WO2009072318A1 - Method of forming black yttrium oxide sprayed coating and member provided with black yttrium oxide sprayed coating - Google Patents

Method of forming black yttrium oxide sprayed coating and member provided with black yttrium oxide sprayed coating Download PDF

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Publication number
WO2009072318A1
WO2009072318A1 PCT/JP2008/062366 JP2008062366W WO2009072318A1 WO 2009072318 A1 WO2009072318 A1 WO 2009072318A1 JP 2008062366 W JP2008062366 W JP 2008062366W WO 2009072318 A1 WO2009072318 A1 WO 2009072318A1
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Prior art keywords
black
alloys
oxide
yttrium
gas
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PCT/JP2008/062366
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French (fr)
Japanese (ja)
Inventor
Yoshio Harada
Junichi Takeuchi
Ryo Yamasaki
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Tocalo Co., Ltd.
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Publication date
Application filed by Tocalo Co., Ltd. filed Critical Tocalo Co., Ltd.
Priority to KR1020087022813A priority Critical patent/KR101133002B1/en
Publication of WO2009072318A1 publication Critical patent/WO2009072318A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying

Definitions

  • the present invention relates to a method for forming a thermal sprayed black yttrium oxide thermal spray coating having excellent properties such as damage resistance and a black yttrium oxide coating material having excellent color design.
  • thermal spraying method a powder of metal, ceramics, cermet or the like is melted by a plasma jet while being burned by a combustion flame, and then sprayed onto the surface of a thermal sprayed body (base material) to thereby surface the base material.
  • This is one of the surface treatment technologies widely used in many industrial fields.
  • the thermal spray coating obtained by applying this thermal spraying method consists of the strength and weakness of the bonding force between the particles that make up this coating, the amount of unbonded particles, and the particles that do not melt (hereinafter referred to as “unmelted particles”). It is known that there are large differences in the mechanical strength and corrosion resistance of the coating depending on the amount.
  • the goal of conventional thermal spraying technology development is to increase the interparticle bonding force and increase the porosity by generating strong collision energy on the surface of the sprayed object, for example, by using a high-temperature heat source such as plasma.
  • the purpose of this was to improve the adhesion between the film and the substrate.
  • Japanese Patent Laid-Open No. Hei 6-196 421 has proposed a method of spraying in a low-pressure inert gas atmosphere (generally, a low pressure plasma spraying method). is called). Specifically, Ar gas is introduced into the vacuum vessel from which air has been exhausted at 50 to 200 h Pa, and plasma spraying is performed in this atmosphere.
  • the thermal spray coating of the oxide-based ceramic is already oxidized in the thermal spray material powder itself, so that it is not oxidized even when sprayed in the atmosphere. Even when sprayed in an Ar gas atmosphere, chemical changes are unlikely to occur in the sprayed particles. For this reason, there are few examples of research and development in the low-pressure plasma spraying method for oxide ceramics compared to atmospheric plasma spraying. In addition, research on conventional thermal spray coatings has been conducted on thermal spray materials such as metals (alloys), ceramics, and cermets in order to improve the hardness, wear resistance, heat resistance, corrosion resistance, and adhesion of the coating.
  • the acid-chromium (C r 2 0 3 ) powder as the thermal spraying material is dark green, which is close to black. When it does, it becomes a black film.
  • the aluminum oxide (A 1 2 0 3 ) powder is white, and the coating obtained by plasma spraying this powder is also white.
  • titanium oxide (T I_ ⁇ 2) powder is a white, becomes film blackish When this plasma spraying.
  • the cause of the change in the color of the thermal spray coating is that, for example, a part of oxygen constituting T i 0 2 disappears in the thermal spray heat source and becomes an oxide represented by (T in O ⁇ -J).
  • the oxide ceramic spray coating generally reproduces the color of the thermal spray powder material as it is, except for some oxides.
  • yttrium oxide Y 2 0 3
  • a 1 2 0 3 acid aluminum
  • the thermal spray coating is also white.
  • ⁇ 2 0 3 is considered to have no change in the bonding state of ⁇ and ⁇ (oxygen) that constitutes ⁇ 2 ⁇ 3 particles even if it is sprayed in a plasma heat source.
  • Both A 1 and ⁇ as metal elements have extremely strong chemical affinity with oxygen, and even in a high-temperature plasma environment, oxygen does not disappear, and even after a sprayed coating, A 1 2 0 3 , Y. Because it is considered that the physical properties of 0 3 are maintained as they are. is there.
  • the above-mentioned ⁇ 2 ⁇ 3 thermal spray coating has excellent heat resistance, high temperature oxidation resistance, corrosion resistance, and excellent resistance (plasma erosion resistance) even in a plasma etching atmosphere using low temperature plasma using halogenated materials.
  • Japanese Patent Laid-Open Nos. 10-004083, 10-163180, 10-547744, 2001-164354, 2003-321760 Japanese Patent Laid-Open Nos. 10-004083, 10-163180, 10-547744, 2001-164354, 2003-321760.
  • the ⁇ 2 ⁇ 3 sprayed coatings disclosed in these documents are all white.
  • these documents change the color of this coating without changing the characteristics of the white ⁇ 2 0 3 thermal spray coating, and use this to improve the product value of color engineering design. It does not suggest a technology to do.
  • JP-A-9-316624 discloses a technique for improving the performance of a film by irradiating a carbide cermet film or a metal film with an electron beam.
  • JP-A-10- two hundred and two thousand seven hundred eighty-two for Z R_ ⁇ 2 based ceramic sprayed coating a technique for laser beam irradiation is disclosed. Further, in Japanese Patent Application Laid-Open No. 2004-100039, when a spray coating of rare earth oxide is formed, the coating is changed from gray to black by adding carbon, Ti, and Mo to the spray material. Technology is disclosed.
  • An object of the present invention by using a thermal spray material consisting of white Upsilon 2 0 3 powder, a black spray coating oxidation Germany Toriumu, without resorting to laser beams or electron beams is proposed a method of directly forming the morphism dissolved Is. This method can solve the following problems of conventional technologies.
  • the present invention adopts the following solutions.
  • the present invention as a mixed gas plasma Jiwetto generating working gas of an inert gas and hydrogen gas, by plasma spraying a white Upsilon 2 0 3 powder, to form a black spray coating oxidation Ittoriumu This is a method for forming a black oxide yttrium sprayed coating.
  • the thermal spray atmosphere in which the thermal spray material flies is maintained in a reduced-pressure environment of 50 to 600 h Pa with an inert gas
  • the black spray coating of the yttrium oxide is ⁇ 2 o 3 _ ⁇ in a state in which some of the oxygen in the Y 2 O 3 powder has disappeared due to the reducing action of atomic hydrogen contained in the plasma jet. It is formed by the accumulation of black particles represented,
  • the spraying atmosphere should be an environment in which non-oxidizing gas is allowed to flow around the plasma spray gun to prevent air from entering the plasma jet toward the surface.
  • the spray material consisting of the white Upsilon 2 ⁇ 3 powder is a particle size is large can of 5 to 80 / zm
  • the working gas for generating plasma 'jet is a gas whose volume ratio of inert gas to hydrogen gas is within the range of 10 1-3 -1;
  • the base material includes various steels including stainless steel, aluminum and alloys thereof, titanium and alloys thereof, tungsten and alloys thereof, molybdenum and alloys thereof, sintered carbon, quartz, glass, plastics, oxides
  • metal-based or non-metallic base materials selected from ceramic and non-oxide ceramic sintered bodies,
  • the undercoat is selected from Ni and alloys thereof, Cr and alloys thereof, W and alloys thereof, Mo and Mo alloys, Ti and Ti alloys, A1 and alloys thereof. Being one or more metals or alloys thereof, it is thought that it will provide a good solution.
  • the present invention also provides that a black sprayed oxide yttrium film having a composition of Y 2 0 3 — x formed by the above method is formed to a thickness of 50 to 2000; zm.
  • a characteristic black oxide yttrium thermal spray coating member is proposed.
  • An undercoat having a film thickness of 50 to 500 ⁇ is provided between the black sprayed coating of yttrium oxide and the base material,
  • the base material includes various steels including stainless steel, aluminum and its alloys, titanium and its alloys, tungsten and its alloys, molypden and And one or more metal-based or non-metallic base materials selected from ceramic alloys, sintered carbon, quartz, glass, plastics, oxide-based and non-acidic ceramics,
  • the undercoat is one selected from Ni and alloys thereof, Cr and alloys thereof, W and alloys thereof, Mo and Mo alloys, Ti and Ti alloys, A1 and alloys thereof.
  • the spraying atmosphere is an environment in which non-oxidizing gas is allowed to flow around the plasma spray gun to prevent air from entering the plasma jet toward the surface.
  • the thermal spray material made of the white Y 2 O 3 powder has a particle size of 5 to 80 ⁇
  • the working gas for generating the plasma jet is a gas having a volume ratio of inert gas to hydrogen gas in the range of 10 Zl to 3 Zl.
  • the present invention adds a highly reducing hydrogen gas to an inert gas for generating a plasma jet as a thermal spraying heat source without using coloring components such as carbon, Ti, and Mo.
  • a commercially available white Y 2 O 3 spray powder for thermal spraying a black yttrium oxide spray coating can be directly formed. Therefore, existing thermal spraying related equipment including low pressure plasma spraying equipment can be used as it is.
  • the processing for secondary blackening such as laser beam or electron beam irradiation can be omitted, so that no high energy irradiation equipment is required. Therefore, in addition to improving workability, there are significant economic effects such as eliminating the need for new equipment.
  • the black oxide yttrium spray coating to which the method of the present invention is applied is white Y W 200
  • Corrosion resistance equivalent to 2 O 3 sprayed coatings, as well as plasma resistance and erosion resistance, can be used in the same applications.
  • the member formed with this black sprayed coating can be used as a heat transfer surface or a heat receiving surface.
  • the heat radiation characteristics and the heat receiving efficiency are improved.
  • the plasma etching rate is improved and the quality is made uniform.
  • a product having a black acid-yttrium spray coating formed in accordance with the present invention maintains a black luster in the entire thickness direction, and therefore, even if a mechanical process such as surface grinding is performed. However, the film is always black, which can increase the product value.
  • the black acid yttrium spray coating member according to the present invention when used in a semiconductor processing apparatus or the like, is less prone to adhesion of reaction products due to the particle etching action. There is no need to clean the equipment, and work efficiency can be improved.
  • the thermal spray coating that is used in semiconductor manufacturing 'processing apparatus are white represented by A 1 2 0 3 Seramitsu click, also formed in the prior art the Y 2 0 3 sprayed coating also white .
  • the black ⁇ 20 3 sprayed coating covering member makes it easy to distinguish between coating materials and improves the accuracy and productivity of maintenance and inspection.
  • Figure 1 is a schematic diagram of a plasma spray gun.
  • Figure 2 is an electron micrograph of the appearance color of the yttrium oxide sprayed coating.
  • a black yttrium oxide film is formed by thermal spraying.
  • an inert gas such as Ar or He is used as the working gas for the plasma spraying method. This is to generate a high-temperature plasma jet as a heat source by flowing an inert gas through the arc in the thermal spray gun obtained by applying a DC voltage.
  • the environment of this plasma jet heat source is composed of a collection of electrons, ions, atoms, and molecules ionized from Ar, He, etc., so the environment is reducible unless air is mixed in from the outside. Is non-oxidizing.
  • the plasma heat source in the spray gun in such a state has white Y 2
  • the sprayed coating obtained when spraying with 3 powders is white, and the appearance color does not change.
  • the reason for this is that the normal plasma spraying method has a low plasma jet reducing power and the spraying atmosphere in which the sprayed particles fly is in the atmosphere, so it is melted by the heat source and sprayed. As the 20 3 particles come into contact with the air, they remain white.
  • the oxygen partial pressure in the spraying atmosphere that is, the spraying environment in which the droplets ejected from the spraying gun fly toward the deposition surface is extremely low, and the oxygen is essentially oxygen-free.
  • a film is formed under a reduced pressure of 50 to 200 h Pa of gas, it may turn gray under weak oxidation, but it does not change to black.
  • the working gas 4 to be introduced into the thermal spray gun 2 installed in the decompression vessel 1 can be mixed with a highly reducing hydrogen gas and introduced.
  • the present invention is characterized in that a mixed gas to which hydrogen gas, which is a reducing gas, is added is used as the plasma generating working gas supplied into the thermal spray gun 2.
  • a mixed gas to which hydrogen gas, which is a reducing gas, is added is used as the plasma generating working gas supplied into the thermal spray gun 2.
  • the thermal spray material introduced into this thermal spray gun 2 (white Y 2 0 3 powder) 5 is reduced.
  • the reduced sprayed material rides on the plasma jet 6 and adheres to the substrate surface.
  • Oxide Ittoriumu thermally sprayed coating 7 formed Te this good Unishi will become those results to be reduced during spraying, black ⁇ 2 ⁇ 3 _ ⁇ spray particles are deposited, it become black sprayed coating.
  • the white Sani ⁇ yttrium arm in "Y 2 0 3 j the oxidation Ittoriumu black comprising the composition of the" ⁇ 2 ⁇ 3 _ ⁇ "obtained according to the application of the present invention I decided to call it “oxidized yttrium”.
  • ⁇ 1 2 0 3 exhibits white even if it is formed using a plasma jet heat source containing hydrogen gas, the blackening phenomenon of ⁇ 2 0 3 is considered to be a phenomenon peculiar to the present invention. .
  • the surface to be treated (base) It was found that when the spraying route of sprayed particles toward the material surface is in the atmosphere (acidic atmosphere), the molten particles return to white or gray again when they come into contact with the air. Therefore, in the present invention, control of the spraying atmosphere (the particle flight route) is also important. That is, in the case of atmospheric plasma spraying (the flight route is under the atmosphere) without using the decompression vessel 1, an environmental shut-off device such as an air is not mixed in the plasma jet 6 is installed.
  • a r around Jiwetto, H e, and flow of the inert gas or less reactive gas such as N 2 is necessary to avoid the direct contact between the spray particles and air to fly in the molten state is there.
  • the use of a low-pressure plasma spraying apparatus that forms a film in a reduced-pressure inert gas atmosphere is advantageous because there is no contact between particles and air (exactly oxygen) during spraying.
  • the amount of H 2 gas added to the plasma generating gas such as Ar or He is preferably set to the following mixing ratio in terms of volume ratio. That is,
  • the mixing ratio of H 2 is less than 10 Zl, preferably 5 Zl, the yttrium oxide is not sufficiently blackened or the color quality is not constant.
  • mixing Ar gas more than 3Z1 will saturate the blackening effect.
  • the object of the invention can be achieved by maintaining the ratio of H 2 gas to the amount of Ar gas alone.
  • the ratio is preferably about 5Zl to 3Zl.
  • Figure 2 (a) ⁇ U) are those according to black oxide I Ttoriumu thermal spray coating and the prior art which is formed by a technique according to the present invention showing the appearance of the Y 2 0 3 film.
  • an Ar / H 2 mixed gas suitable for the present invention is used as a working gas for plasma jet generation, and the thermal spraying environment is also controlled to a non-acidic atmosphere, so that the oxygen partial pressure is reduced.
  • a black oxide yttrium spray coating can be formed by thermal spraying in an atmosphere with little.
  • the particle size of the powder should be in the range of 5-80 ⁇ m, especially 5-50 / im Are preferred. The reason is that powders having a particle size larger than 80 ⁇ often contain unmelted particles that do not completely melt in the thermal spray heat source. The inside of the unmelted particles is not affected by the plasma heat source containing hydrogen gas, and therefore, it is often observed that the white state is maintained, which causes a deterioration in the film quality. On the other hand, particles of 5 m or less completely melt to the inside and turn black, but the feed rate from the powder feeder to the spray gun becomes unstable, or it becomes molten and sublimated in a plasma heat source. This is because it does not become a strength factor for constituting the coating, so that the cross-sectional structure of the thermal spray coating becomes uneven and uneven, and the strength of the coating may deteriorate.
  • Purity Y 2 0 3 powder used in the present invention impurities (e.g. F e, M g, C r , A l, N i, S i , etc.) moderate with less recent inventors As a result of a survey of the commercial products, all of them were 9 8 (mass%) or more, and even if these commercial products were used, they could be formed as a black acid yttrium sprayed coating, so there is no particular limitation.
  • impurities e.g. F e, M g, C r , A l, N i, S i , etc.
  • the target for forming the black spray coating of the above-mentioned yttrium oxide that is, the base material is A 1 and its alloy, stainless steel, Ti and its alloy, ceramic sintered body (for example, oxide, nitriding) Any material such as quartz, glass, plastics, etc. can be used, as well as materials, borides, silicides, and mixtures thereof. In addition, these materials can be used with various vapor-deposited films or adhesive films, and they may be formed directly on the surface of these materials or via an undercoat or intermediate layer. Les.
  • the material for the undercoat includes Ni and its alloys, Cr and its alloys, W and its alloys, Mo and its alloys, Ti and Further, it is preferable to use a metal or an alloy selected from one or more selected from Al, its alloys, Al, its alloys, Mg alloys, and the like to a thickness of about 50 to 500 m.
  • the thermal spray coating of the undercoat is thinner than 50 ⁇ , the effect as an undercoat is weak. It's not a good idea, because it leads to an increase in costs.
  • the undercoat it is preferable to use an electric arc spraying method, a flame spraying method, a high-speed frame spraying method, an atmospheric plasma spraying method, a low pressure plasma spraying method, an explosion spraying method, or the like.
  • the black yttrium yttrium spray coating according to the present invention which will be the top coat, is either formed directly on the surface of the base material or is spray-laminated on the undercoat.
  • the undercoat is formed as an intermediate layer between the black yttrium oxide sprayed coating and the base material, and its role is to exert the adhesion strength with the base material —the black color formed as the top coat.
  • Those that maintain good adhesion with the other yttrium oxide are selected.
  • Metal materials are preferred, such as Ni and its alloys, Cr and its alloys, W and its alloys, Mo and its alloys, Ti and its alloys, A1 and its alloys, Mg It is preferable to use one or more metals or alloys selected from alloys and the like so that the thickness is about 50 to 50 / m.
  • a white spray coating of Y 2 0 3 according to the prior art and a prior art are provided on the surface of a quartz glass protective tube with a built-in heating wire.
  • a white Y 2 O 3 thermal spray coating disclosed in No. 3 black by electron beam irradiation and the black thermal spray coating (50 ⁇ mi ⁇ ) of the yttrium oxide of the present invention.
  • the wavelength emitted from the surface of each coating was investigated by passing an electric current through.
  • the Y 2 O 3 white sprayed coating was about 0.2 to 1 m, while the acid Yittrium black sprayed coating was 0.3 to 5 111 for both the electron beam irradiation treatment and the black coating according to the present invention.
  • infrared emission was observed, and a difference in efficiency as a heater was observed.
  • the above two types of acid wet black spray coating (50 ⁇ m thick) are applied to the surface of the halogen lamp (high brightness lamp). While the wavelength ranged from 0.2 to 0.4 ⁇ , the one with a black sprayed coating would be 0.3 to 10 / m, and can be used in the far infrared region. As a result, the improvement in efficiency was revealed. In the white spray coating Y 2 0 3 according to the prior art, or the same as the state with no facilities E of the thermal spray coating, or less was within the range of wavelengths.
  • the black yttrium oxide spray coating formed by applying the method of the present invention not only improves the plasma erosion resistance but also as a heat source for accelerating the etching processing speed as a member for semiconductor processing equipment. It turned out to be useful.
  • the surface of a test piece of SUS 4 10 steel (5 OmmX 5 OmmX 5 mm) was subjected to blast roughening, and the atmospheric pressure was controlled to 50 to 200 h h Pa with Ar gas.
  • Y 2 0 3 was formed to a thickness of 1 50 ⁇ by the reduced pressure plasma spraying method.
  • the effect was examined on the presence or absence of a test piece in which an Ni 1 A 1 alloy undercoat was applied to a thickness of 100 ⁇ by atmospheric plasma spraying.
  • an Ar / H 2 volume ratio of 5Z1 is used as the working gas.
  • an ArZHe ratio of 5Z1 was used.
  • the test piece with the thermal spray coating is the top coat formed by spraying Y 2 O 3 . After examining the appearance color, the following thermal shock test was conducted to examine the peel resistance of the sprayed coating.
  • test pieces (Nos. 1 to 4) formed under the conditions of Ar ZH 2 volume ratio 5/1 as the working gas of the plasma heat source according to the present invention are black, and hydrogen gas is used.
  • Example 2 all the sprayed specimens shown in Example 2 were formed by an atmospheric plasma spraying method, and the thermal resistance test under the same conditions as in Example 2 was used to investigate the peel resistance of the film.
  • Ar / H 2 volume ratio 4/1 is used, and Ar gas is introduced around the spray gun, particularly near the spray gun outlet. A large amount of air was flown to prevent air from entering the plasma jet.
  • Table 2 shows the results. Even if the black oxide yttrium thermal spray coating was formed by the atmospheric spraying method, the white Y 2 by the conventional technology as well as the reduced pressure plasma spraying method of Example 2 was used. As with the O 3 sprayed coating, it was confirmed that excellent peel resistance was maintained.
  • the thermal spraying uses the atmospheric plasma spraying method, and the gas composition for plasma generation is as follows:
  • the technology according to the present invention can be used not only for blackening yttrium oxide but also for other ceramics, for example, blackening technology such as T i 0 2 and T i 0 2 — A 1 2 0 3. It is applied to the formation of liquid crystal and other materials used in fields such as polymer industry and machine industry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

A technology for forming a black yttrium oxide sprayed coating from a white Y2O3 spray powder material. In this technology, plasma spraying of a white Y2O3 powder material for spray is carried out with the use of a mixed gas obtained by adding hydrogen gas to an inert gas, such as Ar or He, as a working gas for plasma/jet generation to thereby convert the material to black particles of the formula Y2O3-x having a portion of the oxygen of the Y2O3 powder lost by the strong reducing action of atomic hydrogen contained in plasma heat source. Thus, a black yttrium oxide sprayed coating is formed on a surface of base material.

Description

明 細 書 黒色酸化ィットリゥム溶射皮膜の形成方法おょぴ黒色酸化ィットリゥム溶射 皮膜被覆部材 技術分野  Description Black black yttrium spray coating method Opposite black oxide yttrium spray coating material Technical Field
本発明は、 熱放射性ゃ耐損傷性などの特性に優れる黒色酸化ィットリウム 溶射皮膜の形成方法と、 カラーデザィン性に優れる黒色酸化ィットリゥム皮 膜被覆部材に関するものである。 背景技術  The present invention relates to a method for forming a thermal sprayed black yttrium oxide thermal spray coating having excellent properties such as damage resistance and a black yttrium oxide coating material having excellent color design. Background art
溶射法は、 金属やセラミックス、 サーメットなどの粉末を、 プラズマジェ ットゃ燃焼炎によって溶融しつつ、 飛行させ、 被溶射体 （基材） の表面に吹 き付けることによって、 該基材の表面に皮膜を形成する技術であり、 多くの 産業分野において広く採用されている表面処理技術の一つである。 こうした 溶射法を適用して得られた溶射皮膜は、 この皮膜を構成する粒子どうしの結 合力の強弱、結合しない粒子の量、 また、溶融しない粒子 （以下、 「未溶融粒 子」 という） の量などによって、 皮膜の機械的強度や耐食性に大きな差が生 じることが知られている。  In the thermal spraying method, a powder of metal, ceramics, cermet or the like is melted by a plasma jet while being burned by a combustion flame, and then sprayed onto the surface of a thermal sprayed body (base material) to thereby surface the base material. This is one of the surface treatment technologies widely used in many industrial fields. The thermal spray coating obtained by applying this thermal spraying method consists of the strength and weakness of the bonding force between the particles that make up this coating, the amount of unbonded particles, and the particles that do not melt (hereinafter referred to as “unmelted particles”). It is known that there are large differences in the mechanical strength and corrosion resistance of the coating depending on the amount.
このため、 従来の溶射技術開発の目標は、 例えば、 プラズマのような高温 の熱源を用いることによって、 被溶射体の表面に強い衝突エネルギーを発生 させることによって、 粒子間結合力を高めるとともに気孔率を小さくし、 さ らに皮膜と基材との接着力を向上させることにあった。  For this reason, the goal of conventional thermal spraying technology development is to increase the interparticle bonding force and increase the porosity by generating strong collision energy on the surface of the sprayed object, for example, by using a high-temperature heat source such as plasma. The purpose of this was to improve the adhesion between the film and the substrate.
一方、 金属の溶射皮膜は、 これを大気中で形成すると、 すべての溶射粒子 が空気と接触して、 粒子の表面に酸ィ匕膜が生成し、 そのために粒子間結合力 が低下し、 基材との密着性も悪くなる。 従来、 この問題を解決する方法とし て、 例えば、 特開平 6 - 1 9 6 4 2 1号公報では、 低圧の不活性ガス雰囲気 中において溶射する方法が提案されている （一般に、 減圧プラズマ溶射法と 呼ばれている）。具体的には、空気を排出した真空容器中に、 A rガスを 5 0 〜2 0 0 h P a導入し、 この雰囲気中でプラズマ溶射する方法である。 この点に関し、 酸ィ匕物系セラミックの溶射皮膜は、 溶射材料粉末自体が既 に酸ィ匕されているため、大気中で溶射しても酸ィ匕されることはな 一方で、 減圧下の A rガス雰囲気中で溶射しても、 溶射粒子に化学変化が生じにくい という特性がある。 このことから、 酸化物系セラミックスの減圧プラズマ溶 射法は、 大気プラズマ溶射に比較して研究開発例が少ないのが現状である。 また、 従来の溶射皮膜の研究は、 この皮膜が有する硬さ、 耐摩耗性、 耐熱 性、耐食性あるいは密着性などの向上をはかるために、金属 （合金)、セラミ ック、 サーメットなどの溶射材料の種類やィ匕学成分の選定をはじめ、 溶射法 の選択と溶射条件の決定などに重点が置力れている。 従って、 従来の溶射皮 膜については、 皮膜の色彩を工学的に利用したり、 溶射皮膜製品のカラーデ ザイン的商品価値の向上に関する検討は殆ど行われていない。 On the other hand, when a metal sprayed coating is formed in the atmosphere, all the sprayed particles come into contact with the air, and an oxide film is formed on the surface of the particles. Adhesion with the material also deteriorates. Conventionally, as a method for solving this problem, for example, Japanese Patent Laid-Open No. Hei 6-196 421 has proposed a method of spraying in a low-pressure inert gas atmosphere (generally, a low pressure plasma spraying method). is called). Specifically, Ar gas is introduced into the vacuum vessel from which air has been exhausted at 50 to 200 h Pa, and plasma spraying is performed in this atmosphere. In this regard, the thermal spray coating of the oxide-based ceramic is already oxidized in the thermal spray material powder itself, so that it is not oxidized even when sprayed in the atmosphere. Even when sprayed in an Ar gas atmosphere, chemical changes are unlikely to occur in the sprayed particles. For this reason, there are few examples of research and development in the low-pressure plasma spraying method for oxide ceramics compared to atmospheric plasma spraying. In addition, research on conventional thermal spray coatings has been conducted on thermal spray materials such as metals (alloys), ceramics, and cermets in order to improve the hardness, wear resistance, heat resistance, corrosion resistance, and adhesion of the coating. Emphasis is placed on the selection of the spraying method and the determination of the spraying conditions, including the selection of the types and chemical components. Therefore, with regard to conventional thermal spray coatings, there have been little studies on the use of coating colors in engineering or on the improvement of the color design value of thermal spray coating products.
し力 しながら、 セラミック溶射皮膜は、 その外観色を観察すると、 溶射材 料としての酸ィ匕クロム （C r 20 3 ) 粉末は、 黒色に近い濃緑色であるが、 こ れをプラズマ溶射した場合、黒色の皮膜となる。一方、酸化アルミニウム（A 1 2 0 3) 粉末は白色であり、 これをプラズマ溶射して得られる皮膜もまた白 色である。 ただし、 酸化チタン （T i〇2) 粉末は白色系であるが、 これを プラズマ溶射すると黒色系の皮膜になる。 このように、 溶射皮膜の色が変化 する原因は、 溶射熱源中において、 例えば T i 0 2を構成する酸素の一部が 消失して、 （T i n O ^-Jで示される酸化物となるためではないかと考えら れている。 （特開平 9一 0 6 9 5 5 4号公報） However, when the appearance color of the ceramic sprayed coating is observed, the acid-chromium (C r 2 0 3 ) powder as the thermal spraying material is dark green, which is close to black. When it does, it becomes a black film. On the other hand, the aluminum oxide (A 1 2 0 3 ) powder is white, and the coating obtained by plasma spraying this powder is also white. However, titanium oxide (T I_〇 2) powder is a white, becomes film blackish When this plasma spraying. In this way, the cause of the change in the color of the thermal spray coating is that, for example, a part of oxygen constituting T i 0 2 disappears in the thermal spray heat source and becomes an oxide represented by (T in O ^ -J). (Japanese Patent Laid-Open No. 9 0 6 9 5 5 4)
以上、 説明したように、 酸化物系セラミック溶射皮膜は、 一部の酸化物を 除き、 溶射用粉末材料自体の色がそのまま皮膜の色として再現されるのが普 通である。 例えば、 酸化イットリウム （Y 2 0 3) は、 通常、 酸ィ匕アルミ-ゥ ム （A 1 2 0 3) と同じように、 粉末材料の状態はもとより、 この粉末材科を 溶射して得られる溶射皮膜もまた白色系である。 Υ 20 3は、 たとえこれをプ ラズマ熱源中で溶射しても、 Υ 2 Ο 3粒子を構成する Υと ο (酸素） の結合状 態に変化はないと考えられる。 それは、 金属元素としての A 1や Υは、 とも に酸素との化学的親和力が極めて強く、 高温のプラズマ環境中においても酸 素を消失することなく、 溶射皮膜となった後でも、 粉末材料時の A 1 2 0 3、 Y。0 3の物理ィ匕学的特性をそのまま維持しているためと考えられるからで ある。 As explained above, the oxide ceramic spray coating generally reproduces the color of the thermal spray powder material as it is, except for some oxides. For example, yttrium oxide (Y 2 0 3 ) is usually obtained by spraying this powder material as well as the state of the powder material in the same manner as acid aluminum (A 1 2 0 3 ). The thermal spray coating is also white. Υ 2 0 3 is considered to have no change in the bonding state of Υ and ο (oxygen) that constitutes 粒子2 Ο 3 particles even if it is sprayed in a plasma heat source. Both A 1 and Υ as metal elements have extremely strong chemical affinity with oxygen, and even in a high-temperature plasma environment, oxygen does not disappear, and even after a sprayed coating, A 1 2 0 3 , Y. Because it is considered that the physical properties of 0 3 are maintained as they are. is there.
上記 γ2ο3溶射皮膜は、 耐熱性ゃ耐高温酸化性、 耐食性に優れる他、 ハロ ゲンィ匕物を用レ、た低温プラズマによるプラズマエッチング雰囲気中において も、 優れた抵抗性 （耐プラズマエロージョン性） を発揮するが知られている (特開平 10— 004083号公報、 特開平 10— 163180号公報、 特 開平 10— 547744号公報、 特開 2001— 164354号公報、 特開 2003-321760号公報）。 The above-mentioned γ 2 ο 3 thermal spray coating has excellent heat resistance, high temperature oxidation resistance, corrosion resistance, and excellent resistance (plasma erosion resistance) even in a plasma etching atmosphere using low temperature plasma using halogenated materials. ) Are known (Japanese Patent Laid-Open Nos. 10-004083, 10-163180, 10-547744, 2001-164354, 2003-321760) .
これらの文献に開示された γ2ο3溶射皮膜は、すべて白色系である。また、 これらの文献は、 白色系の Υ203溶射皮膜の特性を変化させることなく、 こ の皮膜の色を変化させて、 これを工学的おょぴカラーデザイン的商品価値の 向上に利用する技術を提案するものではない。 The γ 2 ο 3 sprayed coatings disclosed in these documents are all white. In addition, these documents change the color of this coating without changing the characteristics of the white Υ 2 0 3 thermal spray coating, and use this to improve the product value of color engineering design. It does not suggest a technology to do.
基材の表面を改質する技術としては、 上掲の溶射皮膜を被覆形成するもの の他、 電子ビーム照射やレーザビーム照射を利用する技術がある。 例えば、 電子ビーム照射に関しては、 特開昭 61-104062号公報において、 金 属皮膜に電子ビームを照射してこの皮膜を溶融して気孔を消滅させる技術が ある。 また、 特開平 9一 316624号公報には、 炭化物サーメット皮膜や 金属皮膜に対して電子ビームを照射して、 皮膜の性能を向上させる技術が開 示されている。 また、 特開平 10— 202782号公報には、 Z r〇2系セ ラミック溶射皮膜に対して、 レーザビーム照射する技術が開示されている。 さらに、 特開 2004— 100039号公報には、 希土類酸化物の溶射皮膜 を形成する場合に、 溶射材料中にカーボン、 T i、 Moを添加することによ つて、 皮膜を灰色〜黒色に変化させる技術が開示されている。 As a technique for modifying the surface of the substrate, there is a technique using electron beam irradiation or laser beam irradiation in addition to the above-mentioned thermal spray coating coating. For example, regarding electron beam irradiation, Japanese Patent Application Laid-Open No. 61-104062 discloses a technique for irradiating a metal film with an electron beam and melting the film to eliminate pores. JP-A-9-316624 discloses a technique for improving the performance of a film by irradiating a carbide cermet film or a metal film with an electron beam. JP-A-10- two hundred and two thousand seven hundred eighty-two for Z R_〇 2 based ceramic sprayed coating, a technique for laser beam irradiation is disclosed. Further, in Japanese Patent Application Laid-Open No. 2004-100039, when a spray coating of rare earth oxide is formed, the coating is changed from gray to black by adding carbon, Ti, and Mo to the spray material. Technology is disclosed.
し力 し、 これらの開示技術は、 溶射粉末材料への異種成分の添加を必須条 件としているため、 添加作業の増大に加え、 皮膜成分の純度低下による物理 化学的性質の低下を招レ、ている。  However, since these disclosed technologies require the addition of different components to the thermal spray powder material, in addition to an increase in the addition work, physicochemical properties are reduced due to a decrease in the purity of the coating components. ing.
いずれにしても、 これらの先行技術は、 溶射皮膜中の気孔の消滅や密着性 の向上、 または再溶融後の冷却過程を利用して皮膜に縦割れを発生させるこ とを目的とした技術であり、 異種成分の添加なしに溶射皮膜の外観色を変化 させる方法の提案ではな 、。  In any case, these prior arts are technologies aimed at generating vertical cracks in the coating by eliminating pores in the sprayed coating, improving adhesion, or using a cooling process after remelting. Yes, it is not a proposal for a method of changing the appearance color of the thermal spray coating without adding different components.
このような現状に対して、 発明者らは、 かって、 特開 2006— 1180 5 3号公報において開示したように、 白色の Y 20 3溶射皮膜に対し、 レーザ ビームや電子ビームを照射することによって、 これを黒色に変化させること に成功し、 溶射皮膜の黒色ィヒによる熱放射特性およびカラーデザイン的商品 価値を上げることに成功した。 発明の開示 In response to such a current situation, the inventors have previously disclosed Japanese Unexamined Patent Application Publication No. 2006-1180. 5 As disclosed in Gazette No. 3, we succeeded in changing the white Y 2 0 3 sprayed coating to black by irradiating it with a laser beam or electron beam. We succeeded in increasing the value of thermal radiation characteristics and color design products. Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
本発明の目的は、 白色の Υ 20 3粉末からなる溶射材料を用いて、 酸化イツ トリゥムの黒色溶射皮膜を、 レーザビームや電子ビームに頼ることなく、 溶 射によって直接形成する方法を提案するものである。 この方法によれば、 従 来技術が抱えている次のような課題を解決することができる。 An object of the present invention, by using a thermal spray material consisting of white Upsilon 2 0 3 powder, a black spray coating oxidation Germany Toriumu, without resorting to laser beams or electron beams is proposed a method of directly forming the morphism dissolved Is. This method can solve the following problems of conventional technologies.
( 1 ) 従来技術では、 希土類酸化物の溶射皮膜を着色する場合、 溶射粉末中 にカーボンや T i、 M oなどの着色成分を添加しているため、 生産工程の增 加によるコストアップに加え、 異種成分の混入による皮膜純度の低下、 耐食 性、 耐熱性などの物理ィ匕学的性質の劣ィ匕があつた。  (1) In the prior art, when coloring spray coatings of rare earth oxides, coloring components such as carbon, Ti, and Mo are added to the sprayed powder, which increases costs due to an increase in production processes. The film had poor physical properties such as a decrease in film purity, corrosion resistance, and heat resistance due to mixing of different components.
( 2 ) 従来技術では、 酸ィ匕イットリウム溶射皮膜の黒色化の処理は、 白色の Y 20 3溶射皮膜を形成後、その表面をレーザビームや電子ビーム照射するこ とによって行うため、 そのための専用の設備が必要で、 生産性の低下や生産 コストの上昇を招く。 課題を解決するための手段 (2) In the prior art, the process of blackening of Sani匕yttrium sprayed coating, after forming a white Y 2 0 3 thermal spray coating, for the performance of its surface by a laser beam or electron beam irradiation child, for the Dedicated equipment is required, leading to reduced productivity and increased production costs. Means for solving the problem
従来技術が抱えている上述した課題を解決するため、 本発明では、 以下に 述べる解決手段を採用することにした。  In order to solve the above-described problems of the prior art, the present invention adopts the following solutions.
本発明は、 不活性ガスと水素ガスとの混合ガスをプラズマ ·ジヱット発生 用作動ガスとして、 白色の Υ 203粉末をプラズマ溶射することによって、 酸 化ィットリゥムの黒色溶射皮膜を形成することを特徴とする黒色酸化ィット リゥム溶射皮膜の形成方法である。 The present invention, as a mixed gas plasma Jiwetto generating working gas of an inert gas and hydrogen gas, by plasma spraying a white Upsilon 2 0 3 powder, to form a black spray coating oxidation Ittoriumu This is a method for forming a black oxide yttrium sprayed coating.
また、 本発明では、  In the present invention,
( 1 ) 溶射材料が飛行する溶射雰囲気が、 不活性ガスによる 5 0〜 6 0 0 h P aの減圧環境に維持されていること、 (2) 前記酸化ィットリゥムの黒色溶射皮膜は、 前記プラズマ ·ジエツト中 に含まれる原子状水素が有する還元作用によって Y 2 O 3粉末の酸素の一部 が消失した状態の γ2ο3_χで表わされる黒色粒子の堆積によって形成され たものであること、 (1) The thermal spray atmosphere in which the thermal spray material flies is maintained in a reduced-pressure environment of 50 to 600 h Pa with an inert gas, (2) The black spray coating of the yttrium oxide is γ 2 o 3 _ χ in a state in which some of the oxygen in the Y 2 O 3 powder has disappeared due to the reducing action of atomic hydrogen contained in the plasma jet. It is formed by the accumulation of black particles represented,
(3) 溶射雰囲気が、 プラズマ溶射ガンの周囲に非酸化性ガスを流して、 被 表面に向うプラズマ ·ジヱットへの空気の侵入を防止した環境にすること、 (3) The spraying atmosphere should be an environment in which non-oxidizing gas is allowed to flow around the plasma spray gun to prevent air from entering the plasma jet toward the surface.
(4) 前記白色の Υ2〇3粉末からなる溶射材料は、粒径が 5〜80/zmの大 きさであること、 (4) the spray material consisting of the white Upsilon 2 〇 3 powder is a particle size is large can of 5 to 80 / zm,
(5) プラズマ 'ジェット発生のための前記作動ガスは、 不活性ガスと水素 ガスとの容積比が 10 1〜3ノ1の範囲内のガスでぁること、  (5) The working gas for generating plasma 'jet is a gas whose volume ratio of inert gas to hydrogen gas is within the range of 10 1-3 -1;
(6) 前記酸ィ匕イットリウムの黒色溶射皮膜は、 基材の表面に直接、 または アンダーコートを介して形成されていること、  (6) The black sprayed coating of acid yttrium is formed directly on the surface of the substrate or through an undercoat,
(7) 前記基材は、 ステンレス鋼を含む各種の鋼、 アルミユウムおよびその 合金、 チタンおよびその合金、 タングステンおよびその合金、 モリブデンお よびその合金、 焼結炭素、 石英、 ガラス、 プラスチック類、 酸化物系および 非酸化物系のセラミック焼結体から選ばれる一種以上の金属系または非金属 系基材であること、  (7) The base material includes various steels including stainless steel, aluminum and alloys thereof, titanium and alloys thereof, tungsten and alloys thereof, molybdenum and alloys thereof, sintered carbon, quartz, glass, plastics, oxides One or more metal-based or non-metallic base materials selected from ceramic and non-oxide ceramic sintered bodies,
(8) 前記アンダーコートは、 N iおよびその合金、 C rおよびその合金、 Wおよびその合金、 Moおよび Mo合金、 T iおよび T i合金、 A 1およぴそ の合金の中から選ばれる 1種以上の金属もしくはその合金であること、 力 好ましい解決手段を与えることになるものと考えられる。  (8) The undercoat is selected from Ni and alloys thereof, Cr and alloys thereof, W and alloys thereof, Mo and Mo alloys, Ti and Ti alloys, A1 and alloys thereof. Being one or more metals or alloys thereof, it is thought that it will provide a good solution.
また、本発明は、上記の方法によって形成された Y203— xの組成を示す酸 化ィットリゥムの黒色溶射皮膜が、 膜厚が 50〜2000 ;z mの厚さで形成 されていることを特徴とする黒色酸化ィットリゥム溶射皮膜被覆部材を提案 する。 The present invention also provides that a black sprayed oxide yttrium film having a composition of Y 2 0 3 — x formed by the above method is formed to a thickness of 50 to 2000; zm. A characteristic black oxide yttrium thermal spray coating member is proposed.
本発明では、  In the present invention,
( 1 ) 前記酸化ィットリゥムの黒色溶射皮膜と基材との間には、 膜厚が 50 〜500 μπιのアンダーコートを設けてなること、  (1) An undercoat having a film thickness of 50 to 500 μπι is provided between the black sprayed coating of yttrium oxide and the base material,
(2) 前記基材は、 ステンレス鋼を含む各種鋼、 アルミニウムおよびその合 金、 チタンおょぴその合金、 タングステンおよびその合金、 モリプデンおよ びその合金、 焼結炭素、 石英、 ガラス、 プラスチック類、 酸化物系および非 酸ィ匕物系のセラミック焼結体から選ばれる一種以上の金属系または非金属系 基材であること、 (2) The base material includes various steels including stainless steel, aluminum and its alloys, titanium and its alloys, tungsten and its alloys, molypden and And one or more metal-based or non-metallic base materials selected from ceramic alloys, sintered carbon, quartz, glass, plastics, oxide-based and non-acidic ceramics,
(3) 前記アンダーコートは、 N iおよびその合金、 C rおよびその合金、 Wおよびその合金、 Moおよび Mo合金、 T iおよび T i合金、 A 1およびそ の合金の中から選ばれる 1種以上の金属もしくはその合金であること、 (3) The undercoat is one selected from Ni and alloys thereof, Cr and alloys thereof, W and alloys thereof, Mo and Mo alloys, Ti and Ti alloys, A1 and alloys thereof. The above metals or alloys thereof,
(4) 溶射雰囲気が、 プラズマ溶射ガンの周囲に非酸化性ガスを流して、 被 表面に向うプラズマ ·ジェットへの空気の侵入を防止した環境であること、(4) The spraying atmosphere is an environment in which non-oxidizing gas is allowed to flow around the plasma spray gun to prevent air from entering the plasma jet toward the surface.
(5) 前記白色の Y2O3粉末からなる溶射材料は、粒径が 5〜80 μπιの大 きさであること、 (5) The thermal spray material made of the white Y 2 O 3 powder has a particle size of 5 to 80 μπι,
(6) プラズマ ·ジエツト発生のための前記作動ガスは、 不活性ガスと水素 ガスとの容積比が 1 0Zl〜3Zlの範囲内のガスであること、  (6) The working gas for generating the plasma jet is a gas having a volume ratio of inert gas to hydrogen gas in the range of 10 Zl to 3 Zl.
力 好ましい解決手段を与えることになるものと考えられる。 Power It is thought that it will provide a favorable solution.
本発明によれば、 次に示すような効果が期待できる。  According to the present invention, the following effects can be expected.
( 1 ) 本発明は、 溶射熱源としてのプラズマ ·ジェット発生用の不活性ガス 中に、 還元性の強い水素ガスを添加することにより、 カーボンや T i、 Mo のような着色成分を用いることなく、市販の溶射用白色 Y 2 O 3溶射粉末を用 いて、 黒色の酸化ィットリゥムの溶射皮膜を直接形成することができる。 従 つて、 減圧プラズマ溶射装置を含め、 既存の溶射関連装置をそのまま利用す ることができる。 (1) The present invention adds a highly reducing hydrogen gas to an inert gas for generating a plasma jet as a thermal spraying heat source without using coloring components such as carbon, Ti, and Mo. Using a commercially available white Y 2 O 3 spray powder for thermal spraying, a black yttrium oxide spray coating can be directly formed. Therefore, existing thermal spraying related equipment including low pressure plasma spraying equipment can be used as it is.
( 2 ) 本発明によれば、 レーザビームや電子ビーム照射のような二次黒色化 のための処理を省略することができるので、 高エネルギー照射設備などが不 要になる。 従って、 作業性の向上に加え、 新設備が不要になるなどの経済的 効果が大きい。  (2) According to the present invention, the processing for secondary blackening such as laser beam or electron beam irradiation can be omitted, so that no high energy irradiation equipment is required. Therefore, in addition to improving workability, there are significant economic effects such as eliminating the need for new equipment.
(3) 減圧下の無酸素プラズマ溶射法による黒色酸ィ匕ィットリゥム皮膜の形 成方法 （特開 2006— 1 1 8053号公報） では、 灰色から黒色までの濃 淡いろいろな黒色が現れて品質が安定しないが、 本発明方法によれば、 常に 安定した黒色酸化ィットリゥム皮膜が得られ、 品質の向上および生産性の向 上が期待できる。  (3) The formation method of black acid yttrium film by oxygen-free plasma spraying under reduced pressure (JP 2006-1 1 8053 A) shows various black and white colors from gray to black and the quality is improved. Although not stable, according to the method of the present invention, a stable black oxide yttrium film can always be obtained, and an improvement in quality and an improvement in productivity can be expected.
(4) 本発明方法を適用した黒色の酸化ィットリゥム溶射皮膜は、 白色の Y W 200 (4) The black oxide yttrium spray coating to which the method of the present invention is applied is white Y W 200
2 O 3溶射皮膜と同等の耐食†生およぴ耐ブラズマ 'エロージョン性をもってい るので、 同じ用途に使用することができる。 Corrosion resistance equivalent to 2 O 3 sprayed coatings, as well as plasma resistance and erosion resistance, can be used in the same applications.
( 5 ) 本発明によれば、 溶射皮膜自体が黒色になるので、 この黒色溶射皮膜 を形成した部材は、 これを伝熱面ゃ受熱面に用いると、 熱吸収能力や遠赤外 線放射能力の向上が期待できる他、 熱放射特性おょぴ受熱効率が向上する。 とくに、 半導体加工装置に組み込むと、 プラズマエッチングカ卩工速度を向上 させるとともに、 その品質の均一化に効果を発揮する。  (5) According to the present invention, since the sprayed coating itself becomes black, the member formed with this black sprayed coating can be used as a heat transfer surface or a heat receiving surface. The heat radiation characteristics and the heat receiving efficiency are improved. In particular, when incorporated in semiconductor processing equipment, the plasma etching rate is improved and the quality is made uniform.
( 6 ) 本発明に従って形成した黒色の酸ィ匕ィットリゥム溶射皮膜を有する製 品は、 厚み方向の全体が黒い光沢を維持しているため、 たとえ、 表面研削の ような機械的加工を行ったとしても皮膜は常に黒いでの、 商品価値を上げる ことができる。  (6) A product having a black acid-yttrium spray coating formed in accordance with the present invention maintains a black luster in the entire thickness direction, and therefore, even if a mechanical process such as surface grinding is performed. However, the film is always black, which can increase the product value.
( 7 ) 本発明に係る黒色の酸ィヒイットリウム溶射皮膜被覆部材は、 これを半 導体加工装置などに使用した場合、 パーティクルゃェッチング作用による反 応生成物の付着が目立ちにくいため、必要以上に装置を洗浄することがなく、 作業効率の向上が期待できる。  (7) The black acid yttrium spray coating member according to the present invention, when used in a semiconductor processing apparatus or the like, is less prone to adhesion of reaction products due to the particle etching action. There is no need to clean the equipment, and work efficiency can be improved.
( 8 ) 半導体製造'加工装置に用いれている溶射皮膜は、 A 1 20 3セラミツ クで代表される白色系であり、 また、 従来技術で形成された Y 203溶射皮膜 も白色である。 このため、 保守点検時に皮膜材質の区別がつき難く、 損傷を 受けた場合、 対策に手間取ることが多い。 この点、 黒色の Υ 20 3溶射皮膜被 覆部材は、 皮膜材質の区別が容易となり、 保守点検の精度および生産性を向 上させる。 (8) the thermal spray coating that is used in semiconductor manufacturing 'processing apparatus are white represented by A 1 2 0 3 Seramitsu click, also formed in the prior art the Y 2 0 3 sprayed coating also white . For this reason, it is difficult to distinguish between coating materials during maintenance and inspections, and it is often time-consuming to take measures if damaged. In this regard, the black Υ 20 3 sprayed coating covering member makes it easy to distinguish between coating materials and improves the accuracy and productivity of maintenance and inspection.
( 9 ) 本宪明に係る部材によれば、 カラーデザイン的に優れ、 商品価値の高 い半導体加工装置などの工業製品が得られる。 図面の簡単な説明  (9) According to the member according to the present invention, industrial products such as semiconductor processing equipment having excellent color design and high commercial value can be obtained. Brief Description of Drawings
図 1は、 プラズマ溶射ガンの略線図である。  Figure 1 is a schematic diagram of a plasma spray gun.
図 2は、 酸化ィットリゥム溶射皮膜の外観色の電子顕微鏡写真である。 発明の実施形態  Figure 2 is an electron micrograph of the appearance color of the yttrium oxide sprayed coating. Embodiment of the Invention
白色の Υ 203粉末からなる溶射材料を用いて、黒色酸化ィットリゥム溶射 皮膜を形成する方法について説明する。 Using a thermal spray material made of white 溶2 0 3 powder, black oxide yttrium thermal spraying A method for forming a film will be described.
市販の白色の γ 2ο 3粉末からなる溶射材料を用いて、黒色酸化イツトリイ ゥム溶射皮膜を形成するために、 本発明では、 溶射ガン中に熱源として導入 する作動ガスとして、 A rや H eなどの不活性ガスだけでなく、 さらにその 中に水素ガス等の還元性ガスを添加することに併せ、 溶射ガンから基材に向 う溶射粒子の飛行ルートである成膜 （溶射） 雰囲気中の酸素ポテンシャルを 低くすることが必要である。 In order to form a black yttrium oxide thermal spray coating using a thermal spray material made of commercially available white γ 2 o 3 powder, in the present invention, Ar and H are used as working gases introduced as a heat source in the thermal spray gun. In addition to the inert gas such as e, in addition to the addition of reducing gas such as hydrogen gas, the film deposition (spraying) atmosphere is the flight route of the sprayed particles from the spray gun to the substrate. It is necessary to lower the oxygen potential of.
以下に、 溶射によって、 黒色酸化ィットリゥムの皮膜が生成する理由を説 明する。 一般に、 プラズマ溶射法の作動ガスとしては、 A rや H eなどの不 活性ガスが用いられる。 これは、 直流電圧を負荷して得た溶射ガン中のァー ク中に、 不活性ガスを流すことにより、 高温のプラズマ ·ジエツトを発生さ せて、 熱源とするためである。 このプラズマ 'ジェット熱源の環境は、 A r や H eなどから電離した電子、 イオン、 原子、 および分子の集合体から構成 されているので、 環境としては外部から空気が混入しない限り還元性もしく は非酸化性である。  The reason why a black yttrium oxide film is formed by thermal spraying is described below. In general, an inert gas such as Ar or He is used as the working gas for the plasma spraying method. This is to generate a high-temperature plasma jet as a heat source by flowing an inert gas through the arc in the thermal spray gun obtained by applying a DC voltage. The environment of this plasma jet heat source is composed of a collection of electrons, ions, atoms, and molecules ionized from Ar, He, etc., so the environment is reducible unless air is mixed in from the outside. Is non-oxidizing.
しかし、 このような状態にある溶射ガン中のプラズマ熱源に、 白色の Y 2 However, the plasma heat source in the spray gun in such a state has white Y 2
Ο 3粉末を供給して溶射した場合に得られる溶射皮膜は、 白色であり、 外観 色に変化は生じない。 その理由は、 通常のプラズマ溶射法は、 プラズマ .ジ ヱットの還元力が弱いうえ、 溶射粒子が飛行していく溶射雰囲気が大気中に なっているため、 熱源によって溶融されて、 噴射飛行する Υ 203粒子が空気 に接触するため、 白色のままになるのである。 Ο The sprayed coating obtained when spraying with 3 powders is white, and the appearance color does not change. The reason for this is that the normal plasma spraying method has a low plasma jet reducing power and the spraying atmosphere in which the sprayed particles fly is in the atmosphere, so it is melted by the heat source and sprayed. As the 20 3 particles come into contact with the air, they remain white.
ただし、 減圧プラズマ溶射法のように、 溶射雰囲気、 即ち、 溶射ガンから 噴出した溶滴が被着面に向って飛行する溶射環境中の酸素分圧が極めて低く、 実質的に無酸素な A rガスの 5 0〜2 0 0 h P aの減圧下で成膜させた場合 には、 弱酸化性の下で灰色に変化することがあるものの、 黒色までに変化す ることはない。  However, as in the low-pressure plasma spraying method, the oxygen partial pressure in the spraying atmosphere, that is, the spraying environment in which the droplets ejected from the spraying gun fly toward the deposition surface is extremely low, and the oxygen is essentially oxygen-free. When a film is formed under a reduced pressure of 50 to 200 h Pa of gas, it may turn gray under weak oxidation, but it does not change to black.
そこで、 本発明では、  Therefore, in the present invention,
a .減圧容器 1内に設置される溶射ガン 2内に導入する作動ガス 4としては、 従来の A rや H eに加え、 さらに、 還元性の強い水素ガスを混合して導入す ること、 b . 上記溶射ガン 2や被処理基材 3が配置されている減圧容器 1内、 即ち、 溶射雰囲気を、 A rや H eなどの不活性雰囲気に維持すること、 In addition to the conventional Ar and He, the working gas 4 to be introduced into the thermal spray gun 2 installed in the decompression vessel 1 can be mixed with a highly reducing hydrogen gas and introduced. b. Maintaining the inside of the vacuum container 1 in which the spray gun 2 and the substrate 3 to be treated are disposed, that is, the spray atmosphere in an inert atmosphere such as Ar or He;
にしたのである。 It was.
とくに、 本発明では、 溶射ガン 2中に供給するプラズマ発生用作動ガスと して、 還元性ガスである水素ガスを添加した混合ガスを用いる点に特徴があ る。 それは、 このような作動ガスを用いると、 発生するプラズマ中には、 強 い還元性を示す原子状の水素が存在するため、 同じくこの溶射ガン 2中に導 入される溶射材料 （白色 Y 20 3粉末） 5が還元される。 そして、 その還元さ れた溶射材料がプラズマ ·ジェット 6に乗って基材表面に被着する。 このよ うにして形成される酸化ィットリゥム溶射皮膜 7は、 溶射中に還元される結 果、黒色の Υ 2 Ο 3_χ溶射粒子が堆積したものになり、黒色溶射皮膜となるの である。 In particular, the present invention is characterized in that a mixed gas to which hydrogen gas, which is a reducing gas, is added is used as the plasma generating working gas supplied into the thermal spray gun 2. This is because when such a working gas is used, there is atomic hydrogen that exhibits a strong reducibility in the generated plasma. Therefore, the thermal spray material introduced into this thermal spray gun 2 (white Y 2 0 3 powder) 5 is reduced. Then, the reduced sprayed material rides on the plasma jet 6 and adheres to the substrate surface. Oxide Ittoriumu thermally sprayed coating 7 formed Te this good Unishi will become those results to be reduced during spraying, black Υ 2 Ο 3 _ χ spray particles are deposited, it become black sprayed coating.
このことについて、 発明者らは、 黒色酸ィ匕イットリウム溶射皮膜は、 白色 の Υ 2 Ο 3粒子から酸素原子の一部が消失した Υ 2 Ο 3_χのような組成の粒子、 皮膜となるものと考えている。 ここで、 発明者らは、 白色の酸ィ匕イットリウ ムを 「Y 203 jで示し、 本発明の適用に従って得られる前記 「γ 2 ο 3 _χ」 の 組成になる黒色の酸化ィットリゥムについては、 そのまま 「酸化ィットリウ ム」 と呼ぶことにした。 なお、 Α 1 20 3は、 前記水素ガスを含むプラズマ ' ジエツト熱源を用いて成膜しても白色を呈するので、 Υ 203の黒色化現象は 本発明に特有の現象と考えている。 In this regard, the inventors Kokushokusani匕yttrium sprayed coating, the particles of the composition as the white Upsilon 2 Omicron 3 particles from the oxygen atom partially the Υ 2 Ο 3 _ loss χ of the film I believe that. Here, we show the white Sani匕yttrium arm in "Y 2 0 3 j, the oxidation Ittoriumu black comprising the composition of the" γ 2 ο 3 _ χ "obtained according to the application of the present invention I decided to call it “oxidized yttrium”. In addition, since Α 1 2 0 3 exhibits white even if it is formed using a plasma jet heat source containing hydrogen gas, the blackening phenomenon of Υ 2 0 3 is considered to be a phenomenon peculiar to the present invention. .
発明者らの研究によると、 ブラズマ熱源として、 溶射ガン 2中の不活性ガ ス中に水素ガスを添加した混合作動ガス 4を用いた場合であっても、 溶射ガ ンから被処理表面 （基材表面） に向う溶射粒子の飛行ルートが大気中 （酸ィ匕 雰囲気） になると、 溶融粒子が空気に触れてと再び白色や灰色に戻ることが わかった。 従って、 本発明では、 溶射雰囲気 （粒子飛行ルートのこと） の制 御もまた重要である。 即ち、 減圧容器 1を用いることなく、 大気プラズマ溶 射 （飛行ルートが大気下である） する場合は、 前記プラズマ ·ジエツト 6に 空気が混入しなレ、ような環境遮断装置を取り付ける 、 ブラズマ ·ジヱット のまわりに A r、 H e、 N 2などの不活性ガスまたは反応性の低いガスを流 して、 溶融状態で飛行する溶射粒子と空気との直接的な接触を避ける必要が ある。 この点、 減圧の不活性ガス雰囲気で成膜する減圧プラズマ溶射装置を 用いれば、 溶射飛行途中の粒子と空気 （正確には酸素） との接触がないので 好都合である。 According to the inventors' research, even when a mixed working gas 4 in which hydrogen gas is added to an inert gas in the spray gun 2 is used as a plasma heat source, the surface to be treated (base) It was found that when the spraying route of sprayed particles toward the material surface is in the atmosphere (acidic atmosphere), the molten particles return to white or gray again when they come into contact with the air. Therefore, in the present invention, control of the spraying atmosphere (the particle flight route) is also important. That is, in the case of atmospheric plasma spraying (the flight route is under the atmosphere) without using the decompression vessel 1, an environmental shut-off device such as an air is not mixed in the plasma jet 6 is installed. a r around Jiwetto, H e, and flow of the inert gas or less reactive gas such as N 2, is necessary to avoid the direct contact between the spray particles and air to fly in the molten state is there. In this regard, the use of a low-pressure plasma spraying apparatus that forms a film in a reduced-pressure inert gas atmosphere is advantageous because there is no contact between particles and air (exactly oxygen) during spraying.
なお、 A rや Heなどのプラズマ発生ガス中に添加する H2ガス量は、 容 積比で次のような混合比とすることが好ましい。 即ち、 The amount of H 2 gas added to the plasma generating gas such as Ar or He is preferably set to the following mixing ratio in terms of volume ratio. That is,
A rガス/水素ガス = 10 1〜3/1  Ar gas / hydrogen gas = 10 1 to 3/1
H2の混合比が、 10Zl、 好ましくは 5Zlより少ない場合には、 酸ィ匕 イットリウムの黒色化が不十分であったり、 色の品質が一定しない。 一方、 Arガスを 3Z1より多く混合しても、 黒色化の効果が飽和する。 When the mixing ratio of H 2 is less than 10 Zl, preferably 5 Zl, the yttrium oxide is not sufficiently blackened or the color quality is not constant. On the other hand, mixing Ar gas more than 3Z1 will saturate the blackening effect.
プラズマ発生ガスとして、 A rと Heの混合ガスを用いる場合にも、 前記 A rガス単独量に対する H 2ガスの割合を維持することによって発明の目的 を達成することができる。 上記の比率は、 好ましくは 5Zl〜3Zl程度で ある。 Even when a mixed gas of Ar and He is used as the plasma generating gas, the object of the invention can be achieved by maintaining the ratio of H 2 gas to the amount of Ar gas alone. The ratio is preferably about 5Zl to 3Zl.
図 2 (a) 〜 U) は、 本発明に係る技術によって形成された黒色酸化ィ ットリゥム溶射皮膜と従来技術による Y203皮膜との外観を示したもので ある。 この図から明らかなように、 本発明に適合する A r/H2混合ガスを プラズマ ·ジェット発生用作動ガスとして用い、 さらに溶射環境をも非酸ィ匕 性雰囲気に制御して、 酸素分圧の少ない雰囲気下で溶射すれば、 黒色酸化ィ ットリゥム溶射皮膜の形成が可能である。 Figure 2 (a) ~ U) are those according to black oxide I Ttoriumu thermal spray coating and the prior art which is formed by a technique according to the present invention showing the appearance of the Y 2 0 3 film. As is apparent from this figure, an Ar / H 2 mixed gas suitable for the present invention is used as a working gas for plasma jet generation, and the thermal spraying environment is also controlled to a non-acidic atmosphere, so that the oxygen partial pressure is reduced. A black oxide yttrium spray coating can be formed by thermal spraying in an atmosphere with little.
(a) Ar/H2容積比 =4Zlのプラズマ ·ジエツト発生ガスを用い、 A rガス 20 OhP aの雰囲気中で白色の Y203を溶射（マンセノレ記号： N 3、 黒ないしは暗い灰色)。 (a) Thermal spraying of white Y 2 0 3 in the atmosphere of Ar gas 20 OhPa using Ar / H 2 volume ratio = 4Zl plasma jet generating gas (Mansenore symbol: N 3, black or dark gray) .
(b) A rのみをプラズマ 'ジェット発生用作動ガスとして用い、 Arガス 200 h P aの雰囲気中で白色の Y203を溶射 （Ν5、 明るい灰色)。 (b) Using only Ar as the plasma 'jet generating working gas, spraying white Y 2 0 3 in an atmosphere of Ar gas 200 h Pa (Ν5, light gray).
'(c) (a)の条件ガスを用い、大気中で溶射ガンの雰囲気に A rガスを流し つつ白色の Y 2 O 3を溶射 （N4、 中位の灰色)。 '(c) Using the condition gas of (a), white Y 2 O 3 was sprayed while flowing Ar gas in the atmosphere of the spray gun in the atmosphere (N4, medium gray).
(d) (b) の条件ガスを用い、 大気中で白色の Y203を溶射 （Ν9、 白）。 次に本発明に係る黒色酸化ィットリゥム溶射皮膜を形成するための素材と なる Υ203粉末について、 これの粒度と純度について説明する。 (d) Spraying white Y 2 0 3 in the atmosphere using the condition gas of (b) (Ν9, white). Next the material to become Upsilon 2 0 3 powder to form a black oxide Ittoriumu sprayed coating according to the present invention will be described which particle size and purity.
Υ 2 Ο 3粉末の粒度は、 5〜 80 μ mの粒径範囲がよく、 特に 5〜50/im のものが好適である。 その理由は、 粒径が 8 0 μ πιより大きい粉末は、 溶射 熱源中で完全に溶融しない未溶融粒子が含まれることが多いからである。 未 溶融粒子の内部は、水素ガスを含むブラズマ熱源の影響を受けていなレ、ため、 白色の状態を維持している場合がしばしば認められるので、 皮膜品質を低下 させる要因となる。 一方、 5 m以下の粒子は、 内部まで完全に溶融して黒 色化するが、 粉末供給機からの溶射ガンへの送給速度が不安定となったり、 ブラズマ熱源中で溶融昇華状態となって、 皮膜を構成するための強度因子と ならないため、 溶射皮膜としての断面組織が不均等、 不揃いとなるほか、 皮 膜の強度が劣化することがあるからである。 Υ 2 Ο 3 The particle size of the powder should be in the range of 5-80 μm, especially 5-50 / im Are preferred. The reason is that powders having a particle size larger than 80 μπι often contain unmelted particles that do not completely melt in the thermal spray heat source. The inside of the unmelted particles is not affected by the plasma heat source containing hydrogen gas, and therefore, it is often observed that the white state is maintained, which causes a deterioration in the film quality. On the other hand, particles of 5 m or less completely melt to the inside and turn black, but the feed rate from the powder feeder to the spray gun becomes unstable, or it becomes molten and sublimated in a plasma heat source. This is because it does not become a strength factor for constituting the coating, so that the cross-sectional structure of the thermal spray coating becomes uneven and uneven, and the strength of the coating may deteriorate.
本発明に使用する Y 20 3粉末の純度は、 不純物が （例えば F e、 Mg、 C r、 A l、 N i、 S iなど） の少ないものほどよいが、 最近、 発明者らが市 販品を調査したところ、 すべて 9 8 (m a s s %) 以上であり、 これら市販 品を使用しても黒色酸ィ匕イットリウム溶射皮膜と形成することができたので、 特には限定しない。 Purity Y 2 0 3 powder used in the present invention, impurities (e.g. F e, M g, C r , A l, N i, S i , etc.) moderate with less recent inventors As a result of a survey of the commercial products, all of them were 9 8 (mass%) or more, and even if these commercial products were used, they could be formed as a black acid yttrium sprayed coating, so there is no particular limitation.
次に、 黒色酸化ィットリゥム溶射皮膜を形成するための基材について説明 する。 本発明において、 上記の酸化ィットリゥムの黒色溶射皮膜を形成する 対象、 即ち基材は、 A 1およびその合金、 ステンレス鋼、 T iおよびその合 金、 セラミックの焼結体 （例えば、 酸化物、 窒化物、 硼化物、 珪化物および これらの混合物） をはじめ、 石英、 ガラス、 プラスチックなど如何なる素材 も使用が可能である。 また、 これらの素材の上に、 各種の蒸着膜やめつき膜 を施したものを使用することができ、 これらの素材の表面に直接またはァン ダーコートや中間層を介して成膜してもよレ、。  Next, the base material for forming the black oxide yttrium spray coating will be described. In the present invention, the target for forming the black spray coating of the above-mentioned yttrium oxide, that is, the base material is A 1 and its alloy, stainless steel, Ti and its alloy, ceramic sintered body (for example, oxide, nitriding) Any material such as quartz, glass, plastics, etc. can be used, as well as materials, borides, silicides, and mixtures thereof. In addition, these materials can be used with various vapor-deposited films or adhesive films, and they may be formed directly on the surface of these materials or via an undercoat or intermediate layer. Les.
次に、 黒色酸化ィットリゥム溶射皮膜被覆部材の皮膜構造について説明す る。  Next, the coating structure of the black oxide yttrium spray coating member will be described.
本発明に係る部材において、 基材表面に、 上記の酸ィ匕ィットリゥムの黒色 溶射皮膜を直接被覆する場合の他、 この溶射皮膜の形成に先立って、 まず該 基材表面に、 アンダーコートを形成し、 その後、 トップコートとして前記黒 色酸化ィットリゥム溶射皮膜を形成して、 皮膜の密着性を向上させるように してもよい。 この場合、 アンダーコートの材料としては、 N iおよびその合 金、 C rおよびその合金、 Wおよびその合金、 Moおよびその合金、 T iお よびその合金、 A 1およびその合金、 M g合金などから選ばれるいずれか 1 種以上の金属、 合金を用いて、 厚さ 5 0〜5 0 0 m程度に施工することが 好ましい。 In the member according to the present invention, in addition to the case where the surface of the base material is directly coated with the black spray coating of acid yttrium, prior to the formation of the spray coating, first, an undercoat is formed on the surface of the base material. Then, the black oxide yttrium sprayed coating may be formed as a top coat to improve the adhesion of the coating. In this case, the material for the undercoat includes Ni and its alloys, Cr and its alloys, W and its alloys, Mo and its alloys, Ti and Further, it is preferable to use a metal or an alloy selected from one or more selected from Al, its alloys, Al, its alloys, Mg alloys, and the like to a thickness of about 50 to 500 m.
この場合において、 アンダーコートの溶射皮膜が 5 0 μ πιより薄いとアン ダーコートとして作用効果が弱く、 一方、 その厚さが 5 0 0 μ πιを超えると 被覆効果が飽和し、 成膜作業による製作費の向上を招くので得策でなレ、。 なお、 アンダーコートは、 電気アーク溶射法、 フレーム溶射法、 高速フレ ーム溶射法、 大気プラズマ溶射法、 減圧プラズマ溶射法、 爆発溶射法などを 用いることが好ましい。  In this case, if the thermal spray coating of the undercoat is thinner than 50 μπι, the effect as an undercoat is weak. It's not a good idea, because it leads to an increase in costs. For the undercoat, it is preferable to use an electric arc spraying method, a flame spraying method, a high-speed frame spraying method, an atmospheric plasma spraying method, a low pressure plasma spraying method, an explosion spraying method, or the like.
—方、 トップコートとなる本発明に係る黒色の酸ィ匕イットリウム溶射皮膜 は、 基材表面に直接成膜するものであれ、 また前記アンダーコートの上に溶 射積層する場合であれ、 いずれにしても 5 0〜2 0 0 0 μ πιの厚さに施工す ることが好ましい。 5 0 mより薄レ、皮膜では、 耐食性およぴ耐プラズマ · エロージョン性が十分でなく、 一方 2 0 0 0 μ πιより厚くしてもその効果が 飽和して経済的でないからである。  On the other hand, the black yttrium yttrium spray coating according to the present invention, which will be the top coat, is either formed directly on the surface of the base material or is spray-laminated on the undercoat. However, it is preferable to apply the film to a thickness of 50 to 200 μm. This is because a film having a thickness of less than 50 m is insufficient in corrosion resistance and plasma erosion resistance, and on the other hand, even if it is thicker than 200 μm, the effect is saturated and it is not economical.
前記アンダーコートは、 黒色の酸化ィットリゥム溶射皮膜と基材との中間 層として形成するものであって、 その役割は、 基材との密着強さを発揮する —方、 トップコ一トとして形成する黒色の酸化ィットリゥムとも良好な密着 性を維持するものが選ばれる。 材質としては金属質のものが好適であり、 N iおよびその合金、 C rおよびその合金、 Wおよびその合金、 Moおよぴそ の合金、 T iおよびその合金、 A 1およびその合金、 Mg合金などから選ば れるいずれか 1種以上の金属、 合金を用いて、 厚さ 5 0〜5 0 0 / m程度に 施工することが好ましい。  The undercoat is formed as an intermediate layer between the black yttrium oxide sprayed coating and the base material, and its role is to exert the adhesion strength with the base material —the black color formed as the top coat. Those that maintain good adhesion with the other yttrium oxide are selected. Metal materials are preferred, such as Ni and its alloys, Cr and its alloys, W and its alloys, Mo and its alloys, Ti and its alloys, A1 and its alloys, Mg It is preferable to use one or more metals or alloys selected from alloys and the like so that the thickness is about 50 to 50 / m.
この場合において、 アンダーコートの溶射皮膜が 5 より薄いとアン ダーコートとしての作用効果が弱く、 一方、 その厚さが 5 0 0 mを超える と被覆効果が飽和し、 成膜作業による製作費の向上を招くので得策でない。  In this case, if the thermal spray coating of the undercoat is thinner than 5, the effect of the undercoat is weak, while if the thickness exceeds 500 m, the coating effect is saturated and the production cost is increased by the film formation work. Is not a good idea.
(実施例 1 ) (Example 1)
この実施例では、 電熱線を内蔵した石英ガラス製の保護管の表面に、 従来 技術による Y 203の白色溶射皮膜と、 従来技術 （特開 2 0 0 6 - 1 1 8 0 5 3号公報） で開示した白色 Y 2 O 3溶射皮膜を電子ビーム照射によつて黒色化 した皮膜、 および本発明の酸化ィットリゥムの黒色溶射皮膜 （5 0 ^mi¥) を形成した後、 電熱線に電流を通し、 それぞれの皮膜の表面から放出される 波長を調査した。 In this example, a white spray coating of Y 2 0 3 according to the prior art and a prior art (Japanese Patent Laid-Open No. 2 0 0 6-1 1 8 0 5) are provided on the surface of a quartz glass protective tube with a built-in heating wire. After forming the white Y 2 O 3 thermal spray coating disclosed in No. 3) black by electron beam irradiation and the black thermal spray coating (50 ^ mi ¥) of the yttrium oxide of the present invention, The wavelength emitted from the surface of each coating was investigated by passing an electric current through.
その結果、 Y 2 O 3白色溶射皮膜では 0. 2〜 1 m程度であつたが、 酸ィ匕 イツトリゥムの黒色溶射皮膜では電子ビーム照射処理および本発明による黒 色皮膜とも 0. 3〜5 111となり、 赤外線の放出が認められ、 加熱ヒータと しての効率に差が認められた。 As a result, the Y 2 O 3 white sprayed coating was about 0.2 to 1 m, while the acid Yittrium black sprayed coating was 0.3 to 5 111 for both the electron beam irradiation treatment and the black coating according to the present invention. As a result, infrared emission was observed, and a difference in efficiency as a heater was observed.
また、 石英ガラス製のヒー夕に替えて、 ハロゲンランプ （高輝度ランプ） の表面に前記 2種類の酸ィヒィットリゥムの黒色溶射皮膜 (50 μ m厚） を施 ェすると、 皮膜のない状態のランプの波長は 0. 2〜0. 4 μηιの範囲にあ つたのに対し、 黒色溶射皮膜を施したものでは、 0. 3〜1 0 / mとなり、 遠赤外線領域での利用が可能になり、 加熱ヒータとしての効率向上が明らか となった。 なお、 従来技術による Y203の白色溶射皮膜では、溶射皮膜の施 ェがない状態と同一か、 またはそれ以下の波長の範囲内であった。 In addition, instead of using quartz glass, the above two types of acid wet black spray coating (50 μm thick) are applied to the surface of the halogen lamp (high brightness lamp). While the wavelength ranged from 0.2 to 0.4 μηι, the one with a black sprayed coating would be 0.3 to 10 / m, and can be used in the far infrared region. As a result, the improvement in efficiency was revealed. In the white spray coating Y 2 0 3 according to the prior art, or the same as the state with no facilities E of the thermal spray coating, or less was within the range of wavelengths.
以上の結果から、 本発明方法を適用して形成した黒色酸化ィットリゥム溶 射皮膜は、 半導体加工装置用部材として耐プラズマ ·エロージョン性の向上 にとどまらず、 エッチング加工速度を促進させるための熱源としても有用で あることが判明した。  From the above results, the black yttrium oxide spray coating formed by applying the method of the present invention not only improves the plasma erosion resistance but also as a heat source for accelerating the etching processing speed as a member for semiconductor processing equipment. It turned out to be useful.
(実施例 2)  (Example 2)
この実施例では、 SUS 4 1 0鋼 （5 OmmX 5 OmmX 5mm) の試験 片の表面をブラスト粗面化処理を行った後、 A rガスで雰囲気圧力を 5 0〜 20 0 h P aに制御した減圧プラズマ溶射法によって、 Y203を 1 50 μπι 厚に形成した。 その際、 γ2ο3膜の形成に先立って、 大気プラズマ溶射法に よって N i一 A 1合金のアンダーコートを 1 00 μπι厚に施工した試験片の 有無について、 その効果を調べた。 In this example, the surface of a test piece of SUS 4 10 steel (5 OmmX 5 OmmX 5 mm) was subjected to blast roughening, and the atmospheric pressure was controlled to 50 to 200 h h Pa with Ar gas. Y 2 0 3 was formed to a thickness of 1 50 μπι by the reduced pressure plasma spraying method. At that time, prior to the formation of the γ 2 ο 3 film, the effect was examined on the presence or absence of a test piece in which an Ni 1 A 1 alloy undercoat was applied to a thickness of 100 μπι by atmospheric plasma spraying.
また、 減圧プラズマ溶射に際しては、 本発明に係る黒色皮膜を形成する場 合には、作動ガスとして Ar/H2容積比を 5Z1としたものを用い、また、 比較^！の場合には ArZHe比を 5Z1としたものを用いた。 In addition, when forming a black coating according to the present invention during low-pressure plasma spraying, an Ar / H 2 volume ratio of 5Z1 is used as the working gas. In this case, an ArZHe ratio of 5Z1 was used.
溶射皮膜を形成した試験片は、 Y 2 O 3を溶射して形成したトップコートの 外観色を調査した後、 下記の熱衝撃試験を行って、 該溶射皮膜の耐剥離性を 調べた。 The test piece with the thermal spray coating is the top coat formed by spraying Y 2 O 3 . After examining the appearance color, the following thermal shock test was conducted to examine the peel resistance of the sprayed coating.
表 1は、以上の結果を要約したものである。この結果から明らかなように、 本発明に係るブラズマ熱源の作動ガスとして A r ZH 2容積比 5/1の条件 で成膜した試験片 （No. 1〜4) は黒色を呈し、 水素ガスを含まない A r /He容積比 =5/1の条件で形成された試験片 （No. 5〜8) は灰色を 示し黒色にはならなかつた。 Table 1 summarizes these results. As is clear from this result, the test pieces (Nos. 1 to 4) formed under the conditions of Ar ZH 2 volume ratio 5/1 as the working gas of the plasma heat source according to the present invention are black, and hydrogen gas is used. The specimens (Nos. 5 to 8) formed under the conditions of Ar / He volume ratio not containing 5/1 were gray and did not turn black.
これらの試験片を 500 °Cに加熱した電気炉中で 1 5分間維持した後、 2 5 °Cの水中へ投入する操作を 5回繰り返した結果、 全供試皮膜すなわち基材 に、 Y203溶射皮膜を直接形成したもの、 および N i一 A 1合金のアンダー コートを施工したものはもとより、 Y203溶射皮膜の外観色に関係なく、 本 実施例の条件ではすべて優れた耐熱衝撃性を発揮し、 黒色ィ匕による耐剥離性 の低下は認められなかった。 After these specimens were maintained in an electric furnace heated to 500 ° C for 15 minutes and then poured into water at 25 ° C for 5 times, Y 2 0 3 Thermal spray coating directly formed, and Ni 2 A 1 alloy undercoat applied, Y 2 0 3 Demonstrated impact properties, and no degradation of peel resistance due to black wrinkles was observed.
(表 1)  (table 1)
Figure imgf000016_0001
Figure imgf000016_0001
(備考）  (Remarks)
(1)プラズマガス中の Ar/¾比 =5/1 Ar/He比 =5/1  (1) Ar / ¾ ratio in plasma gas = 5/1 Ar / He ratio = 5/1
(2)皮膜厚さ：アンダーコート 100 iim トップコート 150Mtn (2) Film thickness: Undercoat 100 iim Topcoat 150 M tn
(3)熱サイクル数： (500¾ X 15πάη ½5ΐ;水中投下） X 10回繰返し ( 3 ) Number of thermal cycles: (500¾ X 15πάη ½5ΐ; dropped in water) X Repeated 10 times
(実施例 3) (Example 3)
この実施例では、 実施例 2に示した溶射試験片をすべて大気プラズマ溶射法 によって皮膜を形成し、 実施例 2と同条件の熱衝撃試験によって、 皮膜の耐 剥離性を調査した。 なお、 大気プラズマ溶射法では、 Ar/H2容積比 4/ 1を用いるとともに、 溶射ガンの周辺、 特に溶射ガン出口付近に A rガスを 多量に流して、 プラズマ ·ジエツトへの空気の侵入を防止した。 In this example, all the sprayed specimens shown in Example 2 were formed by an atmospheric plasma spraying method, and the thermal resistance test under the same conditions as in Example 2 was used to investigate the peel resistance of the film. In the atmospheric plasma spraying method, Ar / H 2 volume ratio 4/1 is used, and Ar gas is introduced around the spray gun, particularly near the spray gun outlet. A large amount of air was flown to prevent air from entering the plasma jet.
表 2は、 この結果を示したもので、 大気溶射法によつて黒色酸化ィットリ ゥム溶射皮膜を形成しても、 実施例 2の減圧プラズマ溶射法はもとより、 従 来技術による白色の Y 2 O 3溶射皮膜同様、優れた耐剥離性を保持しているこ とが確認された。 Table 2 shows the results. Even if the black oxide yttrium thermal spray coating was formed by the atmospheric spraying method, the white Y 2 by the conventional technology as well as the reduced pressure plasma spraying method of Example 2 was used. As with the O 3 sprayed coating, it was confirmed that excellent peel resistance was maintained.
(表 2)  (Table 2)
Figure imgf000017_0001
Figure imgf000017_0001
(備考)  (Remarks)
(1〉プラスマガス中の Ar/¾比 =4/1 (試験片 No.1〜4) Ar/He比 =4/1 (試験片 No.5〜8)(1> Ar / ¾ ratio in Purasumagasu = 4/1 (test piece No.1~4) Ar / He ratio = 4/1 (test piece Nanba5～8)
(2)皮膜厚さ ：アンダーコート 100/im トップコート Ι^Ομπι (2) Film thickness: Undercoat 100 / im Topcoat Ι ^ Ομπι
(3)熱サイクル数： （500¾Χ15ηΰη<^25¾水中投下） X10回繰返し  (3) Number of thermal cycles: (500¾Χ15ηΰη <^ 25¾ submerged in water) Repeated 10 times
(4) Νο.1、 2の皮膜は、 プラズマ熱源ガスとして Ar/H2比 =4/1に加え、 溶射ガンの周辺、 特にガン出口付近に N2ガスのシ一ルドをして、 プラズマ ·ジエツトへの空気の浸入を防止 した。 (4) The coating of 1ο.1 and 2 has a plasma heat source gas of Ar / H 2 ratio = 4/1, and N 2 gas is shielded around the spray gun, especially near the gun outlet. · Prevents air from entering the jet.
(5) No.5, 6の皮膜は、 プラズマ熱源ガスとして Ar/H2比 =4/1に加え、 溶射ガンの周辺、 特にガン出口付近に N2ガスのシールドをして、 プラズマ■ジエツトへの空気の浸入を防止 した。 (5) The coatings of No.5 and 6 are plasma plasma jets with an Ar / H 2 ratio = 4/1 as a plasma heat source gas and a N 2 gas shield around the spray gun, especially near the gun outlet. Air intrusion was prevented.
(実施例 4) (Example 4)
この実施例では、 5 OmmX 5 OmmX 5 mm厚さのアルミニウム基材を 用いて、 その表面に大気プラズマ溶射法によって、 溶射熱源として組成の異 なるプラズマ ·ジエツト発生用の作動ガスを用いて Y203溶射皮膜と Al 2 03溶射皮膜を 150 m厚さに形成した。 その際、 アンダーコートとして N i一 A 1合金膜（100 μπα)の有無のものについても試験条件に加えた。 その後、 試験片の中央部の表面積 1 OmmX 10 mmの範囲が露出するよう に他の部分をマスクし、 下記条件にて 20時間のプラズマ 'エロージョン試 験を実施した。 なお、 他の表面処理法として、 アルミニウム基材を陽極酸化In this embodiment, 5 OmmX 5 OmmX 5 mm with a thickness of the aluminum substrate by the atmospheric plasma spraying method on the surface, using different plasma Jietsuto working gas for generating composition as spraying heat source Y 2 A 0 3 sprayed coating and an Al 2 0 3 sprayed coating were formed to a thickness of 150 m. At that time, a Ni 1 A 1 alloy film (100 μπα) with or without an undercoat was also added to the test conditions. After that, mask the other part so that the surface area of 1 OmmX 10 mm in the central part of the specimen is exposed, and plasma erosion test for 20 hours under the following conditions The experiment was conducted. As another surface treatment method, anodized aluminum substrate
(アルマイト） したものを比較試料とした。 (Alumite) was used as a comparative sample.
くプラズマエツチング条件 > Plasma etching conditions>
ェツチングガス； C F 4、 A r、 02 (容積比で 10 : 100 : 1) プラズマ出力； 1300W Etching gas; CF 4 , Ar, 0 2 (volume ratio 10: 100: 1) Plasma output; 1300W
試験結果を表 3に示した。 この結果から明らかなように、 比較例の現行技 術による陽極酸化皮膜 （No. 10)、 A 1203溶射皮膜 （No. 7、 8) および B4C溶射皮膜 （No. 9) は、 いずれもプラズマ 'エロージョン量 が大きく、 この種のプラズマ環境中での耐久性に乏しいことがわかる。 これに対して、 本発明に係る黒色酸化ィットリゥム溶射皮膜 (No. ：!〜 4) は、 アンダーコートの有無に関係なく、 優れた耐プラズマ 'エロージョ ン性を発揮した。 なお、 同条件で試験した白色 Y 2 O 3溶射皮膜 （No. 5〜 8 )と比較しても、全く遜色のない耐久性を発揮していることが確認された。 (表 3) The test results are shown in Table 3. As is clear from this result, the anodized film (No. 10), A 1 2 0 3 sprayed film (No. 7, 8) and B 4 C sprayed film (No. 9) by the current technology of the comparative example are Both show that the amount of erosion is large and the durability in this kind of plasma environment is poor. On the other hand, the black yttrium oxide sprayed coating (No .:! To 4) according to the present invention exhibited excellent plasma erosion resistance regardless of the presence or absence of the undercoat. In addition, even when compared with the white Y 2 O 3 sprayed coating (Nos. 5 to 8) tested under the same conditions, it was confirmed that the durability was completely inferior. (Table 3)
Figure imgf000018_0001
Figure imgf000018_0001
(備考)  (Remarks)
(1)溶射は、 大気プラズマ溶射法を用い、 プラズマ発生用ガス組成は次の通り (1) The thermal spraying uses the atmospheric plasma spraying method, and the gas composition for plasma generation is as follows:
Ar/H2=3/1 (Arガスシーノレド） No, 1~4 Ar / H 2 = 3/1 (Ar gassinored) No, 1 ~ 4
Ar/He=4/1 (Arガスシールドなし) No.5~9  Ar / He = 4/1 (No Ar gas shield) No.5 ~ 9
(2)陽極酸化は、 JIS H8601規定の M25に準じて成膜 産業上の利用可能性 (2) Anodization is performed according to JIS H8601 M25 Industrial applicability
本発明に係る技術は、 酸化ィットリゥムの黒色化だけでなく、 他のセラミ ックスの、例えば、 T i 02や T i 02— A 1 20 3などの黒色化技術としても 利用でき、 半導体、 液晶、 その他、 高分子工業や機械工業などの分野で用い られる部材の形成に応用される。 The technology according to the present invention can be used not only for blackening yttrium oxide but also for other ceramics, for example, blackening technology such as T i 0 2 and T i 0 2 — A 1 2 0 3. It is applied to the formation of liquid crystal and other materials used in fields such as polymer industry and machine industry.

Claims

請求の範囲 The scope of the claims
1 . 不活性ガスと水素ガスとの混合ガスをプラズマ ·ジヱット発生用作動ガ スとして、 白色の Y 20 3粉末をプラズマ溶射することによって、 酸化イット リゥムの黒色溶射皮膜を形成することを特徴とする黒色酸化ィットリゥム溶 射皮膜の形成方法。 1. Wherein as an inert gas and mixed gas powered gas for the plasma Jiwetto generation of hydrogen gas by plasma spraying a white Y 2 0 3 powder, to form a black spray coating oxide It Riumu A method of forming a black oxide yttrium spray coating.
2 . 溶射材料が飛行する溶射雰囲気が、 不活性ガスによる 5 0〜6 0 0 h P aの減圧環境に維持されていることを特徴とする請求の範囲 1または 2に記 載の黒色酸化ィットリゥム溶射皮膜の形成方法。  2. The black oxide yttrium according to claim 1 or 2, wherein the thermal spray atmosphere in which the thermal spray material flies is maintained in a reduced pressure environment of 50 to 600 h Pa by an inert gas. A method for forming a thermal spray coating.
3 . 前記酸化ィットリゥムの黒色溶射皮膜は、 前記プラズマ ·ジェット中に 含まれる原子状水素が有する還元作用によって Y 2 o 3粉末の酸素の一部が 消失した状態の Y 2 O 3 - xで表わされる黒色粒子の堆積によつて形成された ものであることを特徴とする請求の範囲 1または 2に記載の黒色酸化ィット リゥム溶射皮膜の形成方法。 3. The black sprayed coating of yttrium oxide is represented by Y 2 O 3 - x in a state where some of the oxygen in the Y 2 O 3 powder has disappeared due to the reducing action of atomic hydrogen contained in the plasma jet. 3. The method for forming a black oxide yttrium spray coating according to claim 1, wherein the black oxide yttrium spray coating is formed by depositing black particles.
4 . 溶射雰囲気を、 プラズマ溶射ガンの周囲に非酸化性ガスを流して、 被表 面に向うプラズマ ·ジヱットへの空気の侵入を防止した環境にすることを特 徴とする請求の範囲 1または 2に記載の黒色酸化ィットリゥム溶射皮膜の形 成方法。 4. The spraying atmosphere is characterized in that a non-oxidizing gas is allowed to flow around the plasma spray gun to prevent the air from entering the plasma jet toward the surface. 2. The method for forming a black yttrium oxide sprayed coating according to 2.
5 . 前記白色の Y 20 3粉末からなる溶射材料は、粒径が 5〜8 0 t mの大き さであることを特徴とする請求の範囲 1または 2に記載の黒色酸ィ匕ィットリ ゥム溶射皮膜の形成方法。 5. The thermal spray material comprising the white Y 2 0 3 powder has a particle size of 5 to 80 tm, and the black acid yttrium according to claim 1 or 2, A method for forming a thermal spray coating.
6 . プラズマ ·ジェット発生のための前記作動ガスは、 不活性ガスと水素ガ スとの容積比が 1 0 / 1〜3 Z lの範囲内のガスであることを特徴とする請 求の範囲 1または 2に記載の黒色酸化ィットリゥム溶射皮膜の形成方法。  6. The scope of claim characterized in that the working gas for plasma jet generation is a gas whose volume ratio of inert gas to hydrogen gas is in the range of 10/1 to 3 Zl The method for forming a black yttrium oxide sprayed coating according to 1 or 2.
7 . 前記酸ィ匕イットリウムの黒色溶射皮膜は、 基材の表面に直接、 またはァ ンダーコートを介して形成されていることを特徴とする請求の範囲 1または 2に記載の黒色酸ィ匕ィットリゥム溶射皮膜の形成方法。 7. The black acid yttrium black spray coating of the acid yttrium is formed directly on the surface of the base material or through an undercoat. A method for forming a thermal spray coating.
8 . 前記基材は、 ステンレス鋼を含む各種の鋼、 アルミニウムおよびその合 金、 チタンおょぴその合金、 タングステンおよびその合金、 モリブデンおよ びその合金、 焼結炭素、 石英、 ガラス、 プラスチック類、 酸化物系おょぴ非 O 2009/072318 酸化物系のセラミック焼結体から選ばれる一種以上の金属系または非金属系 基材であることを特徴とする請求の範囲 1または 2に記載の黒色酸化ィット リゥム溶射皮膜の形成方法。 8. The base material includes various steels including stainless steel, aluminum and its alloys, titanium and its alloys, tungsten and its alloys, molybdenum and its alloys, sintered carbon, quartz, glass, plastics, Oxide-based oppi O 2009/072318 Formation of a black oxide yttrium sprayed coating according to claim 1 or 2, characterized in that it is at least one metal-based or non-metallic substrate selected from oxide-based ceramic sintered bodies Method.
9. 前記アンダーコートは、 N iおよびその合金、 C rおよびその合金、 W およびその合金、 Moおよび Mo合金、 T iおよび T i合金、 A 1およびその 合金の中から選ばれる 1種以上の金属もしくはその合金であることを特徴と する請求の範囲 7に記載の黒色酸化ィットリゥム溶射皮膜の形成方法。  9. The undercoat includes at least one selected from Ni and alloys thereof, Cr and alloys thereof, W and alloys thereof, Mo and Mo alloys, Ti and Ti alloys, A1 and alloys thereof. 8. The method for forming a black yttrium oxide sprayed coating according to claim 7, which is a metal or an alloy thereof.
1 0. 基材表面に、 不活性ガスと水素ガスとの混合ガスをプラズマ ·ジヱッ ト発生用作動ガスとして、 白色の Y 2 O 3粉末をプラズマ溶射することによつ て形成された、 Y203_xの組成を示す酸化ィットリゥムの黒色溶射皮膜が、 膜厚が 5 0〜200 0 imの厚さで形成されていることを特徴とする黒色酸 化ィットリゥム溶射皮膜被覆部材。 1 0. Y formed on the substrate surface by plasma spraying white Y 2 O 3 powder using a mixed gas of inert gas and hydrogen gas as the working gas for plasma jet generation. 2 0 3 black spray coating oxide Ittoriumu showing the composition of a _ x is a thickness 5 0 to 200 0 im black oxidation Ittoriumu thermal spray coating covering member, characterized in that it is formed to a thickness of.
1 1. 前記酸化ィットリゥムの黒色溶射皮膜と基材との間には、 膜厚が 5 0 〜5 00 πιのアンダーコートを設けてなることを特徴とする請求の範囲 1 0に記載の黒色酸化ィットリウム溶射皮膜被覆部材。  1 1. The black oxide according to claim 10, wherein an undercoat having a film thickness of 50 to 500 πι is provided between the black sprayed coating of yttrium oxide and the base material. Yttrium sprayed coating member.
1 2. 前記基材は、 ステンレス鋼を含む各種 ϋ アルミニウムおよびその合 金、 チタンおょぴその合金、 タングステンおよびその合金、 モリブデンおよ びその合金、 焼結炭素、 石英、 ガラス、 プラスチック類、 酸化物系おょぴ非 酸化物系のセラミック焼結体から選ばれる一種以上の金属系または非金属系 基材であることを特徴とする請求の範囲 1 0または 1 1に記載の黒色酸化ィ ットリゥム溶射皮膜被覆部材。  1 2. The substrate is made of various materials including stainless steel ϋ Aluminum and its alloys, Titanium and its alloys, Tungsten and its alloys, Molybdenum and its alloys, Sintered carbon, Quartz, Glass, Plastics, Oxidation The black oxide yttrium according to claim 10 or 11, wherein the black oxide yttrium is one or more metal-based or non-metallic base materials selected from a non-oxide ceramic sintered body. Thermal spray coating coated member.
1 3. 前記アンダーコートは、 N iおよびその合金、 C rおよびその合金、 Wおよびその合金、 Moおよび Mo合金、 T iおよび T i合金、 A 1およびそ の合金の中から選ばれる 1種以上の金属もしくはその合金であることを特徴 とする請求の範囲 1 1に記載の黑色酸化ィットリウム溶射皮膜被覆部材。 1 3. The undercoat is selected from Ni and alloys thereof, Cr and alloys thereof, W and alloys thereof, Mo and Mo alloys, Ti and Ti alloys, A1 and alloys thereof. 12. The amber-colored yttrium oxide spray-coated member according to claim 11, which is the above metal or an alloy thereof.
1 4. 溶射雰囲気を、 プラズマ溶射ガンの周囲に非酸化性ガスを流して、 被 表面に向うプラズマ ·ジエツトへの空気の侵入を防止した環境とすることを 特徴とする請求の範囲 1 0または 1 1に記載の黒色酸化ィットリゥム溶射皮 膜の形成方法。 1 4. The spraying atmosphere is characterized in that a non-oxidizing gas is allowed to flow around the plasma spraying gun to prevent air from entering the plasma jet toward the surface. 11. The method for forming a black yttrium oxide sprayed film according to 1.
1 5. 前記白色の Y203粉末からなる溶射材料は、粒径が 5〜8 0 μτηの大 O 2009/072318 きさであることを特徴とする請求の範囲 1 0または 1 1に記載の黒色酸ィ匕ィ ットリゥム溶射皮膜の形成方法。 1 5. The thermal spray material made of white Y 2 0 3 powder has a particle size of 5 to 80 μτη. O 2009/072318 The method for forming a black acid solution-coated thermal spray coating according to claim 10 or 11, wherein
1 6. プラズマ ·ジヱット発生のための前記作動ガスは、 不活性ガスと水素 ガスとの容積比が 1 0Zl〜3/lの範囲内のガスであることを特徴とする の範囲 10または 1 1に記載の黒色酸化ィットリゥム溶射皮膜の形成方  1 6. The working gas for generating plasma jet is a gas having a volume ratio of inert gas to hydrogen gas in the range of 10 Zl to 3 / l. 10 or 1 1 Of black oxide yttrium spray coating
PCT/JP2008/062366 2007-12-06 2008-07-02 Method of forming black yttrium oxide sprayed coating and member provided with black yttrium oxide sprayed coating WO2009072318A1 (en)

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