JP2022065441A - Heat resistant metal member and method of manufacturing the same, and high-temperature device and method of manufacturing the same - Google Patents

Abstract

To provide a heat resistant metal member and a method of manufacturing the same characterized in that: various metal base materials including general base materials can be used; processes needed for manufacture are simple processes for plating and a subsequent diffusion treatment; when use in an environment where heating and cooling cycles are added in a high-temperature oxidative atmosphere or high-temperature corrosive atmosphere can improve mechanical characteristics of a metal base material in addition to a diffusion barrier function; and high-temperature characteristics that the metal base material has can be maintained for a long period.SOLUTION: A heat resistant metal member has a metal base material (10) such as an Fe-based alloy, a transition layer (20), a W-based or Re-based multi-purpose alloy layer (30), and an Al and/or Cr-containing alloy layer (40). For manufacture of the heat resistant metal member, after at least a Ni layer, a Ni(W) layer, or a Ni(Re) layer is formed on the metal base material one after another, an Al diffusion treatment or Cr diffusion treatment using FeAl or NiAl as an Al steam source is performed.SELECTED DRAWING: Figure 1

Description

The present invention relates to a heat-resistant metal member and a method for manufacturing the same, and a high-temperature device and the method for manufacturing the same. It is suitable for application to members, boilers, internal combustion engines, gas turbines, jet engines, and the like.

Oxidation-resistant coatings are applied to heat-resistant alloy substrates used in various combustion equipment, internal combustion engines, boilers, incinerators, exhaust gas system members, turbines, jet engines, and the like. A typical oxidation-resistant coating is an alloy film containing Al and / or Cr. In particular, an Al-containing alloy is used in a harsh corrosion environment at high temperature, and the surface of the substrate is subjected to Al diffusion permeation treatment, thermal spraying, etc. Formed on the protective alumina (Al ₂ O ₃ ) scale to protect the substrate from high temperature corrosion.

In the heat-resistant alloy base material, however, the Al concentration of the coating film decreases early because Al of the coating film mutually diffuses to the base material side and the elements of the base material to the coating film side, especially during use at high temperature. However, since the coating film loses its oxidation resistance due to the formation and growth of non-protective oxides, a solution is required.

In order to suppress the mutual diffusion of the above-mentioned elements, the present inventors have formed a diffusion barrier layer (DBL: Diffusion Barrier Layer) containing Re, W, etc., Cr, etc. on the substrate, and then the surface thereof. A technique for laminating an Al-containing alloy layer has been proposed. Diffusion Barrier Coating (DBC) including the diffusion barrier layer and the Al-containing alloy layer, and the diffusion barrier coating system (DBC system) as a general term for the base material, the diffusion barrier layer and the Al-containing alloy layer, respectively. It is called. Details of the diffusion barrier layer are described in Patent Documents 1 to 4.

Japanese Patent No. 38576889 Japanese Patent No. 3857690 Japanese Patent No. 391588 Japanese Patent No. 4735720

However, in the above-mentioned diffusion barrier coating, the usable base material is limited to a specific alloy base material, and not only a general-purpose base material made of, for example, Fe, Ni, stainless steel, etc. cannot be used, and also, a general-purpose base material cannot be used. Effective methods for forming the diffusion barrier layer have been limited to slurry coating and subsequent heat treatment.

Therefore, the problem to be solved by the present invention is that various metal substrates including general-purpose substrates can be used, and the process required for manufacturing can be a simple process of plating and subsequent diffusion treatment, and high-temperature oxidation can be performed. When used in an environment where a heating / cooling cycle is added in a sexual atmosphere or a high-temperature corrosive atmosphere, it is possible to improve the mechanical properties of the metal substrate in addition to the diffusion barrier function, and the metal substrate can be improved. It is an object of the present invention to provide a refractory metal member capable of maintaining the high temperature characteristics of the material for a long period of time and a method for manufacturing the same, and a high temperature device including such a refractory metal member and a method for manufacturing the same.

In order to solve the above problems, the present invention
With a metal base material
With the W-based or Re-based multipurpose alloy layer on the metal substrate,
With the Al and / or Cr-containing alloy layer on the multipurpose alloy layer,
The transition layer between the metal substrate and the multipurpose alloy layer,
It is a refractory metal member having.

In the present invention, in the W-based or Re-based multi-purpose alloy layer (MPL), the elements constituting the Al and / or Cr-containing alloy layer are on the metal substrate side, and the elements constituting the metal substrate are present. In addition to the barrier function of suppressing mutual diffusion to the Al and / or Cr-containing alloy layer side, that is, the diffusion barrier ability, improvement of mechanical properties (tensile strength, creep strength, etc.) of the metal substrate, etc. It means an alloy layer that has multi-functionality and can be used for multiple purposes. The W-based multipurpose alloy layer contains W and Ni, and at least one element selected from the group consisting of Co, Al, Cr, Re and the elements constituting the metal substrate. The Re-based multipurpose alloy layer contains Re and Ni, and at least one element selected from the group consisting of Co, Al, Cr, W and the elements constituting the metal substrate. A Cr-based multipurpose alloy layer may be further provided between the multipurpose alloy layer and the Al and / or Cr-containing alloy layer. The thickness of the multipurpose alloy layer is selected as needed, but is generally 10 μm or more and 50 μm or less.

There are three types of Al and / or Cr-containing alloy layers: an Al-containing alloy layer that does not contain Cr, a Cr-containing alloy layer that does not contain Al, and an alloy layer that contains Al and Cr. The Al-containing alloy layer is not particularly limited, but is made of, for example, β-NiAl, γ'-Ni ₃ Al, CoAl, FeAl, and the like. The Al-containing alloy layer may inevitably contain elements contained in the metal base material and the multipurpose alloy layer. The Al-containing alloy layer may also contain Cr particles. The Al-containing alloy layer has a function of forming protective alumina (Al ₂ O ₃ ) on the outermost surface to protect the entire refractory metal member including the metal base material from a high-temperature oxidizing atmosphere. The Cr-containing alloy layer is not particularly limited, but is made of, for example, a Ni—Cr based alloy, preferably γ—Ni (Cr). Here, Ni (Cr) means Ni containing Cr (generally, X (Z) means X containing Z). The Cr-containing alloy layer may inevitably contain elements contained in the metal base material and the multipurpose alloy layer. The Cr-containing alloy layer has a function of forming protective chromium (Cr ₂ O ₃ ) on the outermost surface to protect the entire refractory metal member including the metal base material from a high-temperature corrosive atmosphere. The alloy layer containing Al and Cr is not particularly limited, but is made of, for example, FeCrAl, an Al-containing alloy containing Cr particles, and the like. The alloy layer containing Al and Cr may inevitably contain the elements contained in the metal base material and the multipurpose alloy layer. The alloy layer containing Al and Cr forms protective alumina (Al ₂ O ₃ ) and protective chromium (Cr ₂ O ₃ ) on the outermost surface, and the entire refractory metal member including the metal substrate is highly oxidizable. It has the function of protecting from atmosphere and high temperature corrosive atmosphere. The thickness of the Al and / or Cr-containing alloy layer is selected as needed, but is generally 20 μm or more and 60 μm or less.

The transition layer between the metal base material and the multipurpose alloy layer is a region formed by ensuring the adhesion between the metal base material and the multipurpose alloy layer and fusing (mutually diffusing) the two. The transition layer contains Ni and at least one element among the elements constituting the metal substrate and at least one element among the elements constituting the multipurpose alloy layer. The thickness of the transition layer is generally 5 μm or more and 100 μm or less, preferably 10 μm or more and 60 μm or less, but is not limited thereto.

The metal base material is selected as needed and various types can be used, and is composed of, for example, Fe, Co, Ni, Fe-based alloy, Co-based alloy, Ni-based alloy and the like. Of these, the Fe-based alloy is specifically composed of, for example, SUS430, SUS304, SUS310, Alloy-X, FSX-414 and the like. The shape of the metal base material is not particularly limited and is selected according to the intended use, and is, for example, flat plate-shaped, rod-shaped (square bar, round bar, etc.), tubular, box-shaped, or the like.

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

In addition, this invention
A step of sequentially forming a Ni layer containing at least a Ni layer and a W (that is, a Ni (W) layer) or a Ni layer containing Re (that is, a Ni (Re) layer) on a metal substrate by plating.
By performing Al diffusion treatment or Cr diffusion treatment using FeAl or NiAl as the Al vapor source, a W-based or Re-based multipurpose alloy layer and an Al and / or Cr-containing alloy layer are applied onto the metal substrate via a transition layer. And the process of sequentially forming
It is a manufacturing method of a refractory metal member having.

If necessary, when forming the multipurpose alloy layer, a Ni layer, a Co layer or a Ni (Co) layer is further formed on the Ni (W) layer or the Ni (Re) layer by plating. The thickness of these plating layers is not particularly limited, but for example, the bottom Ni layer (inner Ni layer) is 10 μm or more and 60 μm or less, and the Ni (W) layer or Ni (Re) layer is 20 μm or more and 50 μm or less. The upper Ni layer (outer Ni layer) is 30 μm or more and 60 μm or less. In the Al diffusion treatment, the metal substrate on which the plating layer is formed is typically embedded in a mixed powder of FeAl or NiAl as an Al vapor source, ammonium chloride (NH ₄ Cl) and alumina (Al ₂ O ₃ ). It is carried out by heating in a vacuum or in an inert gas atmosphere at a temperature of 950 ° C. or higher and 1050 ° C. or lower for 1 hour or longer and 10 hours or shorter. The mixing ratio of these powders is not particularly limited, but FeAl or NiAl is preferably 5% by weight or more and 30% by weight or less, NH ₄ Cl is 1% by weight or more and 5% by weight or less, and the remaining Al ₂ O ₃ . .. The composition of FeAl or NiAl as the Al vapor source is selected as needed, but is preferably Fe-50 atomic% Al or Ni-50 atomic% Al. The Cr diffusion treatment typically involves burying the metal substrate on which the plating layer is formed in a Cr vapor source, such as a mixed powder of Cr, NH ₄ Cl and Al ₂ O ₃ , in a vacuum or an inert gas atmosphere. It is carried out by heating at a temperature of 1000 ° C. or higher and 1100 ° C. or lower for 1 hour or more and 10 hours or less. The mixing ratio of these powders is not particularly limited, but preferably, a Cr vapor source, for example, Cr is 5% by weight or more and 30% by weight or less, NH ₄ Cl is 1% by weight or more and 5% by weight or less, and the remaining Al ₂ O. It is ₃ .

In the present invention, the matters other than the above are described in relation to the above invention of the refractory metal member as long as they do not contradict the properties thereof.

In addition, this invention
With a metal base material
With the W-based or Re-based multipurpose alloy layer on the metal substrate,
With the Al and / or Cr-containing alloy layer on the multipurpose alloy layer,
A high temperature device having a refractory metal substrate having a transition layer between the metal substrate and the multipurpose alloy layer.

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

In addition, this invention
A step of sequentially forming a Ni layer containing at least a Ni layer and a W (that is, a Ni (W) layer) or a Ni layer containing Re (that is, a Ni (Re) layer) on a metal substrate by plating.
By performing Al diffusion treatment or Cr diffusion treatment using FeAl or NiAl as the Al vapor source, a W-based or Re-based multipurpose alloy layer and an Al and / or Cr-containing alloy layer are applied onto the metal substrate via a transition layer. It is a manufacturing method of a high temperature apparatus having a step of sequentially forming the above and a step of manufacturing a refractory metal member by executing.

In the invention of the high temperature device and the invention of the method of manufacturing the high temperature device, the matters other than the above are related to the invention of the refractory metal member and the invention of the method of manufacturing the refractory metal member, unless they are contrary to their properties. The explanation is established.

According to the present invention, by having a W-based or Re-based multipurpose alloy layer and an Al and / or Cr-containing alloy layer, various metal substrates including a general-purpose substrate can be used, which is necessary for production. In addition to the diffusion barrier function, when used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere with a heating / cooling cycle added, the simple process of plating and subsequent diffusion treatment is sufficient. The mechanical properties of the metal base material can be improved, and the high temperature characteristics of the metal base material can be maintained for a long period of time.

It is sectional drawing which shows the refractory metal member by 1st Embodiment of this invention. It is sectional drawing which shows the manufacturing method of the refractory metal member by 1st Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 2nd Embodiment of this invention. It is sectional drawing which shows the manufacturing method of the refractory metal member by the 2nd Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 3rd Embodiment of this invention. It is sectional drawing which shows the manufacturing method of the refractory metal member by the 3rd Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 4th Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 5th Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 6th Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 7th Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 8th Embodiment of this invention. It is sectional drawing which shows the manufacturing method of the refractory metal member by the 8th Embodiment of this invention. It is sectional drawing which shows the refractory metal member by the 9th Embodiment of this invention. It is sectional drawing which shows the manufacturing method of the refractory metal member by the 9th Embodiment of this invention. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 1 after plating, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 1 after Al diffusion treatment, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 2 after plating, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 2 after Al diffusion treatment, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 3 after Cr diffusion treatment, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 4 after Cr diffusion treatment and Al diffusion treatment, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 5 after Cr diffusion treatment and Al diffusion treatment, and is the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross section. It is a drawing substitute photograph which shows the cross-sectional structure after the homogenization treatment of the test piece of Example 6, and is the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure after the homogenization treatment of the test piece of Example 7, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of the comparative example 1 after Al diffusion treatment, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a schematic diagram which shows the cycle number dependence of the oxidation amount of the test piece of Example 1, 3 and Comparative Example 2 which performed the heating / cooling cycle oxidation. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 1 after one cycle oxidation, and is the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 1 after 34 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph showing the cross-sectional structure of the test piece of Example 1 after 132 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 1 after 608 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 3 after 608 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 8 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 9 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 10 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 11 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 12 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 13 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 14 before oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 8 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 9 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 10 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 11 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 12 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 13 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a drawing substitute photograph which shows the cross-sectional structure of the test piece of Example 14 after 63 cycles of oxidation, and the schematic diagram which shows the measurement result of the concentration distribution of each element in this cross-section. It is a schematic diagram which shows the oxidation amount after 4 cycles of oxidation of the test piece of Examples 8-14. It is a schematic diagram which shows the oxidation amount after 63 cycles of oxidation of the test piece of Examples 8-14.

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

<First Embodiment>
[Refractory metal members]
FIG. 1 shows a refractory metal member according to the first embodiment. As shown in FIG. 1, in this refractory metal member, a transition layer 20, a W-based multipurpose alloy layer 30, and a β-NiAl layer 40 as an Al-containing alloy layer are sequentially laminated on the surface of the metal base material 10.

The metal base material 10 is selected as needed, and is, for example, selected from those already mentioned. Specifically, for example, Fe, Ni, Co, Fe-based alloy, Ni-based alloy, Co-based alloy, etc. It consists of. The transition layer 20 is composed of an alloy layer containing elements constituting the metal base material 10 and elements constituting the multipurpose alloy layer 30. The multipurpose alloy layer 30 is made of W, W (Cr), and the like. The Al concentration of the β-NiAl layer 40 is not particularly limited, but is typically 30 atomic% or more and 70 atomic% or less. The thickness of the transition layer 20 is preferably 10 μm or more and 60 μm or less. The thickness of the multipurpose alloy layer 30 is typically 10 μm or more and 50 μm or less. The thickness of the β-NiAl layer 40 is typically 20 μm or more and 60 μm or less.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 2, first, the Ni layer 50 and the Ni (W) layer 60 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, and the thickness of the Ni (W) layer 60 is, for example, 10 μm or more and 40 μm or less.

Next, the metal base material 10 on which the Ni layer 50 and the Ni (W) layer 60 are formed is subjected to an Al diffusion treatment using FeAl as an Al vapor source, so that the metal base material is as shown in FIG. A transition layer 20, a W-based multipurpose alloy layer 30, and a β-NiAl layer 40 are formed on the surface of 10. In the Al diffusion treatment, the metal base material 10 on which the Ni layer 50 and the Ni (W) layer 60 are formed is embedded in, for example, a mixed powder (FeAl + NH ₄ Cl + Al ₂ O ₃ ), and is preferably used in a vacuum or in an inert gas atmosphere. Is carried out by heating at a temperature of 950 to 1050 ° C. for 1 to 10 hours in an Ar + 3 vol% H ₂ atmosphere.

As a result, the refractory metal member of interest shown in FIG. 1 is manufactured.

According to the first embodiment, the heat-resistant metal member has the W-based multipurpose alloy layer 30 and the β-NiAl layer 40, so that various metals including a general-purpose base material made of, for example, Fe, Ni, stainless steel, etc. When the base material 10 is used, it is excellent because a protective Al ₂ O ₃ film can be formed on the outermost surface when used in an environment where a heating / cooling cycle is added in a high-temperature oxidizing atmosphere. High temperature oxidation resistance can be obtained, and in addition to the diffusion barrier function, the mechanical properties of the metal base material 10 can be improved, so that a decrease in the mechanical strength of the metal base material 10 can be suppressed, and the metal can be obtained. The high temperature characteristics of the base material 10 can be maintained for a long period of time.

<Second embodiment>
[Refractory metal members]
FIG. 3 shows a refractory metal member according to the second embodiment. As shown in FIG. 3, in this refractory metal member, the transition layer 20, the W-based multipurpose alloy layer 30, and the β-NiAl layer are formed on the surface of the metal base material 10 as in the case of the refractory metal member according to the first embodiment. Although the 40s are sequentially laminated, the difference is that the thickness of the β-NiAl layer 40 is much larger than that of the refractory metal member according to the first embodiment, specifically, for example, 2 to 3 times larger. Other things are the same as the refractory metal member according to the first embodiment.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 4, first, the Ni layer 50, the Ni (W) layer 60, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (W) layer 60 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70 is, for example, 20 μm or more and 50 μm or less.

Next, as shown in FIG. 3, the metal substrate 10 on which the Ni layer 50, the Ni (W) layer 60, and the Ni layer 70 are formed is subjected to an Al diffusion treatment using FeAl as an Al vapor source. , A transition layer 20, a W-based multipurpose alloy layer 30, and a β-NiAl layer 40 are formed on the surface of the metal base material 10. The Al diffusion treatment is performed in the same manner as in the first embodiment.

As a result, the refractory metal member of interest shown in FIG. 3 is manufactured.

According to the second embodiment, in addition to the same advantages as in the first embodiment, the large thickness of the β-NiAl layer 40 allows Al ₂ to be protected on the outermost surface for a longer period of time. The advantage of being able to form an O ₃ film and thus maintaining high temperature oxidation resistance for a longer period of time can be obtained.

<Third embodiment>
[Refractory metal members]
FIG. 5 shows a refractory metal member according to the third embodiment. As shown in FIG. 5, in this refractory metal member, the transition layer 20, the Re-based multipurpose alloy layer 80, and the β-NiAl layer 40 are sequentially laminated on the surface of the metal base material 10. The metal base material 10, the transition layer 20, and the β-NiAl layer 40 are the same as those in the first embodiment. The thickness of the Re-based multipurpose alloy layer 80 is typically 10 μm or more and 50 μm or less.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 6, first, the Ni layer 50, the Ni (Re) layer 90, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (Re) layer 90 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70 is, for example, 20 μm or more and 50 μm or less.

Next, as shown in FIG. 5, the metal substrate 10 on which the Ni layer 50, the Ni (Re) layer 90, and the Ni layer 70 are formed is subjected to an Al diffusion treatment using FeAl as an Al vapor source. , The transition layer 20, the Re-based multipurpose alloy layer 80, and the β-NiAl layer 40 are formed on the surface of the metal base material 10. The Al diffusion treatment is performed in the same manner as in the first embodiment.

As a result, the refractory metal member of interest shown in FIG. 5 is manufactured.

According to the third embodiment, when the refractory metal member has the Re-based multipurpose alloy layer 80 and the β-NiAl layer 40, the same advantages as those of the first embodiment can be obtained.

<Fourth Embodiment>
[Refractory metal members]
FIG. 7 shows a refractory metal member according to the fourth embodiment. As shown in FIG. 7, in this refractory metal member, a transition layer 20, a W (Cr) -based multipurpose alloy layer 100, and a γ—Ni (Cr) layer 110 as a Cr-containing alloy layer are provided on the surface of the metal base material 10. They are stacked sequentially. The metal base material 10 and the transition layer 20 are the same as those in the first embodiment. The thickness of the W (Cr) -based multipurpose alloy layer 100 is typically 10 μm or more and 50 μm or less. The thickness of the γ—Ni (Cr) layer 110 is typically 5 μm or more and 60 μm or less.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 4, first, the Ni layer 50, the Ni (W) layer 60, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (W) layer 60 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70 is, for example, 20 μm or more and 50 μm or less.

Next, the metal base material 10 on which the Ni layer 50, the Ni (W) layer 60, and the Ni layer 70 are formed is subjected to Cr diffusion treatment, so that the surface of the metal base material 10 is subjected to Cr diffusion treatment, as shown in FIG. The transition layer 20, the W (Cr) -based multipurpose alloy layer 100, and the γ—Ni (Cr) layer 110 are formed. In the Cr diffusion treatment, the metal substrate 10 on which the Ni layer 50, the Ni (W) layer 60 and the Ni layer 70 are formed is embedded in, for example, a (Cr + Ni + NH ₄ Cl + Al ₂ O ₃ ) mixed powder, and is used in a vacuum or an inert gas. This is done by heating in an atmosphere, preferably an Ar + 3 vol% H ₂ atmosphere, at a temperature of 1000 to 1100 ° C. for 1 to 10 hours.

As a result, the refractory metal member of interest shown in FIG. 7 is manufactured.

According to the fourth embodiment, the heat-resistant metal member has the W (Cr) -based multipurpose alloy layer 100 and the γ—Ni (Cr) layer 110, so that it is a general-purpose group made of, for example, Fe, Ni, stainless steel, or the like. When various metal base materials 10 including materials are used and used in an environment where a heating / cooling cycle is added in a high-temperature corrosive atmosphere, protective chromia (Cr ₂ O ₃ ) is present on the outermost surface. By being formed, excellent high-temperature corrosion resistance can be obtained, and in addition to the diffusion barrier function, the mechanical properties of the metal base material 10 can be improved, thereby reducing the mechanical strength of the metal base material 10. It can be suppressed and the high temperature characteristics of the metal base material 10 can be maintained for a long period of time.

<Fifth Embodiment>
[Refractory metal members]
FIG. 8 shows a refractory metal member according to the fifth embodiment. As shown in FIG. 8, in this refractory metal member, the transition layer 20, the Re (Cr) -based multipurpose alloy layer 120, and the γ—Ni (Cr) layer 110 are sequentially laminated on the surface of the metal base material 10. The metal base material 10 and the transition layer 20 are the same as those in the first embodiment. The thickness of the Re (Cr) -based multipurpose alloy layer 120 is typically 10 μm or more and 50 μm or less. The thickness of the γ—Ni (Cr) layer 110 is typically 5 μm or more and 60 μm or less.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 6, first, the Ni layer 50, the Ni (Re) layer 90, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (Re) layer 90 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70 is, for example, 20 μm or more and 50 μm or less.

Next, the metal base material 10 on which the Ni layer 50, the Ni (Re) layer 90, and the Ni layer 70 are formed is subjected to Cr diffusion treatment, so that the surface of the metal base material 10 is subjected to Cr diffusion treatment, as shown in FIG. The transition layer 20, the Re (Cr) -based multipurpose alloy layer 120, and the γ—Ni (Cr) layer 110 are formed. The Cr diffusion treatment is performed in the same manner as in the fourth embodiment.

As a result, the refractory metal member of interest shown in FIG. 8 is manufactured.

According to the fifth embodiment, the refractory metal member has the Re (Cr) -based multipurpose alloy layer 120 and the γ—Ni (Cr) layer 110, so that the same advantages as those of the fourth embodiment can be obtained. Can be done.

<Sixth Embodiment>
[Refractory metal members]
FIG. 9 shows a refractory metal member according to the sixth embodiment. As shown in FIG. 9, in this refractory metal member, an alloy containing a transition layer 20, a W (Cr) -based multipurpose alloy layer 100, a Cr-based multipurpose alloy layer 130, and Al and Cr on the surface of the metal base material 10. The Cr particle-containing β-NiAl layer 140 as a layer is sequentially laminated. The metal base material 10 and the transition layer 20 are the same as those in the first embodiment. The thickness of the W (Cr) -based multipurpose alloy layer 100 is typically 10 μm or more and 50 μm or less. The thickness of the Cr-based multipurpose alloy layer 130 is typically 10 μm or more and 50 μm or less. The thickness of the Cr particle-containing β-NiAl layer 140 is typically 10 μm or more and 50 μm or less.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 4, first, the Ni layer 50, the Ni (W) layer 60, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (W) layer 60 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70 is, for example, 20 μm or more and 50 μm or less.

Next, the metal base material 10 on which the Ni layer 50, the Ni (W) layer 60, and the Ni layer 70 are formed is subjected to Cr diffusion treatment, whereby the surface of the metal base material 10 is similarly shown in FIG. The transition layer 20, the W (Cr) -based multipurpose alloy layer 100, and the γ—Ni (Cr) layer 110 are formed on the transition layer 20. The Cr diffusion treatment is performed in the same manner as in the fourth embodiment.

Next, the metal base material 10 on which the transition layer 20, the W (Cr) -based multipurpose alloy layer 100, and the γ—Ni (Cr) layer 110 are formed is subjected to Al diffusion treatment using FeAl as an Al vapor source. As shown in FIG. 9, a transition layer 20, a W (Cr) -based multipurpose alloy layer 100, a Cr-based multipurpose alloy layer 130, and a Cr particle-containing β-NiAl layer 140 are formed on the surface of the metal substrate 10. The Al diffusion treatment is performed in the same manner as in the first embodiment.

As a result, the refractory metal member of interest shown in FIG. 9 is manufactured.

According to the sixth embodiment, the W (Cr) -based multipurpose alloy layer 100, the Cr-based multipurpose alloy layer 130, and the Cr particle-containing β-NiAl layer 140 have the same advantages as those of the first and fourth embodiments. Can be obtained.

<7th embodiment>
[Refractory metal members]
FIG. 10 shows a refractory metal member according to the seventh embodiment. As shown in FIG. 10, in this refractory metal member, a transition layer 20, a Re (Cr) -based multipurpose alloy layer 120, a Cr-based multipurpose alloy layer 130, and a Cr particle-containing β-NiAl layer 140 are formed on the surface of the metal base material 10. Are sequentially laminated. The metal base material 10 and the transition layer 20 are the same as those in the first embodiment. The thickness of the Re (Cr) -based multipurpose alloy layer 120 is typically 10 μm or more and 50 μm or less. The thicknesses of the Cr-based multipurpose alloy layer 130 and the Cr particle-containing β—NiAl layer 140 are the same as those in the sixth embodiment.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 6, first, the Ni layer 50, the Ni (Re) layer 90, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating.

Next, the metal base material 10 on which the Ni layer 50, the Ni (Re) layer 90, and the Ni layer 70 are formed is subjected to Cr diffusion treatment, whereby the surface of the metal base material 10 is similarly shown in FIG. The transition layer 20, the Re (Cr) -based multipurpose alloy layer 120, and the γ—Ni (Cr) layer 110 are formed in the transition layer 20. The Cr diffusion treatment is performed in the same manner as in the fourth embodiment.

Next, the metal base material 10 on which the transition layer 20, the Re (Cr) -based multipurpose alloy layer 120, and the γ—Ni (Cr) layer 110 are formed is subjected to Al diffusion treatment using FeAl as an Al vapor source. As shown in FIG. 10, a transition layer 20, a Re (Cr) -based multipurpose alloy layer 120, a Cr-based multipurpose alloy layer 130, and a Cr particle-containing β-NiAl layer 140 are formed on the surface of the metal base material 10. The Al diffusion treatment is performed in the same manner as in the first embodiment.

As a result, the refractory metal member of interest shown in FIG. 10 is manufactured.

According to the seventh embodiment, the refractory metal member has the Re (Cr) -based multipurpose alloy layer 120, the Cr-based multipurpose alloy layer 100, and the Cr particle-containing β-NiAl layer 140, whereby the first and fourth embodiments are made. The same advantages as in the embodiments can be obtained.

<8th embodiment>
[Refractory metal members]
FIG. 11 shows a refractory metal member according to the eighth embodiment. As shown in FIG. 11, in this refractory metal member, a transition layer 20, a Re-based multipurpose alloy layer 80, a W-based multipurpose alloy layer 30, and a γ'-(Ni, Co) ₃ Al layer are formed on the surface of the metal base material 10. The 150 and the β-CoAl layer 160 are sequentially laminated. The γ'-(Ni, Co) ₃ Al layer 150 and the β-CoAl layer 160 constitute an Al-containing alloy layer. The metal base material 10 and the transition layer 20 are the same as those in the first embodiment. The thicknesses of the Re-based multipurpose alloy layer 80 and the W-based multipurpose alloy layer 30 are the same as those in the first to third embodiments. The thickness of the γ'-(Ni, Co) ₃ Al layer 150 is typically 10 μm or more and 50 μm or less. The thickness of the β-CoAl layer 160 is the same as the thickness of the β-NiAl layer 40.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 12, first, the Ni layer 50, the Re (Ni) layer 170, the Ni (W) layer 60, the Ni layer 70, and the Co layer 180 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Re (Ni) layer 170 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (W) layer 60 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70. The thickness of the Co layer 180 is, for example, 20 μm or more and 50 μm or less, and the thickness of the Co layer 180 is, for example, 20 μm or more and 50 μm or less.

Next, the metal base material 10 on which the Ni layer 50, the Re (Ni) layer 170, the Ni (W) layer 60, the Ni layer 70, and the Co layer 180 are formed is subjected to an Al diffusion treatment using FeAl as an Al steam source. Then, by performing a homogenization treatment, as shown in FIG. 11, a transition layer 20, a Re-based multipurpose alloy layer 80, a W-based multipurpose alloy layer 30, and γ'-(Ni) are formed on the surface of the metal substrate 10. , Co) ₃ The Al layer 150 and the β-CoAl layer 160 are formed. The Al diffusion treatment is performed in the same manner as in the first embodiment. The homogenization treatment is carried out, for example, by heating in the air at a temperature of 1000 to 1200 ° C. for 0.5 to 3 hours.

As a result, the refractory metal member of interest shown in FIG. 11 is manufactured.

According to the eighth embodiment, the same advantages as those of the first embodiment can be obtained.

<9th embodiment>
[Refractory metal members]
FIG. 13 shows a refractory metal member according to the ninth embodiment. As shown in FIG. 13, in this refractory metal member, a transition layer 20, a Re-based multipurpose alloy layer 80, a W-based multipurpose alloy layer 30, and a γ'-(Ni, Fe) ₃ Al layer are formed on the surface of the metal base material 10. 190 and β-NiAl layer 40 are sequentially laminated. The metal base material 10 and the transition layer 20 are the same as those in the first embodiment. The thicknesses of the Re-based multipurpose alloy layer 80 and the W-based multipurpose alloy layer 30 are the same as those in the first to third embodiments. The thickness of the γ'-(Ni, Fe) ₃ Al layer 190 is typically 10 μm or more and 50 μm or less. The thickness of the β—NiAl layer 40 is the same as that of the first embodiment.

[Manufacturing method of refractory metal parts]
A method for manufacturing this refractory metal member will be described.

As shown in FIG. 14, first, the Ni layer 50, the Re (Ni) layer 170, the Ni (W) layer 60, and the Ni layer 70 are sequentially formed on the surface of the metal base material 10 by electroplating. The thickness of the Ni layer 50 is, for example, 5 μm or more and 20 μm or less, the thickness of the Re (Ni) layer 170 is, for example, 5 μm or more and 20 μm or less, the thickness of the Ni (W) layer 60 is, for example, 10 μm or more and 40 μm or less, and the thickness of the Ni layer 70. The size is, for example, 20 μm or more and 50 μm or less.

Next, the metal base material 10 on which the Ni layer 50, the Re (Ni) layer 170, the Ni (W) layer 60, and the Ni layer 70 are formed is subjected to an Al diffusion treatment using FeAl as an Al vapor source. By performing the homogenization treatment, as shown in FIG. 13, the transition layer 20, the Re-based multipurpose alloy layer 80, the W-based multipurpose alloy layer 30, γ'-(Ni, Fe) ₃ are formed on the surface of the metal substrate 10. The Al layer 190 and the β-NiAl layer 40 are formed. The Al diffusion treatment is performed in the same manner as in the first embodiment. The homogenization treatment is carried out in the same manner as in the eighth embodiment.

As a result, the refractory metal member of interest shown in FIG. 13 is manufactured.

According to the ninth embodiment, the same advantages as those of the first embodiment can be obtained.

Examples will be described.

(1) to (7) shown in Table 1 were used as the metal base material 10.
(1) Alloy-X
(2) Ni
(3) Fe
(4) SUS310
(5) SUS430
(6) SUH446
(7) FSX414

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

The SUS310 substrate shown in Table 1 was used as the metal substrate 10. The surface of the test piece formed from this SUS310 substrate was smooth-polished and degreased. Next, (Ni strike plating current density 0.5 A / cm ² thickness 1 μm) → (Ni plating current density 0.06 A / cm ² thickness 10 μm) → (Ni (W) plating current density 0.15 A / cm ² ) A plating layer having a total thickness of about 40 μm was formed by laminating the Ni layer and the Ni (W) layer in order.

A part of the base material / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured with an SEM-EDX device (scanning electron microscope-energy dispersive spectroscopy device). 15A and 15B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 of the photograph shown in FIG. 15A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 15A and 15B, a Ni layer and a Ni (W) layer were sequentially formed on the surface of the test piece. As can be seen from FIG. 15B, the W concentration of the Ni (W) layer is about 18 to 20 atomic%.

Next, the surface of the test piece was subjected to Al diffusion treatment. That is, the test piece on which the plating layer was formed was embedded in a mixed powder of Fe-50 atomic% Al: NH ₄ Cl: Al ₂ O ₃ = 20: 3: 77 (weight ratio), and 1000 in an Ar + 3 vol% H ₂ atmosphere. Al diffusion treatment was performed by heating at ° C. for 4 hours.

A part of the test piece subjected to the Al diffusion treatment was cut, and the cross-sectional structure thereof was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 16A and 16B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 of the photograph shown in FIG. 16A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 16A and 16B, a W-based MPL layer and a β-NiAl layer were sequentially formed on the surface of the test piece from the substrate side via a transition layer. As can be seen from FIG. 16B, the W-based MPL layer has a mixed structure of a Ni—Al alloy phase (composed of γ—Ni (Al) and γ'—Ni ₃ Al) and a W-containing alloy phase. The Al concentration is 9.9 to 15.7 atomic%, the Ni concentration is 9.6 to 57.2 atomic%, and the W concentration is 24.7 to 80.8 atomic%. The Al concentration of the β-NiAl layer is 35 to 58 atomic%, and in particular, the Al concentration in the range of about 10 μm in thickness on the W-based MPL layer side is 50 atomic% or less.

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

First, in the same manner as in Example 1, the surface of the test piece formed of the SUS310 substrate shown in Table 1 was smooth-polished and degreased. Next, (Ni strike plating current density 0.5 A / cm ² thickness 1 μm) → (Ni plating current density 0.06 A / cm ² thickness 10 μm) → (Ni (Re) plating current density 0.15 A / cm ² ) (Thickness 30 μm) → (Ni plating current density 0.06 A / cm ² thickness 30 μm) is performed to form a plating layer with a total thickness of about 70 μm in which the Ni layer, Ni (Re) layer and Ni layer are laminated in order. bottom.

A part of the base material / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 17A and 17B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 of the photograph shown in FIG. 17A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 17A and 17B, a Ni layer, a Ni (Re) layer and a Ni layer were sequentially formed on the surface of the test piece. As can be seen from FIG. 17B, the Re concentration of the Ni (Re) layer is in the range of 25.1 to 27.5 atomic% from the substrate side.

Next, the surface of the test piece was subjected to Al diffusion treatment under the same conditions as in Example 1.

A part of the test piece subjected to the Al diffusion treatment was cut, and the cross-sectional structure thereof was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 18A and 18B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line of the photograph shown in FIG. 18A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 18A and 18B, a Re-based MPL layer and a β-NiAl layer were formed on the upper end surface of the test piece from the base material side via a transition layer. As can be seen from FIG. 18B, the Re concentration of the Re-based MPL layer is 5.8 to 26.7 atomic%. The Al concentration of the β-NiAl layer is 35.9 to 56.6 atomic%.

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

The SUS310 substrate shown in Table 1 was used as the metal substrate 10. The surface of the test piece formed from this SUS310 substrate was smooth-polished and degreased. Next, in the same manner as in Example 2, a Ni layer, a Ni (W) layer, and a Ni layer were laminated in this order to form a plating layer having a total thickness of about 40 μm.

Next, the surface of the test piece was subjected to Cr diffusion treatment. That is, the test piece on which the plating layer is formed is embedded in a mixed powder of Cr: NH ₄ Cl: Al ₂ O ₃ = 20: 3: 77 (weight ratio), and heated at 1100 ° C. for 4 hours in an Ar + 3 vol% H2 atmosphere. As a result, Cr diffusion treatment was applied.

A part of the base material 10 / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 19A and 19B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 of the photograph shown in FIG. 19A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 19A and 19B, a W (Cr) -based MPL layer and a γ-Ni (Cr) layer (partially α-Cr (Ni on the surface) from the substrate side on the upper end surface of the test piece via a transition layer. ) Exists) was formed. Further, as can be seen from FIG. 19B, the W concentration of the W (Cr) -based MPL layer is 2.0 to 19.0 atomic%, the Cr concentration is 10.1 to 12.4 atomic%, and the Fe concentration is 6.6 to 6.6. 22.2 atomic%. The Cr concentration of the γ—Ni (Cr) layer is 19.7 to 31.9 atomic%.

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

As the alloy base material 10, the Alloy-X base material shown in Table 1 was used. The surface of the test piece formed from this Alloy-X substrate was smooth-polished and degreased. Next, a plating layer having a total thickness of about 40 μm was formed in the same manner as in Example 1.

Next, the surface of the test piece was subjected to Cr diffusion treatment under the same conditions as in Example 3.

Next, the surface of the test piece was subjected to Al diffusion treatment under the same conditions as in Example 1.

A part of the base material / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 20A and 20B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG6 of the photograph shown in FIG. 20A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 20A and 20B, β-NiAl in which W (Cr) -based MPL layer, Cr-based MPL layer and Cr particles (white spots) are dispersed from the base material side on the upper end surface of the test piece via a transition layer. A layer was formed. Further, as can be seen from FIG. 20B, the W concentration of the W (Cr) -based MPL layer is 17.0 to 42.1 atomic%, the Cr concentration is 5.1 to 18.0 atomic%, and the Al concentration is 11.6 to 1. It has 23.3 atomic% and a Ni concentration of 33.6 to 44.8 atomic%. The Cr concentration of the Cr-based MPL layer is 52.0 to 73.3 atomic%. The Al concentration of the β—NiAl layer is 43.7 to 56.7 atomic%, and the Cr concentration is 1.0 to 11.4 atomic%.

(Example 5)
The fifth embodiment corresponds to the seventh embodiment.

The SUS310 substrate shown in Table 1 was used as the alloy substrate 10. The surface of the test piece formed from this SUS310 substrate was smooth-polished and degreased. Next, a plating layer having a total thickness of about 40 μm was formed in the same manner as in Example 2.

Next, the surface of the test piece was subjected to Cr diffusion treatment under the same conditions as in Example 3.

Next, the surface of the test piece was subjected to Al diffusion treatment under the same conditions as in Example 1.

A part of the base material / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 21A and 21B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line of the photograph shown in FIG. 21A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 21A and 21B, a Re (Cr) MPL layer, a Cr MPL layer, and an α-Cr-containing β-NiAl layer were formed on the upper end surface of the test piece from the substrate side via a transition layer. .. As can be seen from FIG. 21B, the Re concentration of the Re (Cr) -based MPL layer is 47.9 to 51.3 atomic%, the Cr concentration is 4.3 to 5.1 atomic%, and the Al concentration is 0.0 atom. %, Ni concentration is 36.1 to 36.9 atomic%, Cr concentration of Cr-based MPL layer is 8.5 to 80.3 atomic%, Al concentration is 1.0 to 7.1 atomic%, Re concentration is 0. It is 0.0 to 0.3 atomic%. The Al concentration of the β-NiAl layer is 23.0 to 39.7 atomic%, the Cr concentration is 4.1 to 61.4 atomic%, the Re concentration is 0.0 atomic%, and the Ni concentration is 2.8 to 54.3. Atomic%.

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

The SUS310 substrate shown in Table 1 was used as the metal substrate 10. The surface of the test piece formed from this SUS310 substrate was smooth-polished and degreased. Next, next, (Ni strike plating current density 0.5 A / cm ² 1 minute) → (Re (Ni) plating current density 0.06 A / cm ² 20 minutes) → (Ni (W) plating current density 0. 06A / cm ² 20 minutes) → (Ni plating current density 0.06A / cm ² 10 minutes) → (Co plating current density 0.06A / cm ² 10 minutes), Ni layer, Re (Ni) layer, Ni A plating layer in which the (W) layer, the Ni layer and the Co layer were laminated in this order was formed.

Next, the surface of the test piece was subjected to Al diffusion treatment under the same conditions as in Example 1.

After that, the test piece on which the plating layer was formed was heated in the air at 1100 ° C. for 1 hour for homogenization treatment.

A part of the test piece subjected to the homogenization treatment was cut, and the cross-sectional structure thereof was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 22A and 22B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 of the photograph shown in FIG. 22A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 22A and 22B, from the base material side on the upper end surface of the test piece, the Re-based MPL layer, the W-based MPL layer, the γ'-(Ni, Co) ₃ Al layer and β-CoAl via the transition layer. A layer was formed. An Al ₂ O ₃ layer is formed on the surface of the β-CoAl layer. As can be seen from FIG. 22B, the Re concentration of the Re-based MPL layer is 3 to 35 atomic%, and the W concentration of the W-based MPL layer is 1 to 27 atomic%. The Al concentration of the β-CoAl layer is 38 to 42 atomic%.

(Example 7)
The seventh embodiment corresponds to the ninth embodiment.

The SUS310 substrate shown in Table 1 was used as the metal substrate 10. The surface of the test piece formed from this SUS310 substrate was smooth-polished and degreased. Next, next, (Ni strike plating current density 0.5 A / cm ² 1 minute) → (Re (Ni) plating current density 0.06 A / cm ² 20 minutes) → (Ni (W) plating current density 0. 06A / cm ² 20 minutes) → (Ni plating current density 0.06A / cm ² 20 minutes) to form a plating layer in which the Ni layer, Re (Ni) layer, Ni (W) layer and Ni layer are laminated in order. Formed.

Next, the surface of the test piece was subjected to Al diffusion treatment under the same conditions as in Example 1.

After that, the test piece on which the plating layer was formed was heated in the air at 1100 ° C. for 1 hour for homogenization treatment.

A part of the test piece subjected to the homogenization treatment was cut, and the cross-sectional structure thereof was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. FIGS. 23A and 23B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 of the photograph shown in FIG. 23A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 23A and 23B, from the base material side on the upper end surface of the test piece, the Re-based MPL layer, the W-based MPL layer, the γ'-(Ni, Fe) ₃ Al layer and β-NiAl via the transition layer. A layer was formed. An Al ₂ O ₃ layer is formed on the surface of the β-NiAl layer. As can be seen from FIG. 23B, the Re concentration of the Re-based MPL layer is 3 to 37 atomic%, and the W concentration of the W-based MPL layer is 2 atomic%. The Al concentration of the β-NiAl layer is 40 to 42 atomic%.

(Comparative Example 1)
Comparative Example 1 is different from Example 1 in that FeAl was used as the Al vapor source during the Al diffusion treatment in Example 1, whereas Al was used as the Al vapor source during the Al diffusion treatment.

That is, first, as in Example 1, the SUS310 base material shown in Table 1 was used as the metal base material 10, and the Ni layer and the Ni (W) layer were sequentially laminated on the surface of the test piece formed of the SUS310 base material. A plating layer having a total thickness of about 40 μm was formed.

Next, the surface of the test piece was subjected to Al diffusion treatment. That is, the test piece on which the plating layer was formed was embedded in a mixed powder of Al: NH ₄ Cl: Al ₂ O ₃ = 15: 2: 83 (weight ratio) and heated at 1000 ° C. for 4 hours in an Ar + 3 vol% H ₂ atmosphere. By doing so, Al diffusion treatment was performed.

A part of the base material / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. FIGS. 24A and 24B show the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 of the photograph shown in FIG. 24A) measured by using the cross-sectional SEM photograph and EDX, respectively. As shown in FIGS. 24A and 24B, unlike Example 1, the Al-containing alloy layer (Al concentration is 56 to 56) in which W particles (white spots) are dispersed on the surface of the test piece from the substrate side via the transition layer. 67 atomic%) is formed, and the W-based MPL layer as shown in FIG. 16A is not formed. That is, when Al powder is used as an Al vapor source, an Al-containing alloy layer (β-NiAl phase and Ni 2Al ₃ phase) having a _high Al concentration of 50 atomic% or more is formed, and about 50 atoms are formed in the Ni—Al system. At an Al concentration of% or more, the intrinsic diffusion coefficient of Al is larger than that of Ni, so that the Al-containing alloy layer grows due to the inward diffusion of Al, so that an Al-containing alloy layer containing W or the like is formed. It is understood as a thing.

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

FIG. 25 shows the change in weight of the test pieces of Examples 1 and 3 measured after the lapse of a predetermined number of cycles, that is, the dependence of the amount of oxidation on the number of cycles. FIG. 25 also shows a similar cycle number dependence for the test piece (Comparative Example 2) formed from the SUS310 substrate for comparison.

From FIG. 25, when the oxidation resistance is compared by the number of cycles when the oxidation weight turns to decrease and the oxidation amount is 0, the test piece of Example 3 is about 2.5 as compared with the test piece of Comparative Example 2. It can be seen that the test piece of Example 1 is extended by about 4.5 times.

From the results of the above high-temperature oxidation test, a part of the base material / plating layer construction surface of the test pieces of Examples 1 and 3 after the lapse of the following cycles was cut, and the cross-sectional structure observation and the concentration distribution of each element were observed. The measurement was performed with an SEM-EDX device.

26A and 26B show the concentration distribution of each element measured by using the cross-sectional SEM photograph and EDX of the test piece of Example 1 after one cycle (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 26A). The measurement result is shown.

27A and B show the concentration distribution of each element measured using the cross-sectional SEM photograph and EDX of the test piece of Example 1 after 34 cycles (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 27A). The measurement result is shown.

28A and B show the concentration distribution of each element measured by using the cross-sectional SEM photograph and EDX of the test piece of Example 1 after 132 cycles (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 28A). The measurement result is shown. As shown in FIG. 28B, after 132 cycles, the Al concentration of the β—NiAl layer is in the range of 29.8 to 31.2 atomic%, and the W concentration is negligible. This is because W does not dissolve in the β-NiAl layer.

FIGS. 29A and 29B show the concentration distribution of each element measured by using the cross-sectional SEM photograph and EDX of the test piece of Example 1 after 608 cycles (concentration distribution along the analysis line LG1 in the photograph shown in FIG. 29A). The measurement result is shown.

FIGS. 30A and 30B show the concentration distribution of each element measured using the cross-sectional SEM photograph and EDX of the test piece of Example 3 after 608 cycles (concentration distribution along the analysis line LG2 in the photograph shown in FIG. 30A). The measurement result is shown.

As shown in FIGS. 29B and 30B, after 608 cycles, the Al concentration of the test piece of Example 1 was 3.4 to 3.9 atomic%, and the Al concentration of the test piece of Example 3 was 2.3 to 2. It is 9.9 atomic%. AlN is formed in each of the test pieces of Examples 1 and 3, and the W concentration is 2.1 to 2.6 atomic%.

[Dependence of test piece oxidation characteristics on metal substrate]
In order to investigate the dependence of the oxidation characteristics of the test piece on the metal substrate, a test piece was prepared by applying the same W-based MPL / β-NiAl coating to each of the seven types of metal substrates shown in Table 1.

That is, as the metal base material 10, Fe base material (Example 8), Ni base material (Example 9), SUS430 base material (Example 10), SUH446 base material (Example 11), SUS310 base material (Example 12). ), Alloy-X base material (Example 13), and FSX414 base material (Example 14), the surface of the test piece formed from these base materials was smooth-polished and degreased. Next, (Ni strike plating current density 0.5 A / cm ² thickness 1 μm) → (Ni plating current density 0.06 A / cm ² thickness 10 μm) → (Ni (W) plating current density 0.15 A / cm ² ) (Thickness 30 μm) → (Ni plating current density 0.06 A / cm ² thickness 20 μm) was performed to form a plating layer with a total thickness of about 60 μm in which the Ni layer, Ni (W) and Ni layers were laminated in order. ..

After that, the surface of the test piece was subjected to Al diffusion treatment under the same conditions as in Example 1.

A part of the base material / plating layer construction surface of the test piece was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. 31A and B, FIGS. 32A and B, 33A and B, 34A and B, 35A and B, 36A and B, 37A and B, respectively. The measurement results of the concentration distribution of each element measured using EDX (concentration distribution along the analysis lines of the photographs shown in FIGS. 31A, 32A, 33A, 34A, 35A, 36A, and 37A, respectively) are shown. show. As shown in FIGS. 31A and B, 32A and B, 33A and B, 34A and B, 35A and B, 36A and B, 37A and B, from the substrate side on the surface of each test piece. A W-based MPL layer and a β-NiAl layer were formed via the transition layer.

A high temperature oxidation test was performed on each of the test pieces of Examples 8 to 14. The method of the high temperature oxidation test is as described above. Oxidation was performed for 63 cycles.

After 63 cycles of oxidation, a part of the base material 10 / plating layer construction surface of each test piece of Examples 8 to 14 was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured by the SEM-EDX apparatus. rice field. 38A and B, 39A and B, 40A and B, 41A and B, 42A and B, 43A and B, 44A and B, respectively, are the test pieces of Examples 8 to 14 after 63 cycles of oxidation, respectively. Concentration distribution of each element measured using a cross-sectional SEM photograph and EDX (concentration distribution along the analysis lines of the photographs shown in FIGS. 38A, 39A, 40A, 41A, 42A, 43A, 44A, respectively. ) Is shown.

The metal substrate dependence of the amount of oxidation measured after 4 cycles and 63 cycles of each test piece of Examples 8 to 14 is shown in FIGS. 45 and 46, respectively. From FIGS. 45 and 46, the amount of oxidation of each test piece of Examples 8 to 14 with respect to the metal substrate is as follows.

Oxidation amount (mg / cm ² )
After 4 cycles After 63 cycles Example 8 Fe base material 1.5 × 10 ^-3 1.6 × 10 ^-3
Example 9 Ni base material 0.13 0.09
Example 10 SUS430 base material 6.0 × 10 ⁻²
Example 11 SUH446 base material 0.3
Example 12 SUS310 base material 0.8
Example 13 Alloy-X base material 0.8
Example 14 FSX414 base material 0.7

From these results, the coating composed of W-based MPL layer and β-NiAl layer is applied to Fe base material, Ni base material and Fe-containing alloy base material (SUS430 base material and SUH446 base material) from the initial stage of cycle oxidation. It can be seen that it shows excellent high temperature oxidation resistance. In particular, the Fe base material and the Ni base material maintain excellent high temperature oxidation resistance even after 63 cycles.

[Measurement of test piece strength]
The tensile strength and breaking strain of the test piece in which the W-based MPL layer and the β-NiAl layer were formed on the SUS310 substrate via the transition layer were measured at room temperature. However, for the formation of the W-based MPL layer and the β-NiAl layer, a Ni layer and a Ni (W) layer are formed on the SUS310 substrate as in Example 1 (Example 15), or the same as in Example 2. A Ni layer, a Ni (W) layer and a Ni layer were formed on the SUS310 substrate (Example 16). In the Al diffusion treatment, in both Examples 15 and 16, the test piece on which the plating layer was formed was embedded in a mixed powder of FeAl: NH ₄ Cl: Al ₂ O ₃ = 15: 2: 60 (weight ratio), and Ar + 3 vol% H. This was done by heating at 900 ° C. for 6 hours in _two atmospheres. For comparison, a test piece using the SUS310 base material itself (Comparative Example 3) and a SUS310 base material are heat-treated (the test piece is embedded in Al ₂ O ₃ powder and heated at 900 ° C. for 6 hours in an Ar + 3 vol% H ₂ atmosphere. The test piece (Comparative Example 4) that was subjected to () was also used. Table 2 shows the measurement results of tensile strength and breaking strain. From Table 2, the maximum stress is higher and the strain amount is lower in the test piece on which the W-based MPL layer and the β-NiAl layer are formed, as compared with the SUS310 base material test piece (Comparative Example 4) which has been subjected to only heat treatment. By forming the W-based MPL layer and the β-NiAl layer, the mechanical properties are enhanced.

[Creep strength of test piece]
The creep behavior of the test pieces of Examples 15 and 16 was investigated at 900 ° C., in the air, and at a stress of 30 MPa. As a result, the breaking time was 180 hours for the test pieces of Comparative Examples 3 and 4, and 160 to 190 hours for the test pieces having the W-based MPL layer and β-NiAl layer of Examples 15 and 16. .. As can be seen from this result, the breaking times of the test pieces of Examples 15 and 16 are the same as that of Comparative Examples 3 and 4, and the breaking times are the same W-based MPL layer and β-NiAl layer formed on the metal substrate 10. The rupture time of the metal substrate 10 was the same as that of the metal substrate 10, and no decrease in the creep rupture time was confirmed.

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

10 ... Metal substrate, 20 ... Transition layer, 30 ... W-based multipurpose alloy layer, 40 ... β-NiAl layer, 50, 70 ... Ni layer, 60 ... Ni (W) layer, 80 ... Re-based multipurpose alloy layer, 90 ... Ni (Re) layer, 100 ... W (Cr) -based multipurpose alloy layer, 110 ... γ-Ni (Cr) layer, 120 ... Re (Cr) -based multipurpose alloy layer, 130 ... Cr-based multipurpose alloy layer, 140 ... Cr Containing β-NiAl layer, 150 ... γ'-(Ni, Co) ₃ Al layer, 160 ... β-CoAl layer, 170 ... Re (Ni) layer, 180 ... Co layer

Claims (14)

With a metal base material
With the W-based or Re-based multipurpose alloy layer on the metal substrate,
With the Al and / or Cr-containing alloy layer on the multipurpose alloy layer,
The transition layer between the metal substrate and the multipurpose alloy layer,
Refractory metal member with. The refractory metal member according to claim 1, wherein the multipurpose alloy layer contains W and Ni, Co, Al, Cr, Re, and at least one element selected from the group consisting of the elements constituting the metal substrate. The refractory metal member according to claim 1, wherein the multipurpose alloy layer contains Re and Ni, Co, Al, Cr, W, and at least one element selected from the group consisting of the elements constituting the metal substrate. The refractory metal member according to any one of claims 1 to 3, wherein the Al and / or Cr-containing alloy layer is an Al-containing alloy layer. The refractory metal member according to claim 4, wherein the Al-containing alloy layer is composed of β _- NiAl, γ'-Ni 3Al, CoAl or FeAl. The refractory metal member according to any one of claims 1 to 3, wherein the Al and / or Cr-containing alloy layer is a Cr-containing alloy layer. The refractory metal member according to claim 6, wherein the Cr-containing alloy layer is made of a Ni—Cr based alloy. The refractory metal member according to claim 1, further comprising a Cr-based multipurpose alloy layer between the multipurpose alloy layer and the Al and / or Cr-containing alloy layer. Any one of claims 1 to 8, wherein the transition layer contains Ni, at least one element among the elements constituting the metal substrate, and at least one element among the elements constituting the multipurpose alloy layer. The refractory metal member described in the section. The heat-resistant metal member according to any one of claims 1 to 9, wherein the metal base material is made of Fe, Co, Ni, Fe-based alloy, Co-based alloy, or Ni-based alloy. A step of sequentially forming a Ni layer containing at least a Ni layer and a W or a Ni layer containing Re on a metal substrate by plating, and
By performing Al diffusion treatment or Cr diffusion treatment using FeAl or NiAl as the Al vapor source, a W-based or Re-based multipurpose alloy layer and an Al and / or Cr-containing alloy layer are applied onto the metal substrate via a transition layer. And the process of sequentially forming
A method for manufacturing a refractory metal member having. The method for manufacturing a refractory metal member according to claim 11, wherein a Ni layer containing W or a Ni layer containing Re is further formed by plating a Ni layer, a Co layer or a Ni layer containing Co. With a metal base material
With the W-based or Re-based multipurpose alloy layer on the metal substrate,
With the Al and / or Cr-containing alloy layer on the multipurpose alloy layer,
A high temperature device having a refractory metal member having a transition layer between the metal substrate and the multipurpose alloy layer. A step of sequentially forming a Ni layer containing at least a Ni layer and a W or a Ni layer containing Re on a metal substrate by plating, and
By performing Al diffusion treatment or Cr diffusion treatment using FeAl or NiAl as the Al vapor source, a W-based or Re-based multipurpose alloy layer and an Al and / or Cr-containing alloy layer are applied onto the metal substrate via a transition layer. A method for manufacturing a high-temperature device, which comprises a step of sequentially forming a heat-resistant metal member and a step of manufacturing a refractory metal member by executing.

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