JPWO2013061945A1 - Heat-resistant alloy member and manufacturing method thereof - Google Patents

Abstract

Even when used in an environment where a thermal cycle is added in a high-temperature corrosive atmosphere, cracking and peeling of the protective oxide film formed on the reservoir layer can be suppressed, and the amount of expensive Pt added to the reservoir layer A heat-resistant alloy member that does not require a significant reduction or addition and a manufacturing method thereof.
A diffusion barrier layer 40, a reservoir layer 20, and a stress relaxation layer 50 are sequentially laminated on the surface of the metal substrate 10 to constitute a heat resistant alloy member. The diffusion barrier layer 40 is made of an alloy containing Re. The reservoir layer 20 is made of an alloy containing Al. The stress relaxation layer 50 includes, for example, an oxide containing Zr, Y, O, and at least one metal selected from the group consisting of Ni, Al, Cr, Ti, Hf, Ta, W, Re, Co, and Mo. Made of ceramics. A protective oxide film is formed on the reservoir layer 20.
[Selection] Figure 4

Description

  The present invention relates to a heat-resistant alloy member and a method for manufacturing the same, and is particularly suitable for application to a heat-resistant alloy member used in an environment to which a heat cycle in which heating and cooling are repeated in a high-temperature corrosive atmosphere is added.

In order to improve heat resistance and corrosion resistance, high temperature apparatus members such as boiler heat transfer tubes are often used by forming a heat and corrosion resistant alloy film on the surface of a metal substrate. Examples of the heat-resistant and corrosion-resistant alloy film include diffusion aluminide coating and Ni—Cr alloy overlay coating, and protective oxidation such as alumina (Al ₂ O ₃ ) and chromia (Cr ₂ O ₃ ) on the surface thereof. A physical film is formed to protect the high temperature device member.

Also, in industrial micro gas turbines and gas turbines, an overlay coating of MCrAlY alloy (M = Ni, Co, Fe) is formed on the surface to protect the alloy members from high-temperature combustion gas, and protective Al ₂ is formed on the surface thereof. The alloy member is protected by forming an O ₃ film. Furthermore, in a jet engine, a Ni—Al alloy, a Ni—Al—Pt alloy with Pt added, or the like is used, and a protective Al ₂ O ₃ film is formed to protect the alloy member.

However, when the environment in which the high-temperature device member is used is an extremely high temperature of about 800 to 1300 ° C., elements (for example, Ni, Co, Fe, Ti, Mo, W, W) included in the metal base material constituting the high-temperature device member. Etc.) diffuse and move to the coating layer side, while elements (Al, Cr, etc.) added to the coating layer to form a protective oxide film diffuse and move to the metal substrate side. As a result of this, the concentration of Al, Cr, etc. in the coating layer decreases, and as a result, cracking or peeling of the protective oxide film (eg, Al ₂ O ₃ or Cr ₂ O ₃ ) formed on the surface of the coating layer proceeds. Alternatively, it changes to a non-protective oxide film (for example, NiO, NiAl ₂ O ₄ , NiCr ₂ O _4, etc.) and the protective performance of the coating layer is lost.

  On the other hand, in recent high-efficiency jet engines and gas turbines, the combustion gas temperature is being increased. Accordingly, air cooling and thermal barrier coating (TBC) are applied to alloy members such as turbine blades and stationary blades.

  This TBC is composed of at least two layers of a bond coat and a top coat. MCrAlY alloy (M = Ni, Co), Ni-Al alloy, Ni-Al-Pt alloy, etc. are used for the bond coat, and thermally grown oxide (Thermal Grown Oxide: TGO) is formed on the surface of the bond coat. Protects metal substrates from oxidative and corrosive environments. An oxide having low thermal conductivity is used for the top coat. An example is Yttria Stabilized Zirconia (YSZ). The YSZ of the top coat functions as a heat shielding layer against the high-temperature combustion gas, and maintains the metal substrate and the bond coat at a relatively low temperature by air-cooling the inside of the metal substrate.

The above coating layer and TBC bond coat contain a higher concentration of Al compared to the metal substrate, so during use at high temperatures, Al diffuses from the coating layer or bond coat to the metal substrate. Then, a secondary reaction zone (SRZ) is formed in the metal substrate to reduce the strength of the metal substrate. In addition, a decrease in the Al concentration of the coating layer or bond coat may result in non-protective oxide films (eg, NiAl ₂ O ₄ , NiO, etc.)
Or loss of TGO protection.

  In order to solve this problem, as a result of searching for a diffusion barrier layer that suppresses interdiffusion of elements between a metal substrate and a coating layer (reservoir layer) or a bond coat, the present inventors have found an alloy containing Re. It has been found that a phase (for example, a Re—Cr—Ni-based σ phase) has excellent diffusion barrier properties, and has proposed to use this as a diffusion barrier layer (see Patent Documents 1 to 8). That is, as shown in FIG. 1, conventionally, a reservoir layer 20 containing Al is laminated on a metal substrate 10, and a protective oxide film 30 is formed on the surface of the reservoir layer 20. As shown in FIG. 2, a diffusion barrier layer 40 is formed between the metal substrate 10 and the reservoir layer 20, and a protective oxide film 30 is formed on the surface of the reservoir layer 20. The diffusion barrier layer 40 has a conjugated composition relationship with the crystal phase constituting the metal substrate 10 and the reservoir layer 20 (or bond coat), and is considered to be thermodynamically stable. Thus, the function as a diffusion barrier layer can be maintained (see Non-Patent Documents 1 and 2). The present inventor refers to the diffusion barrier coating including the diffusion barrier layer 40 and the reservoir layer 20 and names the diffusion barrier coating system (Diffusion Barrier Coating System: DBC system) including the metal substrate 10 and the diffusion barrier coating. doing.

According to Non-Patent Documents 1 and 2, the DBC system is based on metal substrates (for example, second generation Ni-based single crystal superalloy (TMS-82), third generation single crystal superalloy (CMSX-4), fourth Generation single crystal superalloy (TMS-138), stainless steel (SUS310S), Ni-Cr-Mo alloy (Hastelloy-X) and Al reservoir layer (for example, Ni-Al-Cr alloy, Pt-added Ni-Cr-Al alloy) ) To effectively suppress interdiffusion of elements between the metal substrate and the Al reservoir layer and to form and maintain a protective oxide film (eg, Al ₂ O ₃ ).

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

T. Narita: Diffusion barrier coating system concept for high temperature applications, Canadian Metallurgical Quarterly, Vol. 50, No. 3 (2011), pp. 278-290 T. Narita: Compatible Coating System to Provide Long-Life and High-Reliability, Materials Science Forum, Vol.696 (2011), pp.12-27 Sudhangshu Bose, High Temperature Coatings, pp.171-172 (2007) Elsevier

  By the way, since a jet engine and a gas turbine frequently start and stop repeatedly, the turbine rotor blade and the stationary blade are subjected to rapid heating and cooling. For this reason, cracking and peeling of the protective oxide film formed on the coating layer proceed due to thermal stress due to a rapid temperature change. In TBC, the formation of cracks in the TGO layer, as well as cracks and delamination of the ceramic layer of the topcoat are problematic.

  On the other hand, in recent years, high efficiency has become essential for jet engines and gas turbines because of the reduction of carbon dioxide emissions. As one method for improving the efficiency, it is effective to increase the temperature of the combustion gas inlet (Turbine Inlet Temperature: TIT). However, the increase in TIT promotes the growth of the TGO layer in the protective oxide film or TBC, peeling of the oxide film due to a rapid temperature change during heating and cooling, cracking of the TGO layer, cracking of the top coat, It will promote peeling.

The present inventor has examined the effects of thermal cyclic oxidation on the adhesion, crack formation and delamination of protective oxide films (eg, Al ₂ O ₃ films) formed on DBC systems as metal substrates. A second generation Ni-based single crystal superalloy (CMSX-4) was used for detailed investigation. For comparison, an Al ₂ O ₃ film formed on a conventional coating layer was also examined.

As a result of the above thermal cycle oxidation test (for example, heating (kept at 1100 ° C. for 1 hour) and cooling (kept at room temperature for 20 minutes)), the Al ₂ O ₃ film was peeled off by 100 cycles in the conventional coating layer. In contrast to the phenomenon that occurred before, it has been found that a diffusion barrier coating composed of a diffusion barrier layer and a Ni—Cr—Al-based reservoir layer starts peeling at a higher cycle number of 150 to 200 cycles.

Furthermore, in Non-Patent Document 1, in a diffusion barrier coating composed of a diffusion barrier layer having a three-layer structure and a Pt-added Ni—Al—Pt-based reservoir layer, peeling of the Al ₂ O ₃ film is not observed up to 400 cycles. It has been reported.

From the above results, the Al ₂ O ₃ film formed on the DBC system has better adhesion, crack resistance, and resistance to the oxide film mainly composed of Al ₂ O ₃ formed on the conventional coating layer. It confirmed that it had peelability. Furthermore, it has been clarified that addition of Pt to the reservoir layer improves the adhesion resistance and peel resistance of Al ₂ O ₃ .

  However, for moving blades and stationary blades of next-generation jet engines, it is desirable to develop a coating that can cope with severe thermal cycle oxidation accompanying an increase in TIT, and to further reduce or eliminate the addition of expensive Pt.

  Therefore, the problem to be solved by the present invention is that cracking and peeling of the protective oxide film formed on the reservoir layer can be suppressed even when used in an environment where a thermal cycle is added in a high temperature corrosive atmosphere. And it is providing the heat-resistant alloy member which does not require the significant reduction of the addition amount of expensive Pt to a reservoir layer, or addition, and its manufacturing method.

  The present inventor has intensively studied to solve the above problems. As a result, when a diffusion barrier layer is provided between the metal substrate and the reservoir layer and a stress relaxation layer made of an oxide ceramic such as YSZ is provided on the reservoir layer, the thermal cycle is performed in a high-temperature corrosive atmosphere. It has been found that even when used in an added environment, cracking and peeling of the protective oxide film formed on the reservoir layer can be suppressed. This is an effect that can hardly be obtained when only the diffusion barrier layer or the stress relaxation layer is used, and is an unexpected effect.

The present invention has been devised as a result of intensive studies based on the above-mentioned knowledge obtained independently by the present inventor.
That is, in order to solve the above problems, the present invention provides:
A metal substrate;
A heat-resistant alloy member having a diffusion barrier layer, a reservoir layer, and a stress relaxation layer made of oxide ceramics laminated in order on the surface of the metal substrate.

In addition, this invention
Forming a diffusion barrier layer on the surface of the metal substrate;
Forming a reservoir layer on the diffusion barrier layer;
And a step of forming a stress relaxation layer made of an oxide ceramic on the reservoir layer.

  The oxide ceramic constituting the stress relaxation layer typically contains at least one metal different from the metal constituting the oxide ceramic, for example, a metal that contributes to a decrease in the thermal conductivity of the oxide ceramic. Examples of the at least one metal include nickel (Ni), aluminum (Al), chromium (Cr), titanium (Ti), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), and cobalt. Although it is at least 1 type of metal chosen from the group which consists of (Co) and molybdenum (Mo), it is not limited to this. The content of these metals is selected as necessary, but the total content is generally greater than 0% and 6% or less, typically 1% or more and 5% or less, more typically 2%. % Or more and 5% or less.

  In the present invention, as the metal base material, any conventionally known material can be used and is selected as necessary. Specifically, for example, a Ni-base superalloy, stainless steel, Ni- An alloy made of a Cr—Mo base alloy (Hastelloy alloy), a Co base alloy, or the like can be used. The diffusion barrier layer is for suppressing interdiffusion of elements contained in the metal substrate and the reservoir layer, and includes an alloy containing Re, for example, a Re—Cr—Ni alloy, Re—W—Cr—. It consists of Ni alloy, Re-Cr-Mo-Ni alloy, etc. The reservoir layer forms and maintains a protective oxide film, and has the ability to regenerate when the protective oxide film peels off. Specifically, for example, an alloy containing Al or further Cr For example, Ni—Al alloy, Ni—Pt—Al alloy, MCrAlY alloy (M is at least one metal selected from the group consisting of Fe, Ni and Co). The stress relaxation layer prevents the protective oxide film formed on the reservoir layer side of the interface between the reservoir layer and this stress relaxation layer from cracking or peeling due to thermal stress generated during heating and cooling. It is for preventing. The stress relaxation layer is preferably one that is thermally stable at a high temperature (for example, 800 ° C. or higher and 1700 ° C. or lower), has low reactivity with the combustion gas atmosphere, and has low thermal conductivity. The stress relaxation layer includes, for example, oxide ceramics containing zirconium, yttrium and oxygen, oxide ceramics containing aluminum, yttrium and oxygen, oxide ceramics containing aluminum, lanthanum and oxygen, aluminum and samarium, Oxide ceramics containing oxygen, oxide ceramics containing cerium and oxygen, oxide ceramics containing thorium and oxygen, and the like. The oxide ceramic containing zirconium, yttrium and oxygen is most preferably yttria stabilized zirconia (YSZ). The thickness of the stress relaxation layer is appropriately selected as necessary. For example, the lower limit is the same thickness as that of the protective oxide film, for example, 1 μm. The upper limit of the thickness of the stress relaxation layer is not particularly limited, but is generally 200 μm. That is, the thickness of the stress relaxation layer is generally 1 μm or more and 200 μm or less, but from the viewpoint of obtaining a sufficient stress relaxation effect, it is preferably 3 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm. Hereinafter, it is more preferably 3 μm or more and 20 μm or less. From the viewpoint of obtaining the effect of reducing thermal conductivity in addition to the effect of stress relaxation, the stress relaxation layer is preferably a low-density porous material. For example, when the stress relaxation layer is made of YSZ, the thermal conductivity depends on the porosity of YSZ, from 1.1 W / mK at a porosity of about 7.5% to about 0.1 at a porosity of about 15%. It changes in a range of 77 W / mK (see, for example, pp. 171-172 of Non-Patent Document 3).

  As a method for forming the diffusion barrier layer, the reservoir layer, and the stress relaxation layer, various conventionally known methods can be used and are selected as necessary. As a method for forming the stress relaxation layer, for example, at least one method selected from the group consisting of an electron beam evaporation method, an electrophoresis method, a slurry coating method, and a thermal spraying method is used. In the case of forming a porous stress relaxation layer, an electrophoresis method is preferably used.

  Although a heat-resistant alloy member is not specifically limited, Specifically, a turbine moving blade and a stationary blade, a jet engine using them, an industrial gas turbine, a micro gas turbine, etc. are mentioned, for example.

  According to this invention, a thermal cycle is added in a high-temperature corrosive atmosphere due to the synergistic effect of providing a diffusion barrier layer between the metal substrate and the reservoir layer and providing a stress relaxation layer on the reservoir layer. Even when used in a dry environment, cracking and peeling of the protective oxide film formed on the reservoir layer can be effectively suppressed. Further, the amount of expensive Pt added to the reservoir layer can be greatly reduced, or the addition of Pt is not necessary.

It is sectional drawing which shows the structure of the conventional high temperature apparatus member. It is sectional drawing which shows the structure of the conventional high temperature apparatus member using a diffusion barrier layer. It is sectional drawing which shows the structure of the conventional high temperature apparatus member using TBC. It is sectional drawing which shows the structure of the heat-resistant alloy member by one embodiment of this invention. It is sectional drawing which shows the state in which the protective oxide film was formed in the reservoir layer in the heat-resistant alloy member by one Embodiment of this invention. 3 is a drawing-substituting photograph showing a cross-sectional structure of the heat-resistant alloy member of Example 1. FIG. 7 is a drawing substitute photograph showing an enlarged structure of a portion where a diffusion barrier layer is sandwiched between a metal substrate and a reservoir layer in the heat resistant alloy member shown in FIG. 6. It is a drawing substitute photograph which shows the cross-section of the heat-resistant alloy member of the comparative example 1 which does not form a stress relaxation layer. 2 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Example 1. FIG. It is a basic diagram which shows the mass increase with respect to the cycle number of the heat-resistant alloy member of Example 1 which performed thermal cycle oxidation on two conditions. It is a basic diagram which shows the change of the density | concentration of each element with respect to the cycle number of the heat-resistant alloy member of Example 1 which performed thermal cycle oxidation on the conditions 1. FIG. It is a basic diagram which shows the change of the density | concentration of each element with respect to the cycle number of the heat-resistant alloy member of the comparative example 1 which performed thermal cycle oxidation on the conditions 1. FIG. It is a basic diagram which shows the change of the density | concentration of each element with respect to the cycle number of the heat-resistant alloy member of Example 1 which performed thermal cycle oxidation on the conditions 2. FIG. It is a basic diagram which shows the change of the density | concentration of each element with respect to the cycle number of the heat-resistant alloy member of the comparative example 1 which performed thermal cycle oxidation on the conditions 2. FIG. 6 is a cross-sectional view showing a configuration of a heat resistant alloy member of Comparative Example 4. FIG. It is a basic diagram which shows the mass increase with respect to the cycle number of the heat-resistant alloy member of Example 2, 3 which performed thermal cycle oxidation on the conditions 1, and the comparative example 4. FIG. 6 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Example 2. FIG. 4 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Example 3. FIG. 6 is a drawing-substituting photograph showing a test piece subjected to thermal cycle oxidation in Comparative Example 4. FIG. It is a basic diagram which shows the change of the density | concentration of each element with respect to the cycle number of the heat-resistant alloy member of Example 2 which performed thermal cycle oxidation on the conditions 1. FIG.

Hereinafter, modes for carrying out the invention (hereinafter simply referred to as “embodiments”) will be described.
FIG. 4 shows a heat-resistant alloy member according to one embodiment. As shown in FIG. 1, in this heat-resistant alloy member, a diffusion barrier layer 40, a reservoir layer 20, and a stress relaxation layer 50 are laminated on the surface of a metal base 10 in order.

  Examples of the metal base 10 include, but are not limited to, a Ni base superalloy, a stainless steel, a Ni—Cr—Mo base alloy (Hastelloy alloy), a Co base alloy, and the like.

  The diffusion barrier layer 40 is made of an alloy containing Re, for example, a Re—Cr—Ni alloy, a Re—W—Cr—Ni alloy, a Re—Cr—Mo—Ni alloy, or the like.

  The reservoir layer 20 is an alloy containing an element (Al, Cr, etc.) that forms a protective oxide film, such as a Ni—Al alloy, a Ni—Pt—Al alloy, or a MCrAlY alloy (M is made of Fe, Ni, and Co). At least one metal selected from the group).

  The stress relaxation layer 50 is an oxide ceramic, for example, an oxide ceramic containing Zr, Y and O, an oxide ceramic containing Al, Y and O, an oxide ceramic containing Al, La and O, It consists of oxide ceramics containing Al, Sm and O, oxide ceramics containing Ce and O, oxide ceramics containing Th and O, and the like. The thickness of the stress relaxation layer 50 is 1 μm or more and 200 μm or less, preferably 3 μm or more and 100 μm or less. The oxide ceramic constituting the stress relaxation layer 50 is typically at least one metal different from the metal constituting the oxide ceramic, for example, Ni, Al, Cr, Ti, Hf, Ta, W, Re, It contains at least one metal selected from the group consisting of Cr and Mo. A specific example of the oxide ceramic constituting the stress relaxation layer 50 is an oxide ceramic containing Zr, Y and O. Typically, this oxide ceramic is composed of this oxide ceramic. In addition to Zr and Y to be contained, it contains at least one metal selected from the group consisting of Ni, Al, Cr, Ti, Hf, Ta, W, Re, Cr and Mo. As a typical example, the oxide ceramic constituting the stress relaxation layer 50 is at least one metal selected from the group consisting of Ni, Al, Cr, Ti, Hf, Ta, W, Re, Cr, and Mo. Containing YSZ.

FIG. 5 shows a state in which a protective oxide film 30 such as Al ₂ O ₃ is formed on the reservoir layer 20. The thickness of the protective oxide film 30 is typically about several μm, for example, but is not limited thereto.

  In order to manufacture this heat-resistant alloy member, the diffusion barrier layer 40, the reservoir layer 20, and the stress relaxation layer 50 are sequentially formed on the surface of the metal substrate 10 by a conventionally known method.

  In one typical manufacturing method, this heat-resistant alloy member is manufactured as follows. That is, first, a Re film is formed on the surface of the metal substrate 10 by a plating method. Next, a Cr diffusion treatment (chromizing treatment) is performed on the Re film, and then a high temperature heat treatment is performed. Thus, the diffusion barrier layer 40 is formed. Next, a Ni film is formed on the diffusion barrier layer 40 by plating. Next, an Al diffusion process (aluminizing process) is performed on the Ni film. Thus, the reservoir layer 20 made of a Ni—Al alloy is formed. Thereafter, a stress relaxation layer 50 made of an oxide ceramic such as YSZ is formed on the reservoir layer 20 by electron beam evaporation.

[Example 1]
Example 1 will be described.
A round bar made of Ni-based single crystal superalloy (CMSX-4) having a diameter of 12.5 mm is cut perpendicularly to the central axis to form a disc having a thickness of about 1.5 mm. did. The surface of the disk-shaped metal substrate 10 was polished with No. 220 SiC water-resistant abrasive paper and then degreased by ultrasonic cleaning in acetone.

Next, a Ni film is formed on the entire surface of the metal base material 10 (both sides and side surfaces of the metal base material 10) by electrolytic plating, and then washed with distilled water, followed by electrolytic plating on the Ni film. Thus, a Re (Ni) film was formed. The formation of the Ni film and the Re (Ni) film was repeated three times to form a total of three layers of Ni / Re (Ni) films. The thicknesses of the Ni film and the Re (Ni) film were each about 2 μm. Next, Cr diffusion treatment (chromizing treatment) was performed on the Ni / Re (Ni) film as follows. The metal substrate 10 on which the Ni / Re (Ni) film was formed was placed in an alumina crucible and embedded in a Cr + Al ₂ O ₃ + NH ₄ Cl mixed powder. The mixed powder is mixed in a weight ratio of Cr: alumina: NH ₄ Cl = 1: 3: 0.1. Next, the mixture was heated in an argon (Ar) gas atmosphere, held at 800 ° C. for 2 hours, and then cooled in the furnace. Thereafter, the metal substrate 10 was buried in a mixed powder of Ni-5Cr-15Al alloy powder + Al ₂ O ₃ , heated in vacuum (10 ⁻³ Pa) at 1280 ° C. for 2 hours, and then cooled in the furnace. Thus, the diffusion barrier layer 40 was formed on the entire surface of the disk-shaped metal substrate 10 (both surfaces and side surfaces of the metal substrate 10).

Next, after a Ni film having a thickness of 20 μm is formed on the diffusion barrier layer 40 thus formed by plating, the Ni film is buried in an Al + NH ₄ Cl + Al ₂ O ₃ mixed powder, and then at 700 ° C. for 30 minutes in an Ar atmosphere. Al diffusion permeation treatment was performed. Thus, the reservoir layer 20 was formed on the entire diffusion barrier layer 40 on the surface of the disk-shaped metal substrate 10 (both surfaces and side surfaces of the metal substrate 10).

Next, a stress made of YSZ on the reservoir layer 20 is formed on one surface of the metal substrate 10 by electron beam evaporation using YSZ (ZrO ₂ ceramics added with 8 mol% Y ₂ O ₃ ) as an oxide ceramic. A relaxation layer 50 was formed. The thickness of the stress relaxation layer 50 was about 200 μm. At this time, the stress relaxation layer 50 was not formed on the other surface and side surface of the metal substrate 10. As a result, the stress relaxation layer 50 made of YSZ is exposed on one surface of the metal substrate 10, and the reservoir layer 20 is exposed on the other surface and side surfaces. Hereinafter, the metal substrate 10 in which the stress relaxation layer 50 is formed on one surface of the metal substrate 10 is referred to as a test piece. The surface side of the test piece on which the stress relaxation layer 50 is formed is the heat resistant alloy member of Example 1, and the other surface side where the stress relaxation layer 50 is not formed and the reservoir layer 20 is exposed is the heat resistant alloy member of Comparative Example 1. It is.

  FIG. 6 shows a cross-sectional scanning electron micrograph (cross-sectional SEM photograph) of the surface side of the test piece on which the stress relaxation layer 50 is formed, that is, the heat-resistant alloy member of Example 1. As shown in FIG. 6, a diffusion barrier layer 40, a reservoir layer 20, a protective oxide film 30 and a stress relaxation layer 50 are formed in this order on the metal substrate 10. A protective copper (Cu) plating layer 999 was formed on the surface of the stress relaxation layer 50 in taking a cross-sectional SEM photograph.

The concentration (atomic%) of each element at the position (001 to 007) designated on the photograph of FIG. 6 was measured using a SEM-EDAX apparatus (scanning electron microscope-energy dispersive spectrometer). Table 1 shows the results.

In the cross-sectional SEM photograph shown in FIG. 6, the photograph which expanded the part by which the diffusion barrier layer 40 was pinched | interposed between the metal base material 10 and the reservoir layer 20 is shown in FIG. Table 2 shows the concentration (atomic%) of each element analyzed along the line shown in FIG.

FIG. 8 shows a cross-sectional SEM photograph of the heat-resistant alloy member of Comparative Example 1, in which the stress relaxation layer 50 of this test piece is not formed and the reservoir layer 20 is exposed. As shown in FIG. 8, a diffusion barrier layer 40, a reaction layer 41, a reservoir layer 20, and a protective oxide film 30 are sequentially formed on the metal substrate 10. A protective copper (Cu) plating layer 999 was formed on the surface of the protective oxide film 30 in taking a cross-sectional SEM photograph. Table 3 shows the concentration (atomic%) of each element analyzed along the line shown in FIG.

In order to confirm the effect of providing the stress relaxation layer 50 on the reservoir layer 20 in the heat-resistant alloy member of Example 1, evaluation was performed by a thermal cycle oxidation test. In the thermal cycle oxidation test, a test piece is directly inserted into an electric furnace maintained at a predetermined temperature in the air, and after a predetermined time has passed, the test piece is pulled out of the furnace and cooled. More specifically, the thermal cycle oxidation test was performed under the following two conditions.
Condition 1: Hold for 1 hour at a temperature of 1100 ° C. and hold for 20 minutes at room temperature alternately.
Condition 2: 1 hour holding at a temperature of 1200 ° C. and 20 minutes holding at room temperature are alternately performed.

  After the thermal cycle oxidation test, the weight change of the test piece was measured, the concentration of each element was measured with an X-ray element analyzer (oxygen O cannot be analyzed), and the test piece was photographed with an optical camera.

FIG. 9A shows a photograph of the appearance of the heat-resistant alloy member of Example 1 on one surface side where the stress relaxation layer 50 of the test piece after applying 700 cycles of thermal cycle oxidation under condition 1, is exposed. FIG. 9B shows an appearance photograph of the other surface side of the test piece where the reservoir layer 20 is exposed, that is, the surface and side surfaces of the heat-resistant alloy member of Comparative Example 1. The portion enclosed by the square in FIG. 9A corresponds to the portion indicated by the arrow in FIG. 9B. The concentration (atomic%) of each element of points (1) to (4) described in the photograph of FIG. 9A was measured. The results are shown in Table 4.

  FIG. 10 shows changes in the mass increase of the heat-resistant alloy member with respect to the square root of the number of cycles when thermal cycle oxidation is added under conditions 1 and 2. As can be seen from FIG. 10, when thermal cycle oxidation is added under condition 1, the number of cycles is about 200 (point C indicated by an arrow), and when thermal cycle oxidation is added under condition 2, the number of cycles is about 30 (arrow). The decrease in the amount of oxidation started at the points S and C shown in FIG.

  FIG. 11 shows the results of measuring the concentration of each element on the surface of the stress relaxation layer 50 with respect to the square root of the number of cycles when thermal cycle oxidation is added under the condition 1 using an X-ray element analyzer. Although not shown in FIG. 11, the Zr and Y concentrations are in agreement with the results shown in Table 4, and change with the number of cycles is small. As can be seen from FIG. 11, the concentrations of Al and Ni, which were hardly observed in the initial stage of oxidation, increased as the number of cycles increased.

  FIG. 12 shows the concentration of each element on the surface of the reservoir layer 20 (including the protective oxide film 30) with respect to the square root of the number of cycles when thermal cycle oxidation was added under the condition 1 was measured with an X-ray element analyzer. Results are shown. As can be seen from FIG. 12, Al and Ni are observed at the initial stage of oxidation, and the Al concentration tends to increase and the Ni concentration tends to decrease as the number of cycles increases. However, at the point C indicated by the arrow in FIG. 12, the Al concentration started to decrease, the Ni concentration started to increase, and other elements were also detected.

  FIG. 13 shows the results of measuring the concentration of each element on the surface of the stress relaxation layer 50 with respect to the square root of the number of cycles when thermal cycle oxidation is added under the condition 2 with an X-ray element analyzer. As can be seen from FIG. 13, the concentrations of Al and Ni, which were hardly observed in the initial stage of oxidation, increased as the number of cycles increased.

  FIG. 14 shows the result of measuring the concentration of each element on the surface of the reservoir layer 20 with respect to the square root of the number of cycles when thermal cycle oxidation is added under condition 2, using an X-ray element analyzer. As can be seen from FIG. 14, Al and Ni are observed at the initial stage of oxidation, and the Al concentration tends to increase and the Ni concentration tends to decrease as the number of cycles increases. However, at the point C indicated by the arrow in FIG. 14, the Al concentration started to decrease, the Ni concentration started to increase, and other elements were also detected. This means that peeling of the protective oxide film 30 from the reservoir layer 20 has started at point C.

The above results are summarized as follows.
<Condition 1>
(1) In the conventional DBC system (Comparative Example 1), peeling occurs in part of the protective oxide film (Al ₂ O ₃ film) around 200 cycles, and becomes more noticeable as the number of cycles increases.
(2) On the other hand, on the surface (Example 1) provided with the stress relaxation layer 50 made of YSZ of the test piece, YSZ has good adhesion with the protective oxide film 30 made of Al ₂ O ₃ , and Also, it does not peel off by heating and cooling.
(3) As the number of cycles increases, Al and Ni are observed on the surface of the stress relaxation layer 50 made of YSZ. The Al and Ni pass through the stress relaxation layer 50 made of YSZ from the reservoir layer 20. It is thought that it has diffused and reached the surface.

<Condition 2>
Although it is the same as (1) to (3) of the above condition 1, the peeling of the protective oxide film 30 from the reservoir layer 20 starts in a shorter time, and the stress relaxation layer 50 made of YSZ Al and Ni were observed on the surface in a shorter time.

[Example 2]
Example 2 will be described.
In Example 2, the Ar gas atmosphere is heated after the metal substrate 10 on which the Ni / Re (Ni) film is formed is placed in an alumina crucible and embedded in a mixed powder of Cr + Al ₂ O ₃ + NH ₄ Cl. The condition is 800 ° C. for 3 hours, and the condition of heating in vacuum after the metal substrate 10 is buried in the mixed powder of Ni-5Cr-15Al alloy powder + Al ₂ O ₃ is 1300 ° C. for 2 hours. Except that, a test piece was formed in the same manner as in Example 1. The surface side of the test piece on which the stress relaxation layer 50 is formed is the heat resistant alloy member of Example 2, and the other surface side where the stress relaxation layer 50 is not formed and the reservoir layer 20 is exposed is the heat resistant alloy of Comparative Example 2. It is a member.

[Example 3]
Example 3 will be described.
In Example 3, a test piece was formed in the same manner as in Example 2. The surface side of the test piece on which the stress relaxation layer 50 is formed is the heat resistant alloy member of Example 3, and the other surface side where the stress relaxation layer 50 is not formed and the reservoir layer 20 is exposed is the heat resistant alloy of Comparative Example 3. It is a member.

[Comparative Example 4]
Comparative example 4 will be described.
In Comparative Example 4, a test piece was formed in the same manner as in Example 1 except that the reservoir layer 20 was not formed and the stress relaxation layer 50 was formed directly on the diffusion barrier layer 40. The cross-sectional structure of this test piece is shown in FIG.

  FIG. 16 shows a change in mass increase of the heat-resistant alloy members of Examples 2 and 3 and Comparative Example 4 with respect to the square root of the number of cycles when thermal cycle oxidation is added under condition 1. From the cycle number dependency of the oxidation amount shown in FIG. 16, when thermal cycle oxidation is added under condition 1, the oxidation amount initially increases with the cycle number, but variation or decrease is observed in the middle. This is because the oxidation of the surface or end surface on which the stress relaxation layer 50 is not formed becomes significant, and a part of the oxide film is peeled off. This critical cycle number is 225 cycles in the second embodiment and 182 cycles in the third embodiment. 17A-E (FIG. 17A is before oxidation, FIG. 17B is after 1 cycle, FIG. 17C is after 225 cycles, FIG. 17D is after 450 cycles, and FIG. 17E is after 505 cycles) and FIGS. Before oxidation, as shown in FIG. 18B after 1 cycle, FIG. 18C after 182 cycles, and FIG. 18D after 412 cycles), from the surface morphology photograph of the stress relaxation layer 50 made of the YSZ layer, 450 cycles in Example 2, In Example 3, in 412 cycles, no separation of the stress relaxation layer 50 is observed. However, in Example 2, the stress relaxation layer 50 was peeled in 505 cycles.

In the result of Example 1 shown in FIG. 10, the critical cycle number is about 200 cycles, which matches the values of Examples 2 and 3. However, in Example 1, no peeling occurred yet even after 700 cycles. These differences are likely to be within experimental error. The amount of oxidation at the critical cycle number was 2 mg / cm ² in Example 1, whereas it was about 0.6 mg / cm ² in Examples 2 and 3.

  In Comparative Example 4, a decrease in the oxidation amount was observed from the first cycle due to the cycle number dependency of the oxidation amount shown in FIG. This is because, in Comparative Example 4, since the reservoir layer 20 is not formed, the diffusion barrier layer 40 is directly oxidized, so that oxidation of the surface or the end surface on which the stress relaxation layer 50 is not formed proceeds rapidly. This is because a non-protective oxide film (which will be described later is due to a sublimable Re oxide) is formed, and a part thereof is peeled off. On the other hand, as shown in FIGS. 19A to 19D (FIG. 19A is before oxidation, FIG. 19B is after one cycle, FIG. 19C is after 100 cycles, and FIG. 19D is after 167 cycles), the surface morphology of the stress relaxation layer 50 composed of the YSZ layer From the photograph, in Comparative Example 4, peeling of the stress relaxation layer 50 is not observed in 100 cycles. However, peeling of the stress relaxation layer 50 occurred in 167 cycles.

From the above results, the following can be understood.
In Examples 2 and 3, the protective oxide film 30 made of Al ₂ O ₃ is formed between the reservoir layer 20 and the stress relaxation layer 50 and has the structure shown in FIG. The peel resistance of the protective oxide film 30 can be improved (twice or more as the number of cycles).

  In Comparative Example 4, as shown in FIG. 15, the reservoir layer 20 that forms the protective oxide film is not formed. Therefore, the protective oxide film is peeled off from the initial stage of the thermal cycle oxidation on the surface where the stress relaxation layer 50 is not formed. On the other hand, the stress relieving layer 50 was in sound contact with each other, and peeling was observed after 167 cycles. Thus, even in a diffusion barrier coating in which the reservoir layer 20 is not formed, the stress relaxation layer 50 can significantly improve the peel resistance of the protective oxide film 30 (100 times or more as the number of cycles).

In Comparative Example 4, the stress relaxation layer 50 showed excellent peeling resistance, which is considered as follows. That is, the diffusion barrier layer 40 contains (20-40) atomic% Cr and 20 atomic% Ni in addition to Re, and a Cr ₂ O ₃ or NiCr ₂ O ₄ film is formed. It is considered that the formation of the non-protective oxide vapor of Re (for example, Re ₂ O ₇ ) is suppressed by the stress relaxation layer 50 made of

  As a result of analyzing the surface of the stress relaxation layer 50 made of the YSZ layer with an X-ray elemental analyzer, it was found that the concentration of Al increased with an increase in the number of oxidation cycles, as shown in FIG. Such an increase in Al concentration is also shown in FIG. It is considered that this Al reaches the surface after the Al of the NiAl alloy constituting the reservoir layer 20 is oxidized and passes through the stress relaxation layer 50 made of a YSZ layer having a thickness of 50 to 150 μm. Until now, there is no report about Al which moves in such a YSZ layer. Further, this increase in Al concentration seems to be related to the start of peeling of the YSZ layer.

  Here, the difference between this heat-resistant alloy member and the conventional thermal barrier coating (TBC) will be described. FIG. 3 shows a conventional TBC. As shown in FIG. 3, a bond coat layer 60, a protective oxide film 30, and a top coat layer 70 made of ceramic are sequentially laminated on the surface of the metal substrate 10. As the topcoat layer 70, an oxide having a low thermal conductivity, such as YSZ, is used, and its thickness is generally 250 μm to 1000 μm, and in many applications, it is necessary to have a thickness of ˜1000 μm. (For example, see pp. 170-171 of Non-Patent Document 3.) In this case, YSZ constituting the top coat layer 70 functions as a heat shield layer against high-temperature combustion gas, and the inside of the metal substrate 10 is air-cooled, so that the metal substrate 10 and the bond coat layer 60 are relatively It is kept at a low temperature. What is important here is that the diffusion barrier layer 40 is not formed between the metal substrate 10 and the bond coat layer 60. For this reason, even if the top coat layer 70 made of YSZ is formed in the same manner as the stress relaxation layer 50, the protective oxide film 30 formed on the bond coat layer 60 can be prevented from cracking or peeling. In other words, the top coat layer 70 cannot be prevented from cracking or peeling.

  As described above, according to the heat-resistant alloy member according to this embodiment, the diffusion barrier layer 40 made of an alloy containing Re between the metal substrate 10 and the reservoir layer 20 made of an alloy containing Al or Cr. And the stress relaxation layer 50 made of oxide ceramics such as YSZ is provided on the reservoir layer 20, so that the reservoir layer can be used even when used in an environment where a thermal cycle is added in a high temperature corrosive atmosphere. The protective oxide film 30 formed on 20 can be very effectively prevented from cracking and peeling. Moreover, it is not necessary to add expensive Pt to the reservoir layer 20, and even if it is added, the amount added can be significantly reduced. The heat-resistant alloy member is suitable for application to, for example, a moving blade and a stationary blade of a turbine, a jet engine using this turbine, an industrial gas turbine, and the like.

  Although one embodiment and example of the present invention have been specifically described above, the present invention is not limited to the above-described embodiment and example, and various types based on the technical idea of the present invention. Deformation is possible.

DESCRIPTION OF SYMBOLS 10 Metal base material 20 Reservoir layer 30 Protective oxide film 40 Diffusion barrier layer 41 Reaction layer 50 Stress relaxation layer 60 Bond coat layer 70 Top coat layer 999 ... Copper plating layer

Claims (17)

A metal substrate;
A heat-resistant alloy member having a diffusion barrier layer, a reservoir layer, and a stress relaxation layer made of oxide ceramics laminated in order on the surface of the metal substrate.   The heat-resistant alloy member according to claim 1, wherein the diffusion barrier layer is made of an alloy containing rhenium.   The heat-resistant alloy member according to claim 1 or 2, wherein the oxide ceramic contains at least one kind of metal different from the metal constituting the oxide ceramic.   The heat-resistant alloy member according to claim 3, wherein the at least one metal is at least one metal selected from the group consisting of nickel, aluminum, chromium, titanium, hafnium, tantalum, tungsten, rhenium, cobalt, and molybdenum.   The heat-resistant alloy member according to any one of claims 1 to 4, wherein the stress relaxation layer has a thickness of 1 µm to 200 µm.   The heat-resistant alloy member according to any one of claims 1 to 5, wherein the reservoir layer is made of an alloy containing aluminum.   The heat-resistant alloy member according to any one of claims 1 to 6, wherein the oxide ceramic contains at least zirconium, yttrium, and oxygen.   The heat-resistant alloy member according to claim 7, wherein the oxide ceramic is yttria-stabilized zirconia. Forming a diffusion barrier layer on the surface of the metal substrate;
Forming a reservoir layer on the diffusion barrier layer;
And a step of forming a stress relaxation layer made of oxide ceramics on the reservoir layer.   The method for producing a heat-resistant alloy member according to claim 9, wherein the diffusion barrier layer is made of an alloy containing rhenium.   The method for producing a heat-resistant alloy member according to claim 9 or 10, wherein the oxide ceramic contains at least one kind of metal different from the metal constituting the oxide ceramic.   The method for producing a heat-resistant alloy member according to claim 11, wherein the at least one metal is at least one metal selected from the group consisting of nickel, aluminum, chromium, titanium, hafnium, tantalum, tungsten, rhenium, cobalt, and molybdenum. .   The method for producing a heat-resistant alloy member according to any one of claims 9 to 12, wherein the stress relaxation layer has a thickness of 1 µm to 200 µm.   The method for producing a heat-resistant alloy member according to any one of claims 9 to 13, wherein the reservoir layer is made of an alloy containing aluminum.   The method for producing a heat-resistant alloy member according to any one of claims 9 to 14, wherein the oxide ceramic contains at least zirconium, yttrium, and oxygen.   The method for producing a heat-resistant alloy member according to claim 15, wherein the oxide ceramic is yttria-stabilized zirconia.   The stress relaxation layer is formed by at least one method selected from the group consisting of an electron beam evaporation method, an electrophoresis method, a slurry coating method, and a thermal spraying method. Manufacturing method for heat-resistant alloy members.