusion barrier layer are formed;
A method for manufacturing a heat-resistant metal member having the following. a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The first Co film, the Re(Ni) film, and the second Co film or Ni film are formed on the metal base material in a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder. A boundary layer containing at least Co, a diffusion barrier layer on the boundary layer whose main component is at least a Co-based alloy containing Re, and an Al-containing alloy on the diffusion barrier layer. forming layers simultaneously;
A method for manufacturing a heat-resistant metal member having the following. 13. The method according to claim 12, wherein after forming the second Co film and before performing the heat treatment, a Pt film is formed on the second Co film by a plating method, or a Pt powder is applied by a slurry method. A method for manufacturing heat-resistant metal parts. a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed contains Ni powder, NiAl powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. By embedding it in the mixed powder and performing heat treatment, a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer whose main component is at least a Co-based alloy containing Re, and a diffusion barrier layer on the diffusion barrier layer are formed. simultaneously forming an Al-containing alloy layer;
A method for manufacturing a heat-resistant metal member having the following. forming at least a Co--Re alloy film containing Ni on the metal substrate by a plating method using a plating solution containing a mixture of a Co plating solution and a Re(Ni) plating solution;
By immersing the metal base material on which the Co(Re) alloy film is formed in a mixed powder containing Ti powder and/or Mg powder and Al ₂ O ₃ powder and performing heat treatment, a boundary containing at least Co is formed. simultaneously forming a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the boundary layer, and an Al-containing alloy layer on the diffusion barrier layer;
A method for manufacturing a heat-resistant metal member having the following. 16. The method for manufacturing a heat-resistant metal member according to claim 15, wherein after forming the Co--Re alloy film and before performing the heat treatment, a Ni film is formed on the Co--Re alloy film by plating. forming at least a Co(Re) alloy film containing Ni on the metal substrate by a plating method using a plating solution containing a mixture of a Co plating solution and a Re(Ni) plating solution;
By immersing the metal base material on which the Co--Re alloy film is formed in a mixed powder containing Cr powder and Al ₂ O ₃ powder and performing heat treatment, a boundary layer containing at least Co and on the boundary layer is formed. simultaneously forming a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component;
forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal base material on which the boundary layer and the diffusion barrier layer are formed;
A method for manufacturing a heat-resistant metal member having the following. 18. The method for manufacturing a heat-resistant metal member according to claim 17, wherein after forming the Co--Re alloy film and before performing the heat treatment, a Co film is formed on the Co--Re alloy film by a plating method. a step of sequentially forming at least a first Co film, a Re(Ni) film, a second Co film, and a Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, the second Co film, and the Ni film are formed is treated with Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. A boundary layer containing at least Co, a diffusion barrier layer on the boundary layer whose main component is at least a Co-based alloy containing Re, and a diffusion barrier layer on the diffusion barrier layer are embedded in a mixed powder containing Co and subjected to heat treatment. simultaneously forming a Cr-containing alloy layer;
converting the Cr-containing alloy layer into an Al-containing alloy layer by performing an Al diffusion treatment on the metal base material on which the boundary layer, the diffusion barrier layer, and the Cr-containing alloy layer are formed;
A method for manufacturing a heat-resistant metal member having the following. a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
The metal base material on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed contains Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder. By embedding it in the mixed powder and performing heat treatment, a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer containing at least a Co-based alloy containing Re, and a diffusion barrier layer on the diffusion barrier layer are formed. simultaneously forming a Cr-containing alloy layer;
A method for manufacturing a heat-resistant metal member having the following. a step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal base material by a plating method;
After applying a slurry containing a mixed powder containing at least Ni powder, Cr powder, NH ₄ Cl powder, and Al ₂ O ₃ powder on the second Co film, the metal base material coated with the slurry is coated with Cr. A boundary layer containing at least Co is formed by embedding it in a mixed powder containing powder and Al ₂ O ₃ powder and heat-treating it, and a Co-based alloy containing Re is the main component on the boundary layer. simultaneously forming a diffusion barrier layer and a Cr-containing alloy layer on the diffusion barrier layer;
A method for manufacturing a heat-resistant metal member having the following. a metal base material;
a diffusion barrier layer containing at least a Co-based alloy containing Re as a main component on the metal base material;
a boundary layer containing at least Co between the metal base material and the diffusion barrier layer;
an Al-containing alloy layer or a Cr-containing alloy layer on the diffusion barrier layer;
A high-temperature device having a heat-resistant metal member. A plating solution that is a mixture of Co plating solution and Re(Ni) plating solution.

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