JP2002332563A - Alloy film, heat resistant member having the film and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alloy film in which corrosive deterioration (such as the one caused by oxidation, the one caused by carburization, the one caused by nitriding, the one caused by sulfidation and the one caused by halogenation), thermal deterioration or the like are hard to be generated, and which can be produced by a simple method at a low cost, and is further applicable even to a part with a complicated shape. SOLUTION: Aluminum and chromium are diffused into a nickel or cobalt based plating film to produce a nickel - chromium - aluminum based alloy film or a cobalt - chromium - aluminum based alloy film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alloy film applied to heat-resistant members used in engines, turbines, various industrial furnaces, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, high-temperature operation and long operation time of engines, turbines, and the like used in cogeneration and the like have been performed in order to improve energy conversion efficiency. Under such severe operating conditions, in particular, the metal parts of the high temperature gas flowing parts such as the combustion part, the exhaust part, the heat exchange part, such as the engine and the turbine, are corroded and deteriorated by oxidation, corroded by carburization, Corrosion deterioration due to nitriding, corrosion deterioration due to sulfuration, corrosion deterioration due to halogenation,
Thermal degradation and the like occur, which is a serious problem in practical use.

For this reason, a nickel-based heat-resistant alloy may be used as a metal member in some cases. However, it has become difficult to provide both high-temperature strength and oxidation resistance with a heat-resistant alloy alone.

Therefore, it has been proposed to apply various coatings to the surface of the metal member in order to suppress the corrosion deterioration and the heat deterioration of the metal member.

[0005] Of these coatings, M-
Some of those subjected to Cr-Al-X alloy thermal spraying have been put to practical use. Here, M is nickel, cobalt, iron and alloys thereof, and X is yttrium, hafnium, scandium, cesium, lanthanum, etc., which are elements having a function of maintaining and reinforcing a protective oxide film such as aluminum oxide and chromium oxide.

[0006] However, metal materials sprayed with an M-Cr-Al-X alloy have excellent oxidation resistance at high temperatures, but have the following problems. 1. During use at a high temperature, aluminum and chromium in the sprayed alloy film diffuse into the metal member, so that the metal material is embrittled. 2. Since chromium and aluminum are uniformly present in this alloy sprayed coating, if chromium oxide and aluminum oxide, which are protective oxide coatings, are formed on the surface due to thermal history, immediately below these protective oxide coatings A chromium and aluminum deficiency layer is formed. As a result, aluminum and chromium that maintain these oxide films are insufficient, and the ability to maintain these protective oxidative films is reduced. It is easy for peeling and damage of the film to occur from the chromium and aluminum deficient layer portion. Cause problems. 3. This alloy sprayed coating has a poor adhesion to a metal substrate, and has a serious problem that the coating is easily peeled off or damaged by heat shock due to heat. 4. When producing this alloy sprayed coating, a large-scale apparatus is required, and there is a restriction that it cannot be applied to a member having a complicated shape. Alloy powders for thermal spraying are also quite expensive and their composition is limited.

[0007]

SUMMARY OF THE INVENTION The main object of the present invention is to:
Corrosion deterioration (oxidation deterioration, carburization deterioration, nitridation deterioration, sulfurization deterioration,
An object of the present invention is to provide an alloy film which is less likely to cause thermal deterioration and the like and is suitable for use in engines, turbines, various industrial furnaces, and the like, and a heat-resistant member using the alloy film.

Another object of the present invention is to provide a method of manufacturing an alloy film which can be manufactured at a low cost by a simple method and can be easily applied to a complicated shape portion.

[0009]

Means for Solving the Problems The present inventor has conducted intensive studies in view of the above-mentioned problems of the prior art, and as a result, after forming a nickel or cobalt-based plating film on a metal substrate, Or, by diffusing aluminum and chromium into the cobalt-based plating film, both the chromium content and the aluminum content gradually decrease in the depth direction from the surface, or nickel in which the total content of chromium and aluminum decreases (or It has been found that a (cobalt) -aluminum-chromium alloy film can be formed. When the alloy film is formed on a metal substrate, it has been found that the problems of the prior art can be significantly reduced or eliminated, and the above object can be achieved. Based on this, the present invention has been completed. Was.

That is, the present invention provides the following alloy film, a heat-resistant member using the same, and a method for producing the same. Item 1. A nickel-chromium-aluminum-based alloy film or a cobalt-chromium-aluminum-based alloy film formed by diffusing chromium and aluminum into a nickel or cobalt-based plating film. Item 2. In the nickel or cobalt plating film,
Item 2. The alloy film according to item 1, wherein the alloy film contains an element having a function of maintaining and reinforcing the protective oxide film or an oxide thereof. Item 3. Item 3. The alloy film according to Item 2, wherein the element having a function of maintaining reinforcement of the protective oxide film is at least one selected from the group consisting of yttrium, hafnium, scandium, cesium, and lanthanum. Item 4. The nickel-chromium-aluminum-based alloy coating or cobalt-chromium-aluminum-based alloy coating is
Item 4. The alloy film according to any one of Items 1 to 3, wherein both the chromium content and the aluminum content decrease from the surface in the depth direction, or the total content of chromium and aluminum decreases. Item 5. The nickel-chromium-aluminum-based alloy film or the cobalt-chromium-aluminum-based alloy film is a chromium-aluminum diffusion layer in which chromium and aluminum are diffused in a nickel-based plating or a cobalt-based plating film, and chromium and aluminum are not diffused. Consisting of a nickel or cobalt plating layer consisting of only a nickel or cobalt plating film,
5. The alloy film according to any one of items 1 to 4, wherein a ratio of these film thicknesses is chromium-aluminum diffusion layer: nickel or cobalt-based plating layer = 1: 99 to 99: 1. Item 6. Item 6. A heat-resistant member having the alloy film according to any one of Items 1 to 5 on a metal substrate. Item 7. Item 7. The heat-resistant member according to Item 6, which is a member for a combustion portion, an exhaust portion, or a heat exchange portion of an engine or a turbine. Item 8. Engine or turbine piston top, piston ring, cylinder liner, exhaust valve back,
Item 8. The heat-resistant member according to Item 7, which is a member for a turbine combustor, a moving blade, a stationary blade, a shroud, a turbine casing, a turbocharger exhaust turbine, a wastegate valve, an exhaust manifold, an exhaust flue, an oil cooler, or an aftercooler. Item 9. Item 9. An engine or turbine provided with the heat-resistant member according to any one of the above items 6 to 8. Item 10. Item 7. The heat-resistant member according to Item 6, which is a member for an industrial furnace. Item 11. Burner, radiant tube, muffle,
Item 11. The heat-resistant member according to item 10, which is a member for a recuperator, a roller hearth, a transport belt, a skid hardware, a heat shield plate, or a metal melting pot. Item 12. Item 12. An industrial furnace provided with the heat-resistant member according to any one of items 6, 10 and 11. Item 13. Item 13. The industrial furnace according to Item 12, which is a heating furnace, an annealing furnace, a heat treatment furnace, a carburizing furnace, a nitriding furnace, a firing furnace, or an incinerator. Item 14. After forming a nickel or cobalt plating film on a metal substrate, heat treatment is performed in a penetrant containing chromium and aluminum to diffuse chromium and aluminum into the nickel or cobalt plating film. A method for producing a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film. Item 15. Item 15. The method according to Item 14, wherein the nickel or cobalt-based plating film contains an element having a function of maintaining and reinforcing the protective oxide film or an oxide thereof. Item 16. After forming a nickel or cobalt plating film on a metal substrate, a chromium and aluminum film is formed, and then heat treatment is performed to diffuse chromium and aluminum into the nickel or cobalt plating film. And a method for producing a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film. Item 17. Item 17. The method according to Item 16, wherein the nickel or cobalt-based plating film contains an element having a function of maintaining and reinforcing the protective oxide film or an oxide thereof. Item 18. Item 18. The method according to Item 16 or 17, wherein the method for forming the chromium and aluminum film is an electrolytic plating method, a hot-dip plating method, a metal spraying method, a vacuum evaporation method, a cathode sputtering method, or an ion plating method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The alloy film of the present invention is a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film obtained by diffusing chromium and aluminum into a nickel or cobalt-based plating film. Further, the heat-resistant member of the present invention has the above-mentioned alloy film on a metal substrate.

The kind of the metal serving as the base of the heat-resistant member of the present invention is not particularly limited as long as it is a metal forming the heat-resistant member used for engines, turbines, various industrial furnaces, and the like. Steel, special steel, heat-resistant steel, stainless steel, etc.), copper, copper alloy, nickel, nickel alloy,
Cobalt, a cobalt alloy and the like can be mentioned.

In order to form a nickel-aluminum-chromium alloy film or a cobalt-chromium-aluminum alloy film on such a metal substrate, first, a nickel or cobalt-based plating film is formed on the metal substrate.
Chromium and aluminum may be diffused into the formed plating film.

Formation of Nickel or Cobalt-based Plating Film The method for forming the nickel or cobalt-based plating film is not particularly limited. However, if a plating treatment is performed according to a conventional method using an electrolytic plating solution or an electroless plating solution. Good.

The nickel or cobalt plating film is
Nickel metal alone, cobalt metal alone, in addition to nickel, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, palladium, platinum,
It may be a nickel-based alloy plating film containing one or more alloying elements such as copper, silver, gold, zinc, cadmium, boron, and phosphorus. In addition to cobalt, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper,
A cobalt-based alloy plating film containing one or more alloying elements such as silver, gold, zinc, cadmium, boron, and phosphorus may be used.

In such a nickel or cobalt-based alloy plating film, the content of the main nickel or cobalt is about 50% by weight or more, specifically 50% by weight, based on the nickel or cobalt and the alloy metal.
It is preferably about 90% by weight.

Further, the nickel or cobalt-based plating film may contain an element such as yttrium, hafnium, scandium, cesium, lanthanum or an oxide of these elements, which has a function of maintaining and reinforcing the protective oxide film. . Here, the reinforcement maintaining function of the protective oxide film means an effect of stabilizing the protective oxide film such as chromium oxide or aluminum oxide and suppressing peeling. Preferred are yttrium, hafnium, yttrium oxide and hafnium oxide. These elements or oxides have an average particle size of 0.01 to 20 μm.
m, preferably 0.05 to 10 μm. The content of these elements or oxides is 1 to 1 in the plating film.
It is preferable to set it to about 0% by weight.

Further, when an electroless plating solution is used,
Phosphorus or boron which is a component in the reducing agent is taken into the plating film. The content of phosphorus or boron derived from these reducing agents is about 0.1 to 15% by weight in the nickel or cobalt-based plating film for phosphorus, and 0.1 to 10% by weight in the nickel or cobalt-based plating film for boron. It is preferable to set the degree.

The types of the electrolytic plating solution and the electroless plating solution are not particularly limited, and various known electrolytic plating solutions or electroless plating solutions containing a nickel salt or a cobalt salt as an essential component can be used. .

As a plating method, electrolytic plating or electroless plating may be performed after pretreatment such as degreasing and pickling, according to a conventional method. Further, in order to improve the adhesion of the nickel or cobalt plating film to the substrate, the nickel or cobalt plating film may be formed after performing strike plating by a known method, if necessary. When performing electroless plating directly on a substrate having no catalytic activity for electroless plating, the electroless plating may be performed after applying a catalyst according to a conventional method.

The thickness of the nickel or cobalt plating film varies depending on the material and shape of the member, the type of environment in which the member is used, and the like.
It may be about μm, preferably 20 to 500 μm.

Nickel (or cobalt) -chromium-al
Formation of Minium-Based Alloy Film As a method of diffusing chromium and aluminum into a nickel or cobalt-based plating film, the following methods can be exemplified.

(1) In the first method, after forming a nickel or cobalt plating film, a member having the nickel or cobalt plating film formed thereon is subjected to a penetrating agent containing chromium and aluminum metal powder (for example, chromium powder and aluminum This is a method in which chromium and aluminum are diffused and penetrated into a nickel or cobalt-based plating film by performing a heat treatment in a powdery penetrant containing metal powder).

The heat treatment is performed at a temperature of about 800 to 1200 ° C. for about 1 to 20 hours, preferably 850 to 1100 ° C.
It may be heated for about 5 to 15 hours. The heating atmosphere may be a non-oxidizing atmosphere such as nitrogen or argon.

As an example of the composition of the powdery penetrant, about 10 to 30% by weight of chromium,
A powdery composition composed of about 20% by weight, about 0.1 to 5% by weight of ammonium chloride and the balance of alumina can be exemplified. These penetrants can be prepared by mixing chromium, aluminum, ammonium chloride, and alumina powder. Also,
The mixing method is not limited, and examples thereof include shaking in a container and stirring with a screw. In addition, the following particles are mixed after obtaining or preparing particles of such a size in advance.

The particle size of the powdery penetrant is not particularly limited, but is usually not more than about 50 mesh (size of sieve: 300 μm), preferably not more than about 100 mesh (size of sieve: 150 μm), and further, Preferably, the mesh size is about 200 mesh (size of sieve: 75 μm) or less.

(2) As a second method for diffusing chromium and aluminum into a nickel or cobalt plating film, a nickel or cobalt plating film is formed, and then a chromium and aluminum film is formed on the plating film. Then, heat treatment is performed to diffuse chromium and aluminum into the nickel or cobalt-based coating.

In the present invention, the “chromium and aluminum film” may be a two-layer film of a chromium film and an aluminum film, or a film containing both chromium and aluminum. At this time, there is no limitation on the order in which the “chromium and aluminum film” is formed on the nickel or cobalt-based plating film.
An aluminum film, a nickel or cobalt plating film → aluminum film → chrome film, a nickel or cobalt plating film → a film containing both chromium and aluminum may be formed in this order.

I) Method of Forming Chromium Film The method of forming a chromium film on a nickel or cobalt-based plating film or on an aluminum film described later is not particularly limited. , A metal spraying method, a vacuum evaporation method, a cathode sputtering method, an ion plating method and the like can be employed. The specific conditions of these methods are not particularly limited, and may be in accordance with ordinary methods.

For example, when a chromium film is formed by an electrolytic plating method, the type of the chromium plating solution is not particularly limited, and an ordinary Sargent chromium plating bath,
A fluoride-added chromium plating bath, a black chromium plating bath, or the like can be used. In addition, the plating conditions may be appropriately determined according to the type of plating solution to be used. Generally, the same solution temperature, pH, current density, etc. as in the case of normal chromium plating are employed to form a nickel or cobalt-based plating film. Or a chromium plating film may be formed on an aluminum film described later.

Hot-dip plating, metal spraying, vacuum evaporation,
There is no particular limitation on the cathode sputtering method, the ion plating method, and the like, and any conventional method may be used.

The thickness of the chromium film is not particularly limited, and may be appropriately determined according to the amount of chromium to be diffused and infiltrated. Usually, the thickness of the chromium film is set so that chromium does not excessively diffuse and adversely affect the metal substrate. It is preferable that the thickness be less than half the thickness of the nickel or cobalt plating film. Specifically, it is about 1 to 250 μm, preferably about 5 to 125 μm.

Ii) Method of forming aluminum film The method of forming the aluminum film on the nickel or cobalt plating film or on the above-mentioned chromium film is not particularly limited. , A metal spraying method, a vacuum evaporation method, a cathode sputtering method, an ion plating method and the like can be employed. The specific conditions of these methods are not particularly limited, and may be in accordance with ordinary methods.

For example, when an aluminum film is formed by an electrolytic plating method, the type of aluminum plating solution is not particularly limited, and a general nonaqueous solvent-based plating bath, for example, an aluminum chloride-sodium chloride molten salt bath, An aluminum chloride-dimethyl sulfone bath or the like can be used. In addition, the plating conditions may be appropriately determined according to the type of the plating solution to be used, and generally, the same solution temperature, pH, current density, etc. as in the case of ordinary aluminum plating are employed to form a nickel or cobalt-based plating film. Alternatively, an aluminum plating film may be formed on the chromium film.

Hot-dip plating, metal spraying, vacuum evaporation,
There is no particular limitation on the cathode sputtering method, the ion plating method, and the like, and any conventional method may be used.

The thickness of the aluminum film is not particularly limited, and may be appropriately determined according to the amount of aluminum to be diffused and infiltrated. Usually, the thickness of the aluminum film is set so that aluminum does not excessively diffuse and adversely affect the metal substrate. It is preferable that the thickness be less than half the thickness of the nickel or cobalt plating film. Specifically, it is about 1 to 250 μm, preferably about 5 to 125 μm.

The total thickness of the chromium film and aluminum film formed by the above methods i) and ii) may be appropriately determined according to the amounts of chromium and aluminum to be diffused and infiltrated. The thickness is preferably not more than half the thickness of the nickel or cobalt plating film so that excessive diffusion does not adversely affect the metal substrate. Specifically, 2 to 500 μm, preferably 10 to
It is about 250 μm.

Iii) Formation of film containing both chromium and aluminum The method for forming a film containing both chromium and aluminum on the nickel plating film is not particularly limited.
For example, an electrolytic plating method, a hot-dip plating method, a metal spraying method, a vacuum evaporation method, a cathode sputtering method, an ion plating method, or the like can be employed. The specific conditions of these methods are not particularly limited, and may be in accordance with ordinary methods.
Specifically, chromium-aluminum alloy plating, chromium-aluminum alloy spraying and the like can be exemplified.

The thickness of the film containing both chromium and aluminum is not particularly limited, and may be appropriately determined according to the amounts of chromium and aluminum to be diffused and infiltrated.
Usually, the thickness is preferably not more than half the thickness of the nickel or cobalt plating film so that chromium and aluminum do not excessively diffuse and adversely affect the metal substrate. Specifically, 2 to 500 μm, preferably 10 to 2 μm
It is about 50 μm.

Regarding the heat treatment method after the formation of the film, for example, heating may be performed at a temperature of about 800 to 1200 ° C. for about 1 to 20 hours, preferably at about 900 to 1100 ° C. for about 5 to 15 hours. Regarding the atmosphere of the heat treatment,
A non-oxidizing atmosphere such as nitrogen or argon may be used.

Nickel (or cobalt) -chromium-a
Luminium-based alloy film By the above method, chromium and aluminum are diffused into a nickel- or cobalt-based plating film to form a nickel-chromium-aluminum-based alloy film or a cobalt-chromium-aluminum-based alloy film. The formed nickel-chromium-aluminum-based alloy film or cobalt-chromium-aluminum-based alloy film has the highest total content of chromium and aluminum on the surface and gradually increases the total content of aluminum and chromium in the depth direction. Is reduced.

In general, both the chromium content and the aluminum content are the largest on the surface portion, and the respective contents gradually decrease in the depth direction. In particular, such a structure is obtained when the method (1) is employed.

The content of chromium and aluminum in the nickel-chromium-aluminum alloy film or the cobalt-chromium-aluminum alloy film is not particularly limited, and is about 20 to 70% by weight at the surface of the alloy film. Preferably, however, higher or lower amounts of chromium and aluminum may be included in the surface portion of the alloy coating.

When the heat-resistant member is used at 800 ° C. or higher, it is preferable that the surface has a large amount of Al. When the heat-resistant member is used at 800 ° C. or lower, it is preferable that the surface has a large amount of Cr.

In the present invention, in order to prevent adverse effects due to diffusion of chromium or aluminum in the metal substrate of the heat-resistant member, the metal substrate comes into contact with a metal substrate of a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film. It is preferable that the portion is made of only a nickel or cobalt plating film without diffusion of chromium or aluminum. Usually, a portion (chromium-aluminum diffusion layer) in which chromium and aluminum diffuse into the nickel or cobalt-based plating film to form a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film, The film thickness ratio of the portion (nickel or cobalt-based plating layer) consisting only of the nickel or cobalt-based alloy in which aluminum is not diffused is as follows: chromium-aluminum diffusion layer: nickel or cobalt-based plating layer = 1: 99 to 9
The ratio may be about 9: 1, preferably about 10:90 to 90:10, and more preferably about 30:70 to 90:10.

Further, in the film obtained by the production method of the above (2), the chromium-aluminum diffusion layer
Chromium and aluminum diffuse into the nickel or cobalt-based plating film to form a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum-based alloy film. Alternatively, a portion (layer) in which one of aluminum is diffused to form a nickel (cobalt) -chromium alloy film or a nickel (cobalt) -aluminum alloy film may be included.

The thickness ratio between the chromium-aluminum diffusion layer and the nickel or cobalt plating layer can be appropriately set by adjusting the thickness of the chromium-aluminum film to be formed, the heat treatment temperature and the heat treatment time. .

According to the present invention, a heat-resistant member can be obtained by a simple method and at low cost by diffusing chromium and aluminum into a nickel or cobalt plating film. And such a nickel-chromium-aluminum-based alloy coating or cobalt-chromium-
The heat-resistant member on which the aluminum-based alloy film is formed hardly causes corrosion deterioration, heat deterioration, and the like, and has excellent characteristics as a heat-resistant member.

When this alloy film is used at a high temperature, chromium and aluminum form protective oxide films, chromium oxide and aluminum oxide, respectively. Chromium oxide has excellent resistance to oxidation and sulfuration corrosion at 800 ° C. or less, and aluminum oxide has excellent resistance to oxidation at 800 ° C. or more.

Further, yttrium, hafnium, which are elements having the function of maintaining and reinforcing the protective oxide film described above,
When scandium, cesium, and lanthanum are contained in the nickel-chromium-aluminum-based alloy film or the cobalt-chromium-aluminum-based alloy film, the resistance to corrosion deterioration, heat deterioration, and the like at higher temperatures is further increased. This is because aluminum oxide and chromium oxide, which are protective oxidizing films, are stabilized and have an effect of suppressing peeling and the like.

Further, since the chromium and aluminum in the nickel-chromium-aluminum-based alloy coating or the cobalt-chromium-aluminum-based alloy coating decrease in the depth direction, the portions in contact with the metal substrate are:
Chromium and aluminum do not diffuse at all, or only a small amount of chromium and aluminum diffuse into the nickel or cobalt plating film even when used at high temperature for a long time. For this reason, aluminum and chromium diffuse into the inside of the base metal member during use at high temperature, which is a problem of the conventional nickel-cobalt-chromium-aluminum alloy spray coating, and embrittlement of the metal material occurs. Can prevent it from happening.

The portions to which the nickel-chromium-aluminum alloy coating or the cobalt-chromium-aluminum alloy coating of the present invention is applied include a combustion portion, an exhaust portion, and a heat exchange portion of an engine or a turbine.

The combustion section includes a piston top surface, a piston ring, a cylinder liner, an exhaust valve backside, a turbine combustor, a moving blade, a stationary blade, a shroud or a turbine casing. The exhaust unit includes a turbocharger exhaust turbine, a wastegate valve, an exhaust manifold, an exhaust flue, and the like. The heat exchange unit includes an oil cooler, an after cooler, and the like.

The member of the present invention can be effectively used as a material of a heat-resistant member used in these engines or turbines.

The heat-resistant member of the present invention can be used as a member for various industrial furnaces such as a heating furnace, an annealing furnace, a heat treatment furnace, a firing furnace, a carburizing furnace, a nitriding furnace, and an incinerator. Specifically, it can be used as a member for burners, radiant tubes, muffles, recuperators, roller hearths, conveyor belts, skid hardware, various heat shield plates, metal melting pots, and other metal parts.

Further, the members of the present invention are used for liquefaction and gasification of coal, oil shale and tar sand refining equipment, power boilers, petroleum refining, petrochemical industry, other reaction vessels, reaction tubes, heat exchangers, etc. It can be used as a container, a transfer pipe, and various other high-temperature members, and is a member with extremely high utility value.

[0057]

According to the present invention, the nickel-chromium-aluminum alloy film or the cobalt-chromium-aluminum alloy film of the present invention has corrosion deterioration (corrosion deterioration by oxidation, corrosion deterioration by carburization, corrosion deterioration by nitriding, corrosion deterioration by sulfuration, (E.g., corrosion deterioration due to halogenation), heat deterioration, and the like are less likely to occur, and can be manufactured at a low cost by a simple method.

Further, according to the surface treatment method employed in the present invention, even a member having a complicated shape can be easily manufactured.

[0059]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

Embodiment 1 1. Formation of Nickel-Yttrium Oxide Composite Plating Film Electrolytic plating was performed as described below.

1) Preparation of Nickel Strike Plating Solution A plating solution having the following composition was prepared. Nickel chloride 245 g / l Hydrochloric acid 120 g / l 2) Preparation of electrolytic nickel-yttrium oxide composite plating solution A composite plating solution having the following composition was prepared. Nickel sulfate 280 g / l Nickel chloride 45 g / l Boric acid 30 g / l Yttrium oxide powder (average particle size 1 μm) 20 g / l 3) Plating method The following was used as a material to be plated. Turbine blade Material: Ni heat resistant alloy MAR-M247 (Co: 10% by weight, Cr: 9% by weight, Mo: 0.8% by weight, W: 10% by weight, Al: 5.5% by weight, Ti: 1) 0.2% by weight, C:
0.1% by weight) Dimensions: Height 52mm, Width 15mm, Depth 40mm-Turbine stationary blade Material: Co heat-resistant alloy MAR-M509 (Ni: 10% by weight, Cr: 24% by weight, W: 7% by weight, Ti : 0.2% by weight) Dimensions: height 25mm, width 15mm, depth 45mm ・ Test piece (material: SUS310S, 50mm × 50mm,
(Thickness: 3 mm) After the above moving blade, stationary blade and test piece were degreased with an alkaline degreasing solution, they were used as a negative electrode and plated by the following method.

First, a nickel strike treatment was carried out for 2 minutes at a solution temperature of 25 ° C. and a current density of 10 A / dm ² using a nickel strike bath containing a nickel strike plating solution having the composition of 1) above.

Next, the electrolytic nickel of the composition of the above 2)
Using a plating tank containing an yttrium oxide composite plating solution, electrolytic plating was performed until the film thickness became 100 μm while stirring with a screw under the conditions of a liquid temperature of 50 ° C., a pH of 4.0, and a current density of 2 A / dm ² . An electrolytic nickel-yttrium oxide composite plating film was formed. After the plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.

2. The material to be plated having the aluminum-chromium diffusion treatment and the electrolytic nickel-yttrium oxide composite plating film formed thereon was powdered (100
It was buried in a SUS304 container filled with a penetrant (mesh or less) and heated at 900 ° C. for 10 hours in an argon atmosphere.

[0065] <penetrant Composition> Aluminum 7.0 weight percent chromium 25.0 wt% ammonium hydroxide 3.0 wt% alumina 65.0 wt% 3. Analysis and Test Results Using the test piece, the surface of the nickel-chromium-aluminum-yttrium-based alloy film was subjected to quantitative analysis using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.). Met.

Ni: 60% by weight, Cr: 16% by weight, A
l: 20% by weight, Y: 2% by weight, O: 2% by weight Further, when the cross section of the test piece was analyzed by the same apparatus, the diffusion layer of aluminum and chromium was about 50 μm.
m. The nickel-yttrium oxide composite plating layer in which aluminum and chromium are not diffused is about 5
It was 0 μm. Aluminum content is 20 at the surface
It was 12% by weight at a depth of 10 μm from the surface, 8% by weight at a depth of 30 μm from the surface, and 5% by weight at a depth of 50 μm from the surface. Had decreased. It was not detected at a depth of 51 μm from the surface.

The chromium content was 16% by weight on the surface, but was 10% by weight at a depth of 10 μm from the surface, 6% by weight at a depth of 30 μm from the surface, and 5% by weight from the surface.
At a depth of 0 μm, the content was 3% by weight, and the chromium content decreased in the depth direction. It was not detected at a depth of 51 μm from the surface.

The rotor blade and the stationary blade having the nickel-chromium-aluminum-yttrium alloy coating formed thereon were
First stage of kW gas turbine (atmospheric temperature 115
0 ° C.) and operated for 1000 hours.

Nickel chromium after 1000 hours of operation
When the rotor blade and stationary blade on which the aluminum-yttrium alloy alloy film was formed were cut and the cross section was analyzed with a metallurgical microscope,
The nickel-chromium-aluminum-yttrium-based alloy coating protects the Ni alloy base and the Co alloy base,
There was no oxide scale layer, and there was no oxidative deterioration of the Ni alloy substrate and the Co alloy substrate.

Further, SUS310 having the above-mentioned nickel-chromium-aluminum-yttrium alloy film formed thereon
S test piece was solid carburizing agent (K
G-30), and was immersed in an alumina crucible filled with G-30) and kept in an electric furnace at 950 ° C. for 1000 hours.

Nickel-chromium after holding for 1000 hours
When the test piece on which the aluminum-yttrium-based alloy film was formed was cut and the cross section was analyzed with a metallurgical microscope, the SUS310S base material was protected by the nickel-chromium-aluminum-yttrium-based alloy film, and there was no carburized layer.
There was no carburizing deterioration of the SUS310S base material.

Embodiment 2 1. Nickel-cobalt-yttrium oxide composite plating
Formation of film Electroplating was performed as described below.

1) Preparation of Nickel Strike Plating Solution A plating solution having the following composition was prepared. Nickel chloride 245 g / l Hydrochloric acid 120 g / l 2) Preparation of electrolytic nickel-cobalt-yttrium oxide composite plating solution A plating solution having the following composition was prepared. Nickel sulfate 240 g / l Nickel chloride 45 g / l Boric acid 30 g / l Cobalt sulfate 15 g / l Yttrium oxide powder (average particle size 1 μm) 20 g / l 3) Plating method The same moving blade, stationary blade and test piece as in Example 1 Was degreased with an alkaline degreasing solution in the same manner as in Example 1, and then subjected to a nickel strike treatment in the same manner as in Example 1 using a nickel strike tank containing a nickel strike plating solution having the composition described in 1) above.

Next, using a plating bath containing an electrolytic nickel-cobalt-yttrium oxide composite plating solution having the composition of 2) above, at a solution temperature of 60 ° C., a pH of 4.0 and a current density of 2 A / dm ² , Electrolytic plating was performed until the film thickness became 100 μm while stirring with a screw to form an electrolytic nickel-cobalt-yttrium oxide composite plating film. After the plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.

2. An aluminum-chromium diffusion treatment and a plating material having an electrolytic nickel-cobalt-yttrium oxide composite plating film formed thereon were filled with a powdery (100 mesh or less) penetrating agent having the following composition.
04, immersed in a container, 900 ° C under argon atmosphere
For 10 hours.

[0076] <penetrant Composition> Aluminum 7.0 weight percent chromium 25.0 wt% ammonium hydroxide 3.0 wt% alumina 65.0 wt% 3. Analysis and Test Results Using the test piece, the surface of the nickel-cobalt-chromium-aluminum-yttrium-based alloy film was quantitatively analyzed using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.). It was as follows.

Ni: 48% by weight, Co: 12% by weight,
Cr: 16% by weight, Al: 20% by weight, Y: 2% by weight,
O: 2% by weight In the same apparatus, analysis of the cross-section depth direction of the test piece revealed that the diffusion layer of aluminum and chromium was about 50 μm.
m. The nickel-cobalt-yttrium oxide composite plating layer in which aluminum and chromium were not diffused was about 50 μm. The aluminum content was 20% by weight at the surface, 12% by weight at a depth of 10 μm from the surface, 8% by weight at a depth of 30 μm from the surface, and 5% by weight at a depth of 50 μm from the surface, The aluminum content decreased in the depth direction. 5 from the surface
It was not detected at a depth of 1 μm. The content of chromium was 16% by weight on the surface, but was 10 μm from the surface.
10% by weight at a depth of 6 mm and 6% at a depth of 30 μm from the surface
% By weight, 3% by weight at a depth of 50 μm from the surface,
The chromium content decreased in the depth direction. 51 from the surface
It was not detected at a depth of μm.

The moving blade and the stationary blade on which the nickel-cobalt-chromium-aluminum-yttrium alloy film was formed were installed at the first stage (atmospheric temperature 1150 ° C.) of a 2000 kW gas turbine and operated for 1000 hours. .

The blade and the stationary blade on which the nickel-cobalt-chromium-aluminum-yttrium alloy film was formed after the operation for 1000 hours were cut, and the sections were analyzed by a metallographic microscope. Ni alloy substrate and Co
The alloy substrate was protected, there was no oxide scale layer, and there was no oxidative degradation of the Ni alloy substrate and the Co alloy substrate.

Further, the S-coated nickel-cobalt-chromium-aluminum-yttrium alloy film was formed.
The US310S test piece was buried in an alumina crucible filled with a solid carburizing agent (KG-30, manufactured by Parker Heat Treatment Industry Co., Ltd.), and kept in an electric furnace at 950 ° C. for 1000 hours.

A test piece on which a nickel-cobalt-chromium-aluminum-yttrium-based alloy film formed after holding for 1000 hours was cut, and a cross section was analyzed with a metallographic microscope. Protected the SUS310S base material, there was no carburized layer, and there was no carburization deterioration of the SUS310S base material.

Embodiment 3 1. Formation of Cobalt-based Plating Film Electrolytic plating was performed as described below.

1) Preparation of Nickel Strike Plating Solution A plating solution having the following composition was prepared. Nickel chloride 245 g / l Hydrochloric acid 120 g / l 2) Preparation of electrolytic cobalt-yttrium oxide composite plating solution A plating solution having the following composition was prepared. Cobalt sulfate 300 g / l Cobalt chloride 50 g / l Boric acid 30 g / l Yttrium oxide powder (average particle size 1 μm) 20 g / l 3) Plating method The same moving blade, stationary blade and test piece as in Example 1 were used. After degreasing with an alkaline degreasing solution in the same manner as in Example 1, a nickel strike treatment was performed in the same manner as in Example 1 using a nickel strike tank containing a nickel strike plating solution having the composition described in 1) above.

Next, using a plating bath containing the electrolytic cobalt-yttrium oxide composite plating solution having the composition of the above 2), the solution temperature was 50 ° C., the pH was 4.0, and the current density was 2 A / dm.
Under the conditions of ² , while stirring with a screw, the film thickness is 100μ.
m, to form an electrolytic cobalt-yttrium oxide composite plating film. After the plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.

[0085] 2. The material to be plated having the aluminum-chromium diffusion treatment and the electrolytic cobalt-yttrium oxide composite plating film formed thereon was powdered (100
It was buried in a SUS304 container filled with a penetrant (mesh or less) and heated at 900 ° C. for 10 hours in an argon atmosphere.

[0086] <penetrant Composition> Aluminum 7.0 weight percent chromium 25.0 wt% ammonium hydroxide 3.0 wt% alumina 65.0 wt% 3. Analysis and Test Results Using the test piece, the surface of the cobalt-chromium-aluminum-yttrium-based alloy film was quantitatively analyzed using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.). Met.

Co: 60% by weight, Cr: 16% by weight, A
l: 20% by weight, Y: 2% by weight, O: 2% by weight Further, when the cross section of the test piece was analyzed by the same apparatus, the diffusion layer of aluminum and chromium was about 50 μm.
m. The cobalt-yttrium oxide composite plating layer in which aluminum and chromium are not diffused is about 5
It was 0 μm. Aluminum content is 20 at the surface
It was 12% by weight at a depth of 10 μm from the surface, 8% by weight at a depth of 30 μm from the surface, and 5% by weight at a depth of 50 μm from the surface. Had decreased. It was not detected at a depth of 51 μm from the surface. The chromium content was 16% by weight on the surface, but 1% at a depth of 10 μm from the surface.
It was 0% by weight, 6% by weight at a depth of 30 μm from the surface, and 3% by weight at a depth of 50 μm from the surface, and the chromium content decreased in the depth direction. It was not detected at a depth of 51 μm from the surface.

The moving blade and the stationary blade having the cobalt-chromium-aluminum-yttrium alloy film formed thereon were
First stage of kW gas turbine (atmospheric temperature 115
0 ° C.) and operated for 1000 hours.

After operating for 1000 hours, cobalt-chromium-
When the rotor blade and stationary blade on which the aluminum-yttrium alloy alloy film was formed were cut and the cross section was analyzed with a metallurgical microscope,
The cobalt-chromium-aluminum-yttrium-based alloy film protects the Ni alloy substrate and the Co alloy substrate,
There was no oxide scale layer, and there was no oxidative deterioration of the Ni alloy substrate and the Co alloy substrate.

Further, SUS310 on which the above-mentioned cobalt-chromium-aluminum-yttrium alloy film was formed.
S test piece was solid carburizing agent (K
G-30), and was immersed in an alumina crucible filled with G-30) and kept in an electric furnace at 950 ° C. for 1000 hours.

Cobalt-chromium after holding for 1000 hours
When the test piece on which the aluminum-yttrium-based alloy film was formed was cut and the cross section was analyzed with a metallurgical microscope, the SUS310S base material was protected by the cobalt-chromium-aluminum-yttrium-based alloy film, and there was no carburized layer.
There was no carburizing deterioration of the SUS310S base material.

Embodiment 4 1. Formation of Nickel-Based Plating Film Electroless plating was performed as described below.

1) Preparation of Nickel Strike Plating Solution A plating solution having the following composition was prepared. Nickel chloride 245 g / l Hydrochloric acid 120 g / l 2) Preparation of electroless nickel-boron-yttrium oxide composite plating solution A plating solution having the following composition was prepared. Nickel sulfate 27 g / l Sodium succinate 55 g / l Ammonium chloride 30 g / l Sodium citrate 30 g / l Boric acid 30 g / l Dimethylamine borane 3 g / l Yttrium oxide powder (average particle size 1 μm) 20 g / l 3) Plating method The same blades, vanes and test pieces as in Example 1 were degreased with an alkaline degreasing solution in the same manner as in Example 1, and then a nickel strike tank containing a nickel strike plating solution having the composition 1) was used. Nickel strike treatment was performed in the same manner as in No. 1.

Next, using a plating bath containing an electroless nickel-boron-yttrium oxide composite plating solution having the composition of 2), the film was stirred with a screw under the conditions of a solution temperature of 65 ° C. and a pH of 6.5. Electroless plating was performed until the thickness became 100 μm to form an electroless nickel-boron-yttrium oxide composite plating film. After the plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.

[0095] 2. An aluminum-chromium diffusion treatment and a material to be plated having an electroless nickel-boron-yttrium oxide composite plating film formed thereon were filled with a powdery (100 mesh or less) penetrant having the following composition.
04, immersed in a container, 900 ° C under argon atmosphere
For 10 hours.

[0096] <penetrant Composition> Aluminum 7.0 weight percent chromium 25.0 wt% ammonium hydroxide 3.0 wt% alumina 65.0 wt% 3. Analysis and Test Results Using the test piece, a quantitative analysis of the surface of the nickel-boron-chromium-aluminum-yttrium-based alloy film was performed using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.). It was as follows.

Ni: 59% by weight, B: 1% by weight, Cr:
16% by weight, Al: 20% by weight, Y: 2% by weight, O: 2
In addition, when the cross section of the test piece was analyzed by the same apparatus in the depth direction, the diffusion layer of aluminum and chromium was about 50 μm.
m. The nickel-boron-yttrium oxide composite plating layer in which aluminum and chromium were not diffused was about 50 μm. The aluminum content was 20% by weight at the surface, 12% by weight at a depth of 10 μm from the surface, 8% by weight at a depth of 30 μm from the surface,
At a depth of 50 μm from the surface, the content was 5% by weight, and the aluminum content decreased in the depth direction. 51μ from the surface
It was not detected at m depth. The chromium content was 16% by weight on the surface, but was 10% by weight at a depth of 10 μm from the surface, 6% by weight at a depth of 30 μm from the surface, and 3% by weight at a depth of 50 μm from the surface. And the chromium content decreased in the depth direction. 51 μm from the surface
Not detected at depth.

The rotor blade and the stationary blade on which the nickel-boron-chromium-aluminum-yttrium alloy coating was formed were installed at the first stage of a 2000 kW gas turbine (atmospheric temperature of 1150 ° C.) and operated for 1000 hours. .

Nickel-boron after 1000 hours of operation
The blades and stationary blades on which the chromium-aluminum-yttrium alloy film was formed were cut, and the sections were analyzed with a metallurgical microscope. As a result, the nickel-boron-chromium-aluminum-yttrium alloy film formed a Ni alloy substrate and a Co alloy base. The material was protected, there was no oxide scale layer, and there was no oxidative degradation of the Ni alloy substrate and the Co alloy substrate.

Further, the nickel-boron-chromium-
SU with aluminum-yttrium alloy coating
The S310S test piece was buried in an alumina crucible filled with a solid carburizing agent (KG-30 manufactured by Parker Heat Treatment Industry Co., Ltd.), and kept in an electric furnace at 950 ° C. for 1000 hours.

Nickel-boron after holding for 1000 hours
When the test piece on which the chromium-aluminum-yttrium-based alloy film was formed was cut and the cross section was analyzed with a metallographic microscope, the SUS310S base material was protected by the nickel-boron-chromium-aluminum-yttrium-based alloy film and there was no carburized layer And SUS310S substrate did not have carburizing deterioration.

Embodiment 5 1. Formation of Nickel-Yttrium Oxide Composite Plating Film Electrolytic plating was performed as described below. 1) Preparation of nickel strike plating solution A plating solution having the following composition was prepared. Nickel chloride 245 g / l Hydrochloric acid 120 g / l 2) Preparation of electrolytic nickel-yttrium oxide composite plating solution A composite plating solution having the following composition was prepared. Nickel sulfate 280 g / l Nickel chloride 45 g / l Boric acid 30 g / l Yttrium oxide powder (average particle size 1 μm) 20 g / l 3) Plating method The following was used as a material to be plated. Turbine rotor blade Material: Ni heat resistant alloy MAR-M247 (Co: 10% by weight, Cr: 9% by weight, Mo: 0.8% by weight, W: 10% by weight, Al: 5.5% by weight, Ti: 1) 0.2% by weight, C:
0.1% by weight) Dimensions: Height 52mm, Width 15mm, Depth 40mm-Turbine stationary blade Material: Co heat-resistant alloy MAR-M509 (Ni: 10% by weight, Cr: 24% by weight, W: 7% by weight, Ti : 0.2% by weight) Dimensions: height 25mm, width 15mm, depth 45mm ・ Test piece (material: SUS310S, 50mm × 50mm,
(Thickness: 3 mm) The above moving blade, stationary blade and test piece were degreased with an alkali degreasing solution, and then used as a negative electrode and plated by the following method.

First, a nickel strike treatment was carried out for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm ² using a nickel strike bath containing a nickel strike plating solution of the above composition 1).

Next, the electrolytic nickel of the composition 2)
Using a plating tank containing an yttrium oxide composite plating solution, electrolytic plating was performed until the film thickness became 100 μm while stirring with a screw under the conditions of a liquid temperature of 50 ° C., a pH of 4.0, and a current density of 2 A / dm ² . An electrolytic nickel-yttrium oxide composite plating film was formed.

[0105] 2. Formation of Chromium Plating Film Next, using a material to be plated on which an electrolytic nickel-yttrium oxide composite plating film was formed as a negative electrode, a plating bath containing an electrolytic chromium plating solution having the following composition, a liquid temperature of 50 ° C. and a current density of 20 A Under the condition of / dm ² , electrolytic plating was performed until the film thickness became 20 μm to form a chromium plating film. After plating, wash with water and 5
Dried for minutes.

[0106] <electrolytic chromium plating solution composition> chromic anhydride 200 g / L sulfuric acid 2 g / l 3. Formation of aluminum plating film Further, a material to be plated having a chromium plating film formed on an electrolytic nickel-yttrium oxide composite plating film
It was immersed in a molten aluminum plating bath at 00 ° C. for 1 minute to perform molten aluminum plating (20 μm). afterwards,
Cooled to 25 ° C.

[0107] 4. Diffusion treatment of chromium and aluminum A material to be plated having a chromium plating film and an aluminum plating film formed on the electrolytic nickel-yttrium oxide composite plating film obtained by the above method is placed in a nitrogen stream at 90%.
After heating at 0 ° C. for 3 hours, the mixture was cooled to 25 ° C. to form a nickel-chromium-aluminum-yttrium alloy film.

[0108] 5. Analysis and Test Results Using the test piece, the surface of the nickel-chromium-aluminum-yttrium-based alloy film was subjected to quantitative analysis using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.). Met.

Ni: 32% by weight, Cr: 25% by weight, A
1: 40% by weight, Y: 1% by weight, O: 2% by weight The same apparatus was used to analyze the specimen in the cross-sectional depth direction.
m. The nickel-yttrium oxide composite plating layer in which aluminum and chromium are not diffused is about 5
It was 0 μm. Aluminum content is 40 at the surface
It was 20% by weight at a depth of 10 μm from the surface, 10% by weight at a depth of 30 μm from the surface, and 5% by weight at a depth of 50 μm from the surface. Had decreased. It was not detected at a depth of 51 μm from the surface. The content of chromium was 25% by weight on the surface, but 40% by weight at a depth of 10 μm from the surface, 20% by weight at a depth of 30 μm from the surface,
At a depth of 50 μm from the surface, it was 10% by weight. It was not detected at a depth of 51 μm from the surface.

The rotor blade and the stationary blade having the nickel-chromium-aluminum-yttrium alloy film formed thereon were
First stage of kW gas turbine (atmospheric temperature 115
0 ° C.) and operated for 1000 hours.

Nickel chromium after 1000 hours of operation
When the rotor blade and stationary blade on which the aluminum-yttrium alloy alloy film was formed were cut and the cross section was analyzed with a metallurgical microscope,
The nickel-chromium-aluminum-yttrium-based alloy coating protects the Ni alloy base and the Co alloy base,
There was no oxide scale layer, and there was no oxidative deterioration of the Ni alloy substrate and the Co alloy substrate.

Further, SUS310 having the above-mentioned nickel-chromium-aluminum-yttrium alloy film formed thereon.
S test piece was solid carburizing agent (K
G-30), and was immersed in an alumina crucible filled with G-30) and kept in an electric furnace at 950 ° C. for 1000 hours.

Nickel-chromium after holding for 1000 hours
When the test piece on which the aluminum-yttrium-based alloy film was formed was cut and the cross section was analyzed with a metallurgical microscope, the SUS310S base material was protected by the nickel-chromium-aluminum-yttrium-based alloy film, and there was no carburized layer.
There was no carburizing deterioration of the SUS310S base material.

Comparative Example 1 A rotor and a stationary blade similar to those in Example 1 were coated on the first stage of a 2000 kW turbine (atmospheric temperature 1) without coating.
(100 ° C.) and operated for 1000 hours. 1
After cutting the moving blades and stationary blades that have not been coated after running for 000 hours, and analyzing the cross section with a metallographic microscope,
In each case, an oxide scale layer of about 100 μm was observed, and the nickel alloy of the moving blade and the cobalt alloy of the stationary blade were oxidized and degraded.

Further, SU without coating was used.
The S310S test piece was buried in an alumina crucible filled with a solid carburizing agent (KG-30 manufactured by Parker Heat Treatment Industry Co., Ltd.), and kept in an electric furnace at 950 ° C. for 1000 hours.

After holding for 1000 hours, the uncoated SUS310S test piece was cut, and the cross section was analyzed with a metallographic microscope. As a result, a carburized layer of about 100 μm was found, and the SUS310S base material was carburized and deteriorated.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C22C 19/07 C22C 19/07 GH C23C 14/14 C23C 14/14 G 28/02 28/02 C25D 5 / 50 C25D 5/50 (72) Inventor Taichi Nagashima 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Inside Osaka Gas Co., Ltd. (72) Inventor Akio Maeda 4-chome, Hirano-cho, Chuo-ku, Osaka-shi, Osaka No. 2 F-term in Osaka Gas Co., Ltd. (reference) 4K024 AA03 AB02 AB03 AB15 BA02 BA04 BA07 BB27 BB28 BC09 BC10 CA03 CA04 CA06 CA10 CB21 DA04 DB01 GA01 GA04 4K029 BA03 BA07 BB02 BC10 BD03 CA01 CA03 CA05 GA01 4K044 AA02 AA03 BA10 BA12 BB03 BB04 BC02 BC11 CA11 CA12 CA13 CA15 CA18 CA24 CA62

Claims (18)

[Claims] A nickel or cobalt-based plating film in which chromium and aluminum are diffused;
Chromium-aluminum alloy film or cobalt-chromium-aluminum alloy film. 2. The alloy film according to claim 1, wherein the nickel or cobalt plating film contains an element having a function of maintaining and reinforcing the protective oxide film or an oxide thereof. 3. The element having a function of maintaining and reinforcing the protective oxide film includes yttrium, hafnium, scandium,
The alloy film according to claim 2, wherein the alloy film is at least one selected from the group consisting of cesium and lanthanum. 4. The nickel-chromium-aluminum alloy coating or the cobalt-chromium-aluminum alloy coating, wherein both the chromium content and the aluminum content decrease from the surface in the depth direction, or chromium and aluminum 2. The total content of is reduced.
4. The alloy film according to any one of items 1 to 3. 5. A chromium-aluminum diffusion layer in which chromium and aluminum are diffused in a nickel-based plating or cobalt-based plating film, wherein the nickel-chromium-aluminum-based alloy film or the cobalt-chromium-aluminum-based alloy film is chromium and aluminum. And a nickel- or cobalt-based plating layer consisting only of a nickel-based plating film or a cobalt-based plating film in which no chromium-aluminum diffusion layer:
Nickel or cobalt based plating layer = 1: 99-99:
The alloy film according to any one of claims 1 to 4, which is 1. 6. A heat-resistant member having the alloy film according to claim 1 on a metal substrate. 7. The heat-resistant member according to claim 6, which is a member for a combustion part, an exhaust part, or a heat exchange part of an engine or a turbine. 8. A piston top surface of an engine or turbine,
For piston rings, cylinder liners, exhaust valve backs, turbine combustors, rotor blades, vanes, shrouds, turbine casings, turbocharger exhaust turbines, wastegate valves, exhaust manifolds, exhaust flue, oil coolers or aftercoolers The heat-resistant member according to claim 7, which is a member. 9. An engine or turbine provided with the heat-resistant member according to claim 6. 10. The heat-resistant member according to claim 6, which is a member for an industrial furnace. 11. The heat-resistant member according to claim 10, which is a member for a burner, a radiant tube, a muffle, a recuperator, a roller hearth, a conveyor belt, a skid hardware, a heat shield plate, or a metal melting pot. 12. An industrial furnace comprising the heat-resistant member according to claim 6, 10 or 11. 13. A heating furnace, an annealing furnace, a heat treatment furnace, a carburizing furnace,
The industrial furnace according to claim 12, which is a nitriding furnace, a firing furnace, or an incinerator. 14. After forming a nickel or cobalt plating film on a metal substrate, heat treatment is performed in a penetrant containing chromium and aluminum to diffuse chromium and aluminum into the nickel or cobalt plating film. A method for producing a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film, characterized in that: 15. The production method according to claim 14, wherein the nickel or cobalt-based plating film contains an element having a function of maintaining and reinforcing the protective oxide film or an oxide thereof. 16. After forming a nickel or cobalt plating film on a metal substrate, a chromium and aluminum film is formed, and then heat treatment is performed to diffuse chromium and aluminum into the nickel or cobalt plating film. A method for producing a nickel-chromium-aluminum alloy film or a cobalt-chromium-aluminum alloy film, characterized in that: 17. The method according to claim 16, wherein the nickel or cobalt-based plating film contains an element having a function of maintaining and reinforcing the protective oxide film or an oxide thereof. 18. The method according to claim 16, wherein the method for forming the chromium and aluminum film is an electrolytic plating method, a hot-dip plating method, a metal spraying method, a vacuum deposition method, a cathode sputtering method, or an ion plating method. .