JP4358803B2 - Rotary machine parts and rotary machines - Google Patents

Rotary machine parts and rotary machines Download PDF

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JP4358803B2
JP4358803B2 JP2005255481A JP2005255481A JP4358803B2 JP 4358803 B2 JP4358803 B2 JP 4358803B2 JP 2005255481 A JP2005255481 A JP 2005255481A JP 2005255481 A JP2005255481 A JP 2005255481A JP 4358803 B2 JP4358803 B2 JP 4358803B2
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fluororesin
plating film
rotating machine
plating
particles
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JP2007071032A (en
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豊明 安井
義和 山田
勝保 花中
聰 秦
有三 津留崎
修 伊住
一秀 齊藤
憲一 根本
友喜治 鈴木
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Mitsubishi Heavy Industries Ltd
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本発明は、蒸気タービン、圧縮機等の回転機械に関し、さらに詳しくは、微粒子を含む気体が動翼や静翼等の部品に接触した場合に、微粒子の付着を抑制できる回転機械の部品及び回転機械に関する。   The present invention relates to a rotary machine such as a steam turbine and a compressor, and more specifically, a rotary machine component and a rotation that can suppress adhesion of fine particles when a gas containing fine particles comes into contact with a component such as a moving blade or a stationary blade. Related to machinery.

蒸気タービンは、作動流体である蒸気がタービンの動翼に噴射されて駆動される。蒸気タービンが備える動翼や静翼等の部品は、直接蒸気と接触する。また、化学プラント等で各種のガスを圧縮する圧縮機は、外部から動力を与えられてインペラが回転し、前記ガスを圧縮する。このような圧縮機では、インペラやデフューザー等の部品が直接ガスに接触する。   The steam turbine is driven by injecting steam, which is a working fluid, onto the rotor blades of the turbine. Parts such as moving blades and stationary blades provided in the steam turbine are in direct contact with steam. Moreover, the compressor which compresses various gas in a chemical plant etc. is powered by the outside, and an impeller rotates, and compresses the said gas. In such a compressor, components such as an impeller and a diffuser are in direct contact with the gas.

蒸気タービンの作動流体である蒸気や、圧縮機の圧縮対象気体である各種ガスには、これらに含まれる微粒子状のシリカ、酸化鉄、あるいはハイドロカーボン等の微粒子が含まれている。前記動翼やインペラ等は、直接蒸気や各種ガスに接触するので、前記微粒子が動翼やインペラ等に付着して、効率が低下するという問題があった。この対策として、フッ素樹脂を含有する有機塗料を最上層に備える３層皮膜を、蒸気タービンの動翼や圧縮機のインペラ等の表面に形成する技術が知られている（例えば非特許文献１）。   Steam, which is a working fluid of a steam turbine, and various gases, which are gas to be compressed by a compressor, include particulates such as particulate silica, iron oxide, or hydrocarbon contained therein. Since the moving blades, impellers and the like are in direct contact with steam and various gases, there is a problem that the fine particles adhere to the moving blades, the impellers, etc. and the efficiency is lowered. As a countermeasure, a technique is known in which a three-layer coating having an organic paint containing a fluororesin as the uppermost layer is formed on the surface of a moving blade of a steam turbine or an impeller of a compressor (for example, Non-Patent Document 1). .

PERFORMANCE MAINTENANCE OF CENTRIFUGAL COMPRESSORS THROUGHTHE USE OF COATINGS TO REDUCE HYDROVARBON FOULING BY RONALD CHOW NOVACOR CHEMICALS, BRUCE McMORDIE SERMATECH INTERNATIONAL, RICHARD WIEGAND ELLIOTT COMPANYPERFORMANCE MAINTENANCE OF CENTRIFUGAL COMPRESSORS THROUGHTHE USE OF COATINGS TO REDUCE HYDROVARBON FOULING BY RONALD CHOW NOVACOR CHEMICALS, BRUCE McMORDIE SERMATECH INTERNATIONAL, RICHARD WIEGAND ELLIOTT COMPANY

しかしながら、非特許文献１に開示された技術では、シリカ、酸化鉄等の微粒子の付着を抑制するという点で不十分であり、改善の余地がある。そこで、この発明は、上記に鑑みてなされたものであって、シリカ、酸化鉄その他の微粒子を含む気体を取り扱う回転機械において、気体中に含まれる微粒子の付着を効果的に抑制できる回転機械の部品及び回転機械を提供することを目的とする。   However, the technique disclosed in Non-Patent Document 1 is insufficient in terms of suppressing adhesion of fine particles such as silica and iron oxide, and there is room for improvement. Therefore, the present invention has been made in view of the above, and in a rotating machine that handles gas containing silica, iron oxide, and other fine particles, the rotating machine that can effectively suppress the adhesion of the fine particles contained in the gas. The object is to provide parts and rotating machinery.

上述した課題を解決し、目的を達成するために、本発明に係る回転機械の部品は、微粒子を含む気体を取り扱う回転体に用いられ、かつ微粒子を含む気体が接触する構造体であって、第１のフッ素樹脂粒子が第１のめっきマトリックスに含有され、かつ前記第１のフッ素樹脂粒子の一部は、前記第１のめっきマトリックスの表面から露出する第１フッ素樹脂含有めっき皮膜と、前記第１フッ素樹脂含有めっき皮膜の表面に形成され、かつ前記第１のフッ素樹脂粒子よりも直径が小さい第２のフッ素樹脂粒子が第２のめっきマトリックスに含有され、かつ前記第２のフッ素樹脂粒子及び前記第１のフッ素樹脂粒子の一部は、前記第２のめっきマトリックスの表面から露出する第２フッ素樹脂含有めっき皮膜と、を含むめっき皮膜が表面に設けられることを特徴とする。   In order to solve the above-described problems and achieve the object, the rotating machine component according to the present invention is a structure that is used in a rotating body that handles gas containing fine particles and that is in contact with gas containing fine particles, A first fluororesin particle is contained in the first plating matrix, and a part of the first fluororesin particle is exposed from a surface of the first plating matrix; Second fluororesin particles formed on the surface of the first fluororesin-containing plating film and having a diameter smaller than that of the first fluororesin particles are contained in the second plating matrix, and the second fluororesin particles And a part of the first fluororesin particles is provided with a plating film including a second fluororesin-containing plating film exposed from the surface of the second plating matrix on the surface. And wherein the Rukoto.

この回転機械の部品は、蒸気タービンや圧縮機等の回転機械に用いられる、動翼や静翼等の部品である。そして、第１のフッ素樹脂粒子を含む第１のフッ素樹脂含有めっき皮膜の表面に、第１のフッ素樹脂粒子よりも直径の小さい第２のフッ素樹脂粒子を含む第２のフッ素樹脂含有めっき皮膜が形成される。これによって、第１フッ素樹脂含有めっき皮膜の表面に露出した第１のフッ素樹脂粒子の間に、第２フッ素樹脂含有めっき皮膜が優先的に析出する。その結果、めっき皮膜の表面における、第１及び第２のフッ素樹脂粒子による表面占有率を容易に大きくすることができる。そして、シリカや酸化鉄等の微粒子を含む気体が接触しても、フッ素樹脂含有めっき皮膜の表面から露出したフッ素樹脂粒子によって、前記微粒子の付着を効果的に抑制できる。   The parts of the rotating machine are parts such as moving blades and stationary blades used in rotating machines such as steam turbines and compressors. And on the surface of the 1st fluororesin containing plating film containing the 1st fluororesin particle, the 2nd fluororesin containing plating film containing the 2nd fluororesin particle whose diameter is smaller than the 1st fluororesin particle It is formed. As a result, the second fluororesin-containing plating film is preferentially deposited between the first fluororesin particles exposed on the surface of the first fluororesin-containing plating film. As a result, the surface occupancy ratio by the first and second fluororesin particles on the surface of the plating film can be easily increased. And even if the gas containing microparticles | fine-particles, such as a silica and iron oxide, contacts, the adhesion of the said microparticles | fine-particles can be effectively suppressed by the fluororesin particle | grains exposed from the surface of the fluororesin containing plating film.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記めっき皮膜は、前記第１のフッ素樹脂含有めっき皮膜と前記構造体の表面との間に設けられる、金属の中間めっき皮膜を備えることを特徴とする。   The rotating machine component according to the present invention is the rotating machine component, wherein the plating film is provided between the first fluororesin-containing plating film and the surface of the structure. It is provided with a film.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用・効果を奏する。さらにこの回転機会では、第１フッ素樹脂含有めっき皮膜を、回転機械の部品の表面に成膜された金属の中間めっき皮膜の表面に成膜する。これによって、第１フッ素樹脂含有めっき皮膜と回転機械の部品の基材との密着性を向上させて、回転体の表面に形成されるめっき皮膜の割れに対する耐性（耐割れ性）を向上させることができる。その結果、回転体の表面に形成されるめっき皮膜の脱落を抑制できる。また、回転機械の部品の表面に形成されるめっき皮膜の割れを起点として、回転機械の部品を構成する基材の疲労強度が低下するが、この回転機械の部品では回転体の表面に形成されるめっき皮膜の耐割れ性が向上するので、回転機械の部品を構成する基材の疲労強度低下も抑制できる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Further, in this rotation opportunity, the first fluororesin-containing plating film is formed on the surface of the metal intermediate plating film formed on the surface of the rotating machine component. This improves the adhesion between the first fluororesin-containing plating film and the base material of the rotating machine component, thereby improving the resistance (cracking resistance) to cracking of the plating film formed on the surface of the rotating body. Can do. As a result, dropping of the plating film formed on the surface of the rotating body can be suppressed. In addition, the fatigue strength of the base material that forms the rotating machine component is reduced starting from cracks in the plating film formed on the surface of the rotating machine component. However, the rotating machine component is formed on the surface of the rotating body. Since the cracking resistance of the plating film is improved, it is possible to suppress a decrease in fatigue strength of the base material constituting the rotating machine component.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記中間めっき皮膜は、電気めっきにより成膜されることを特徴とする。   In the rotating machine component according to the present invention, the intermediate plating film is formed by electroplating in the rotating machine component.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、中間めっき皮膜を電気めっきにより成膜する。これによって、フッ素樹脂含有めっき皮膜の耐割れ性をさらに向上させることができる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Furthermore, in this rotating machine component, an intermediate plating film is formed by electroplating. Thereby, the crack resistance of the fluororesin-containing plating film can be further improved.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記中間めっき皮膜は、Ｎｉであることを特徴とする。   The rotating machine component according to the present invention is characterized in that in the rotating machine component, the intermediate plating film is Ni.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、中間めっき皮膜をＮｉとする。これによって、フッ素樹脂含有めっき皮膜と回転機械の部品の基材との密着性をさらに向上させて、フッ素樹脂含有めっき皮膜の耐割れ性をさらに向上させることができる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Furthermore, in this rotating machine component, the intermediate plating film is Ni. Thereby, the adhesion between the fluororesin-containing plating film and the base material of the rotating machine component can be further improved, and the crack resistance of the fluororesin-containing plating film can be further improved.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記回転機械の部品の表面には、前記めっき皮膜が形成される部分の疲労強度を向上させる表面改質処理が施されることを特徴とする。   In the rotating machine component according to the next aspect of the invention, the surface of the rotating machine component is subjected to a surface modification treatment for improving the fatigue strength of the portion where the plating film is formed. It is characterized by that.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、回転機械の部品の表面に、前記中間めっき層あるいはフッ素樹脂含有めっき皮膜が形成される部分の疲労強度を向上させる表面改質処理が施される。一般に、めっきを施した基材は疲労強度が低下するが、この回転機械の部品は、めっき皮膜を成膜する前に、予め基材の疲労強度を向上させるので、めっき皮膜を成膜することによって疲労強度が低下しても、その影響を最小限に抑えることができる。ここで、表面改質処理には、例えば窒化処理やショットピーニング処理がある。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Further, in this rotating machine component, a surface modification treatment for improving the fatigue strength of the portion where the intermediate plating layer or the fluororesin-containing plating film is formed is performed on the surface of the rotating machine component. In general, the base material on which plating is applied has a reduced fatigue strength. However, the components of this rotating machine improve the fatigue strength of the base material in advance before forming the plating film. Even if the fatigue strength is reduced, the effect can be minimized. Here, the surface modification treatment includes, for example, nitriding treatment and shot peening treatment.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記第１のフッ素樹脂粒子の直径は１μｍ以上２０μｍ以下であることを特徴とする。   The rotating machine component according to the present invention is characterized in that, in the rotating machine component, the diameter of the first fluororesin particles is not less than 1 μm and not more than 20 μm.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、第１のフッ素樹脂粒子の直径を１μｍ以上２０μｍ以下とする。かかる範囲であれば、第１フッ素樹脂粒子の間に、第２フッ素樹脂含有めっき皮膜を効果的に優先析出させることができる。また、めっき液中において、第１のフッ素樹脂粒子の均一分散性を長時間にわたって維持できるので、第１フッ素樹脂含有めっき皮膜に第１フッ素樹脂粒子を均一に分布させることができる。これによって、第１及び第２フッ素樹脂粒子の偏在を抑制できる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Furthermore, in this rotating machine component, the diameter of the first fluororesin particles is 1 μm or more and 20 μm or less. Within such a range, the second fluororesin-containing plating film can be effectively preferentially deposited between the first fluororesin particles. Moreover, since the uniform dispersibility of the first fluororesin particles can be maintained for a long time in the plating solution, the first fluororesin particles can be uniformly distributed in the first fluororesin-containing plating film. Thereby, uneven distribution of the first and second fluororesin particles can be suppressed.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記第１のフッ素樹脂粒子又は前記第２のフッ素樹脂粒子は、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリビリニデンフルオライド（ＰＶＤＦ）、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）の少なくとも１種類であることを特徴とする。この発明において、フッ素樹脂含有めっき皮膜を構成する前記フッ素樹脂粒子には、これらの材料を用いることができる。   The rotating machine component according to the present invention is the rotating machine component, wherein the first fluororesin particles or the second fluororesin particles are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoro. Propylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoro It is at least one kind of ethylene copolymer (ETFE). In the present invention, these materials can be used for the fluororesin particles constituting the fluororesin-containing plating film.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記第２フッ素樹脂含有めっき皮膜の表面に、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリビリニデンフルオライド（ＰＶＤＦ）、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）の少なくとも１種類からなるフッ素樹脂皮膜が形成されることを特徴とする。   The rotating machine component according to the present invention is a rotating machine component comprising: a polytetrafluoroethylene (PTFE) -tetrafluoroethylene-hexafluoropropylene copolymer (PTFE) on the surface of the second fluororesin-containing plating film ( FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer ( A fluororesin film comprising at least one kind of ETFE) is formed.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、第２フッ素樹脂含有めっき皮膜の表面に、フッ素樹脂からなるフッ素樹脂皮膜が形成される。これによって、シリカや酸化鉄等の微粒子の付着を、さらに効果的に抑制できる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Furthermore, in this rotating machine component, a fluororesin film made of a fluororesin is formed on the surface of the second fluororesin-containing plating film. Thereby, adhesion of fine particles such as silica and iron oxide can be more effectively suppressed.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記第１のめっきマトリックス及び前記第２のめっきマトリックスは、Ｎｉ又はＮｉ基の金属であることを特徴とする。   The rotating machine component according to the present invention is characterized in that, in the rotating machine component, the first plating matrix and the second plating matrix are Ni or a Ni-based metal.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、第１及び第２のめっきマトリックスに、Ｎｉ又はＮｉ基の金属を用いる。これにより、耐腐食性を向上させることができる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Further, in this rotating machine component, Ni or Ni-based metal is used for the first and second plating matrices. Thereby, corrosion resistance can be improved.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、平面視において、前記第１のフッ素樹脂粒子及び前記第２のフッ素樹脂粒子の露出した部分が、前記第２フッ素樹脂含有めっき皮膜の表面を占める面積の割合が１０％以上であることを特徴とする。   In the rotating machine component according to the present invention, in the rotating machine component, the exposed portions of the first fluororesin particles and the second fluororesin particles in the plan view include the second fluororesin. The ratio of the area occupying the surface of the plating film is 10% or more.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、平面視において、第２フッ素樹脂含有めっき皮膜の全面積に対して、第１及び第２のフッ素樹脂粒子が前記第２フッ素樹脂含有めっき皮膜の表面から露出した部分が占める面積の割合が１０％以上とする。これにより、シリカや酸化鉄等の微粒子の付着を、効果的に抑制できる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Furthermore, in this rotating machine component, in plan view, the first and second fluororesin particles are exposed from the surface of the second fluororesin-containing plating film with respect to the entire area of the second fluororesin-containing plating film. The ratio of the area occupied by the portion is 10% or more. Thereby, adhesion of fine particles, such as a silica and iron oxide, can be suppressed effectively.

次の本発明に係る回転機械の部品は、前記回転機械の部品において、前記第１フッ素樹脂粒子含有めっき皮膜又は前記第２フッ素樹脂粒子含有めっき皮膜のうち少なくとも一方は、無電解めっきにより成膜されることを特徴とする。   The rotating machine component according to the present invention is the rotating machine component, wherein at least one of the first fluororesin particle-containing plating film and the second fluororesin particle-containing plating film is formed by electroless plating. It is characterized by being.

この回転機械の部品は、前記回転機械の部品と同様の構成を備えるので、前記回転機械の部品と同様の作用、効果を奏する。さらに、この回転機械の部品では、第１又は第２フッ素樹脂粒子含有めっき皮膜のうち少なくとも一方を、無電解めっきにより成膜する。これによって、回転機械の部品が複雑な３次元形状であっても、均一にフッ素樹脂粒子含有めっき皮膜を形成できる。   Since the rotating machine component has the same configuration as the rotating machine component, the same operation and effect as the rotating machine component are achieved. Furthermore, in this rotating machine component, at least one of the first or second fluororesin particle-containing plating film is formed by electroless plating. Thereby, even if the components of the rotating machine have a complicated three-dimensional shape, the fluororesin particle-containing plating film can be formed uniformly.

次の本発明に係る回転機械は、前記回転機械の部品を、微粒子を含む気体が接触する回転部分に備えることを特徴とする。   The rotating machine according to the next aspect of the present invention is characterized in that a part of the rotating machine is provided in a rotating part in contact with a gas containing fine particles.

この回転機械は、前記回転機械の部品を備えるので、シリカ、酸化鉄その他の微粒子を含む気体を取り扱う回転機械において、気体中に含まれる微粒子の付着を効果的に抑制できる。   Since the rotating machine includes the rotating machine parts, the rotating machine that handles gas containing silica, iron oxide, and other fine particles can effectively suppress adhesion of fine particles contained in the gas.

以上説明したように、この発明に係る回転機械の部品及び回転機械は、シリカ、酸化鉄その他の微粒子を含む気体を取り扱う回転機械において、気体中に含まれる微粒子の付着を効果的に抑制できる。   As described above, the rotating machine component and the rotating machine according to the present invention can effectively suppress the adhesion of fine particles contained in the gas in the rotary machine that handles gas containing silica, iron oxide, and other fine particles.

以下、この発明につき図面を参照しつつ詳細に説明する。なお、この発明を実施するための最良の形態によりこの発明が限定されるものではない。また、下記実施例における構成要素には、当業者が容易に想定できるもの、あるいは実質的に同一のものが含まれる。なお、本発明は、蒸気タービンや圧縮機等の回転機械であって、シリカ等の微粒子を含む気体を取り扱うものにおいて、前記気体が接触する前記回転機械の部品に対して好ましく適用できる。すなわち、前記気体が接触するものであれば、運動する部品、回転する部品、静止している部品を問わず、本発明は適用できる。以下においては、回転機械の回転部品（例えば動翼やローター）を例として説明するが、本発明の適用対象はこれに限定されるものではない。   Hereinafter, the present invention will be described in detail with reference to the drawings. The present invention is not limited to the best mode for carrying out the invention. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same. Note that the present invention is preferably applicable to rotating machine parts such as a steam turbine and a compressor that handle gas containing fine particles such as silica, and the parts of the rotating machine that come into contact with the gas. That is, the present invention can be applied to any part that moves, rotates, or is stationary as long as the gas contacts. In the following, a rotating part (for example, a moving blade or a rotor) of a rotating machine will be described as an example, but the application target of the present invention is not limited to this.

この実施例に係るめっき皮膜で被覆した回転機械の部品は、フッ素樹脂粒子をめっきマトリックスに含有させた第１フッ素樹脂含有めっき皮膜と、この第１フッ素樹脂含有めっき皮膜上に形成され、かつ前記第１フッ素樹脂ファン有めっき皮膜に含有されるフッ素樹脂粒子よりも直径の小さいフッ素樹脂粒子を含有する第２フッ素樹脂含有めっき皮膜と、が表面に形成される点に特徴がある。   A rotating machine component coated with a plating film according to this embodiment is formed on a first fluorine resin-containing plating film containing fluorine resin particles in a plating matrix, and on the first fluorine resin-containing plating film, and The second fluororesin-containing plating film containing fluororesin particles having a smaller diameter than the fluororesin particles contained in the first fluororesin fan-plated film is characterized in that it is formed on the surface.

図１は、この実施例に係るフッ素樹脂粒子含有めっき皮膜で表面を被覆した動翼を備える蒸気タービンのタービン室周辺を示す断面図である。この実施例に係る回転機械である蒸気タービン２０は、蒸気入口弁２１で開閉制御される蒸気供給管２５から供給される蒸気の蒸気圧力を、回転動力に変換するものである。回転動力は、減速機を介して発電機等に使用される。回転動力を取り出すためのローター軸２２には、タービンディスク２６が複数取り付けられる。タービンディスク２６の外周には、複数の動翼２３が一列に取り付けられて動翼列を形成する。動翼２３は、上記蒸気供給管２５から供給される蒸気を受けてローター軸２２を回転させる。   FIG. 1 is a cross-sectional view showing the periphery of a turbine chamber of a steam turbine including a moving blade whose surface is coated with a fluororesin particle-containing plating film according to this embodiment. A steam turbine 20 that is a rotating machine according to this embodiment converts steam pressure of steam supplied from a steam supply pipe 25 that is controlled to open and close by a steam inlet valve 21 into rotational power. The rotational power is used for a generator or the like via a speed reducer. A plurality of turbine disks 26 are attached to the rotor shaft 22 for extracting rotational power. On the outer periphery of the turbine disk 26, a plurality of moving blades 23 are attached in a row to form a moving blade row. The moving blade 23 receives the steam supplied from the steam supply pipe 25 and rotates the rotor shaft 22.

動翼２３間には、複数のノズルベーンを備えるノズル仕切り板２４が配置され、ノズルベーンを蒸気が通過する際に、当該蒸気を整流して動翼２３に効率よく当てる。図１に示すように、蒸気タービン２０が複数の動翼列を備える場合は、ノズルベーンも複数枚設けられる。この場合、各ノズル仕切り板２４が個々に有するノズルベーンの枚数、大きさは異なることが多いが、どれも同様の構成である。   A nozzle partition plate 24 having a plurality of nozzle vanes is disposed between the moving blades 23, and when the steam passes through the nozzle vanes, the steam is rectified and efficiently applied to the moving blades 23. As shown in FIG. 1, when the steam turbine 20 includes a plurality of moving blade rows, a plurality of nozzle vanes are also provided. In this case, the number of nozzle vanes and the size of each nozzle partition plate 24 are often different, but all have the same configuration.

図２は、この実施例に係るフッ素樹脂粒子含有めっき皮膜で表面を被覆した、蒸気タービンの動翼を示す斜視図である。図３は、図２のＡ−Ａ断面図である。回転機械である蒸気タービン２０の部品である動翼２３は、ベース２３Ｂに翼２３Ｗが取り付けられている。また、ベース２３Ｂの翼２３Ｗとは反対側に、翼固定部２３Ｔが設けられる。翼固定部２３Ｔは、タービンディスク２６の外周部に形成される、翼固定部２３Ｔと同形状の翼取り付け溝にはめ込まれて、タービンディスク２６に取り付けられる。   FIG. 2 is a perspective view showing a moving blade of a steam turbine whose surface is coated with a fluororesin particle-containing plating film according to this embodiment. FIG. 3 is a cross-sectional view taken along the line AA of FIG. A rotor blade 23 that is a component of a steam turbine 20 that is a rotating machine has a blade 23W attached to a base 23B. A blade fixing portion 23T is provided on the opposite side of the base 23B from the blade 23W. The blade fixing portion 23T is fitted into the turbine disk 26 by being fitted into a blade attachment groove having the same shape as the blade fixing portion 23T formed on the outer peripheral portion of the turbine disk 26.

蒸気タービン２０が備える動翼２３は、高温、高圧の蒸気が動翼２３へ噴射されて、タービンディスク２６とともに回転する。このため、動翼２３には、大きな遠心加速度が作用するとともに、高温にさらされる。したがって、動翼２３は、高強度、かつ耐熱性を有する材料で製造される。この実施例において、動翼２３は、マルテンサイト系のステンレス鋼で製造される。   The moving blade 23 included in the steam turbine 20 is rotated together with the turbine disk 26 by injecting high-temperature and high-pressure steam onto the moving blade 23. For this reason, a large centrifugal acceleration acts on the moving blade 23 and is exposed to a high temperature. Therefore, the moving blade 23 is manufactured from a material having high strength and heat resistance. In this embodiment, the rotor blade 23 is made of martensitic stainless steel.

蒸気タービン２０において、動翼２３の表面２３Ｓやノズルベーンの表面には、蒸気に含まれるＳｉＯ2や酸化鉄（Ｆｅ3Ｏ4）等の微粒子が付着する。また、圧縮機のような回転機械でも、圧縮対象のガスに含まれるハイドロカーボン（ＨＣ）やシリカ等の微粒子等が、ガスの接触する部品の表面に付着する。そして、長期間の運転により、前記微粒子が動翼２３の表面２３Ｓやノズルベーンの表面等に体積して、蒸気タービンの熱効率や、圧縮機の圧縮効率を低下させてしまう。 In the steam turbine 20, fine particles such as SiO 2 and iron oxide (Fe 3 O 4 ) contained in the steam adhere to the surface 23 S of the rotor blade 23 and the surface of the nozzle vane. Further, even in a rotating machine such as a compressor, fine particles such as hydrocarbon (HC) and silica contained in a gas to be compressed adhere to the surface of a part in contact with the gas. Then, due to a long-term operation, the fine particles are increased in volume on the surface 23S of the moving blade 23, the surface of the nozzle vane, and the like, thereby reducing the thermal efficiency of the steam turbine and the compression efficiency of the compressor.

かかる問題を解決するため、この実施例においては、動翼２３の表面２３Ｓに、フッ素樹脂の粒子を含有するめっき皮膜で被覆する。これによって、蒸気中の微粒子が、動翼２３の表面２３Ｓに付着することを抑制する。次に、この実施例に係るめっき皮膜について説明する。   In order to solve this problem, in this embodiment, the surface 23S of the rotor blade 23 is covered with a plating film containing fluororesin particles. Thereby, the fine particles in the vapor are prevented from adhering to the surface 23S of the moving blade 23. Next, the plating film according to this embodiment will be described.

図４は、この実施例に係る動翼の表面を示す模式図である。この図は、この実施例に係る動翼２３の表面２３Ｓを拡大して（図３のＢで囲んだ部分）、これを模式的に表したものである。この実施例に係る動翼２３は、回転機械である蒸気タービン２０の部品であって、微粒子を含む気体を取り扱う回転体に用いられ、かつ微粒子を含む気体が接触する構造体である。そして、動翼２３は、基材（この実施例ではマルテンサイト系ステンレス鋼）１の表面に、めっき皮膜１０が成膜されている。このめっき皮膜１０は、動翼２３の基材１の上に成膜される、フッ素樹脂粒子を含有しない中間めっき皮膜１１と、この中間めっき皮膜１１の上に成膜される第１フッ素樹脂含有めっき皮膜１２と、第１フッ素樹脂含有めっき皮膜１２上に成膜される第２フッ素樹脂含有めっき皮膜１４とで構成される。   FIG. 4 is a schematic view showing the surface of the rotor blade according to this embodiment. This figure is an enlarged view of the surface 23S of the rotor blade 23 according to this embodiment (portion surrounded by B in FIG. 3), and schematically shows this. The rotor blade 23 according to this embodiment is a component of the steam turbine 20 that is a rotating machine, and is a structure that is used in a rotating body that handles gas containing fine particles and that contacts with gas containing fine particles. The moving blade 23 has a plating film 10 formed on the surface of a base material (in this embodiment, martensitic stainless steel) 1. This plating film 10 is formed on the base material 1 of the rotor blade 23 and includes an intermediate plating film 11 that does not contain fluororesin particles, and a first fluorine resin containing film that is formed on the intermediate plating film 11. It comprises a plating film 12 and a second fluorine resin-containing plating film 14 formed on the first fluorine resin-containing plating film 12.

第１フッ素樹脂含有めっき皮膜１２は、第１のフッ素樹脂粒子（以下第１フッ素樹脂粒子）１３Ｐが第１のめっきマトリックス（以下第１めっきマトリックス）１３Ｍで包含される。第１フッ素樹脂含有めっき皮膜１２は、図４に示すように、表面に第１フッ素樹脂粒子１３Ｐの一部が露出している。第２フッ素樹脂含有めっき皮膜１４は、第１フッ素樹脂含有めっき皮膜１２と同様に、第２のフッ素樹脂粒子（以下第２フッ素樹脂粒子）１４Ｐが第２のめっきマトリックス（以下第２めっきマトリックス）１４Ｍで包含される。そして、第２フッ素樹脂含有めっき皮膜１４は、図４に示すように、表面に第２フッ素樹脂粒子１４Ｐの一部が露出している。ここで、第２フッ素樹脂粒子１４Ｐの直径Ｄ２は、第１フッ素樹脂粒子１３Ｐの直径Ｄ１よりも小さい。   The first fluororesin-containing plating film 12 includes first fluororesin particles (hereinafter referred to as first fluororesin particles) 13P in a first plating matrix (hereinafter referred to as first plating matrix) 13M. As shown in FIG. 4, the first fluororesin-containing plating film 12 has a part of the first fluororesin particles 13P exposed on the surface. Similarly to the first fluororesin-containing plating film 12, the second fluororesin-containing plating film 14 is composed of the second fluororesin particles (hereinafter referred to as second fluororesin particles) 14P and the second plating matrix (hereinafter referred to as second plating matrix). 14M. And as shown in FIG. 4, as for the 2nd fluorine resin containing plating film 14, a part of 2nd fluorine resin particle 14P is exposed on the surface. Here, the diameter D2 of the second fluororesin particles 14P is smaller than the diameter D1 of the first fluororesin particles 13P.

これによって、第１フッ素樹脂含有めっき皮膜１２の表面に露出した第１フッ素樹脂粒子１３Ｐの間に、第２フッ素樹脂含有めっき皮膜１４が優先的に析出する。その結果、第１フッ素樹脂粒子１３Ｐの間を、第２フッ素樹脂粒子１４Ｐで埋めることができる。このとき、第２フッ素樹脂含有めっき皮膜１４の表面には、第１フッ素樹脂粒子１３Ｐ及び第２フッ素樹脂粒子１４Ｐの両方が露出することになる。これによって、めっき皮膜１０の表面において、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐが占める割合を容易に大きくすることができる。その結果、動翼２３の表面２３Ｓに付着する、蒸気に含まれるＳｉＯ2や酸化鉄（Ｆｅ3Ｏ4）等の微粒子の量を効果的に低減できる。 As a result, the second fluororesin-containing plating film 14 is preferentially deposited between the first fluororesin particles 13P exposed on the surface of the first fluororesin-containing plating film 12. As a result, the space between the first fluororesin particles 13P can be filled with the second fluororesin particles 14P. At this time, both the first fluororesin particles 13P and the second fluororesin particles 14P are exposed on the surface of the second fluororesin-containing plating film 14. Accordingly, the ratio of the first and second fluororesin particles 13P and 14P on the surface of the plating film 10 can be easily increased. As a result, the amount of fine particles such as SiO 2 and iron oxide (Fe 3 O 4 ) contained in the vapor attached to the surface 23S of the rotor blade 23 can be effectively reduced.

第１フッ素樹脂含有めっき皮膜１２に含まれる第１フッ素樹脂粒子１３Ｐの直径Ｄ１は、１μｍ以上２０μｍ以下が好ましく、第２フッ素樹脂含有めっき皮膜１４に含まれる第２フッ素樹脂粒子１４Ｐの直径Ｄ２は、１μｍ未満が好ましい。第２フッ素樹脂粒子１４Ｐの直径Ｄ２は、１μｍ未満であって可能な限り小さいことが好ましいが、めっき液中への分散や生産性を考慮して、０．１μｍ以上であることが好ましい。また、第１フッ素樹脂粒子１３Ｐの直径Ｄ１と、第２フッ素樹脂粒子１４Ｐの直径Ｄ２との比Ｄ１／Ｄ２は、２．５以上２５以下が好ましい。   The diameter D1 of the first fluororesin particles 13P included in the first fluororesin-containing plating film 12 is preferably 1 μm or more and 20 μm or less, and the diameter D2 of the second fluororesin particles 14P included in the second fluororesin-containing plating film 14 is It is preferably less than 1 μm. The diameter D2 of the second fluororesin particles 14P is preferably less than 1 μm and as small as possible, but is preferably 0.1 μm or more in consideration of dispersion in the plating solution and productivity. The ratio D1 / D2 between the diameter D1 of the first fluororesin particles 13P and the diameter D2 of the second fluororesin particles 14P is preferably 2.5 or more and 25 or less.

第１フッ素樹脂含有めっき皮膜１２に含まれる第１フッ素樹脂粒子１３Ｐは、めっき後において、第１フッ素樹脂含有めっき皮膜１２の表面からある程度露出する必要がある。このため、第１フッ素樹脂粒子１３Ｐの直径Ｄ１を上記のように設定する。第１フッ素樹脂粒子１３Ｐの直径Ｄ１が１μｍ未満の場合、第１フッ素樹脂粒子１３Ｐの露出量が小さく、その上に成膜される第２フッ素樹脂含有めっき皮膜１４の優先析出が低下してしまう。その結果、めっき皮膜１０の表面におけるフッ素樹脂粒子の表面占有率が低下してしまい、気体に含まれる粒子の付着抑制効果が十分に発揮されなくなってしまう。一方、第１フッ素樹脂粒子１３Ｐの直径Ｄ１が２０μｍを越えると、めっき液中での均一分散性を長時間にわたって維持することが困難となり、得られる第１フッ素樹脂含有めっき皮膜１２の第１フッ素樹脂粒子１３Ｐが不均一となる。その結果、気体に含まれる粒子の付着抑制効果が十分に発揮されなくなってしまう。また、第１フッ素樹脂含有めっき皮膜１２の皮膜厚さは、第１フッ素樹脂粒子１３Ｐの直径Ｄ１よりも小さくすることが好ましい。このようにすれば、第１フッ素樹脂粒子１３Ｐの一部が、第１フッ素樹脂含有めっき皮膜１２の表面からより確実に露出するようになる。   The first fluororesin particles 13P included in the first fluororesin-containing plating film 12 need to be exposed to some extent from the surface of the first fluororesin-containing plating film 12 after plating. For this reason, the diameter D1 of the first fluororesin particles 13P is set as described above. When the diameter D1 of the first fluororesin particles 13P is less than 1 μm, the exposure amount of the first fluororesin particles 13P is small, and the preferential deposition of the second fluororesin-containing plating film 14 formed thereon is reduced. . As a result, the surface occupancy ratio of the fluororesin particles on the surface of the plating film 10 is reduced, and the effect of suppressing the adhesion of particles contained in the gas is not sufficiently exhibited. On the other hand, when the diameter D1 of the first fluororesin particles 13P exceeds 20 μm, it is difficult to maintain the uniform dispersibility in the plating solution for a long time, and the first fluorine of the obtained first fluororesin-containing plating film 12 is obtained. The resin particles 13P are not uniform. As a result, the effect of suppressing the adhesion of particles contained in the gas is not sufficiently exhibited. The film thickness of the first fluororesin-containing plating film 12 is preferably smaller than the diameter D1 of the first fluororesin particles 13P. In this way, a part of the first fluororesin particles 13P is more reliably exposed from the surface of the first fluororesin-containing plating film 12.

ここで、第１及び第２フッ素樹脂粒子１３Ｐの直径Ｄ１、Ｄ２は、例えば、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐを分級する際に用いるメッシュの粗さにより規定する。すなわち、メッシュが正方形である場合、前記メッシュの１辺の長さが第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐの直径に相当する。また、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐの直径は、平均値である。   Here, the diameters D1 and D2 of the first and second fluororesin particles 13P are defined by the roughness of the mesh used when classifying the first and second fluororesin particles 13P and 14P, for example. That is, when the mesh is square, the length of one side of the mesh corresponds to the diameter of the first and second fluororesin particles 13P and 14P. The diameters of the first and second fluororesin particles 13P and 14P are average values.

この実施例において、第１及び第２フッ素樹脂含有めっき皮膜１２、１４のめっきマトリックス１３Ｍ、１４Ｍは、Ｎｉ基の金属であり、例えば、Ｎｉ‐ＰやＮｉ‐Ｂが用いられる。この実施例においては、Ｎｉ‐Ｐが用いられる。Ｎｉ基の金属をめっきマトリックスとして選択することにより、成膜した第１及び第２フッ素樹脂含有めっき皮膜１２、１４に耐食性を付与することができる。また、第１及び第２フッ素樹脂含有めっき皮膜１２、１４を成膜するために用いるめっき液は、Ｐ濃度が５〜１５％のＮｉ‐Ｐ無電解めっき液、Ｂ濃度が１〜１０％の無電解めっき液を用いることができる。   In this embodiment, the plating matrices 13M and 14M of the first and second fluororesin-containing plating films 12 and 14 are Ni-based metals, for example, Ni-P or Ni-B. In this embodiment, Ni-P is used. By selecting a Ni-based metal as a plating matrix, corrosion resistance can be imparted to the first and second fluororesin-containing plating films 12 and 14 formed. The plating solution used to form the first and second fluororesin-containing plating films 12 and 14 is a Ni-P electroless plating solution having a P concentration of 5 to 15% and a B concentration of 1 to 10%. An electroless plating solution can be used.

この実施例においては、フッ素樹脂粒子を含有しない中間めっき皮膜１１を設けることにより、基材１とフッ素樹脂含有めっき皮膜との密着性を向上させる。ここで、フッ素樹脂粒子を含有しない中間めっき皮膜１１は、フッ素樹脂含有めっき皮膜１２のめっきマトリックス１３Ｍと同様にＮｉ基の金属であり、例えば、Ｎｉ‐ＰやＮｉ‐Ｂが用いられる。また、中間めっき皮膜１１は、Ｎｉめっきとしてもよい。   In this embodiment, the adhesion between the substrate 1 and the fluororesin-containing plating film is improved by providing the intermediate plating film 11 containing no fluororesin particles. Here, the intermediate plating film 11 containing no fluororesin particles is a Ni-based metal like the plating matrix 13M of the fluororesin-containing plating film 12, and for example, Ni-P or Ni-B is used. Further, the intermediate plating film 11 may be Ni plating.

図５は、この実施例に係るめっき皮膜を生成する手順を示すフローチャートである。まず、被めっき部材である動翼２３の表面に、電解めっきによって中間めっき皮膜１１を成膜する（ステップＳ１０１）。中間めっき皮膜１１は、電気Ｎｉめっき液を用いて、ワット浴等の電気めっきにより作製することが好ましい。これにより、めっき皮膜１０（図４）の耐割れ性が向上する。   FIG. 5 is a flowchart showing a procedure for generating a plating film according to this embodiment. First, the intermediate plating film 11 is formed by electrolytic plating on the surface of the rotor blade 23 that is a member to be plated (step S101). The intermediate plating film 11 is preferably produced by electroplating such as a watt bath using an electric Ni plating solution. Thereby, the crack resistance of the plating film 10 (FIG. 4) improves.

特に、蒸気タービン２０の動翼２３ような、回転機械の回転部品においては強度が要求されるが、電気めっきを用いて中間めっき皮膜１１をＮｉで成膜すると、めっき皮膜１０の耐割れ性を向上させることができるので好ましい。また、中間めっき皮膜１１は、Ｎｉで成膜した方が、Ｎｉ‐Ｐで成膜するよりも、フッ素樹脂含有めっき皮膜１２の密着性が向上するので、好ましい。このように、中間めっき皮膜１１を設けると、めっき皮膜１０の耐割れ性を向上させることができるので、特に大きな加速度が作用する動翼やローター等に、本発明は好ましく適用できる。   In particular, strength is required for rotating parts of rotating machines such as the rotor blades 23 of the steam turbine 20, but if the intermediate plating film 11 is formed of Ni using electroplating, the crack resistance of the plating film 10 is improved. Since it can improve, it is preferable. Further, it is preferable that the intermediate plating film 11 is formed of Ni because the adhesiveness of the fluororesin-containing plating film 12 is improved rather than the film formation of Ni-P. Thus, when the intermediate plating film 11 is provided, the crack resistance of the plating film 10 can be improved, and therefore the present invention can be preferably applied to a moving blade, a rotor, or the like on which a large acceleration acts.

なお、中間めっき皮膜１１は、Ｎｉ‐Ｐ等の無電解めっき液を用いた無電解めっき（例えば、次に説明する周期律表の第８属金属の自己触媒作用を利用する方法）により作製してもよい。このようにすれば、３次元形状に対しても、均一に中間めっき皮膜１１を形成できる。また、この実施例において、中間めっき皮膜１１の厚さは特に限定されるものではないが、０．５μｍ〜１０μｍ程度が適当である。   The intermediate plating film 11 is prepared by electroless plating using an electroless plating solution such as Ni-P (for example, a method using the autocatalytic action of a group 8 metal in the periodic table described below). May be. In this way, the intermediate plating film 11 can be uniformly formed even for a three-dimensional shape. Further, in this embodiment, the thickness of the intermediate plating film 11 is not particularly limited, but about 0.5 μm to 10 μm is appropriate.

次に、中間めっき皮膜１１上に第１フッ素樹脂含有めっき皮膜１２を成膜する。第１フッ素樹脂含有めっき皮膜１２は、めっき液中に第１フッ素樹脂粒子１３Ｐを添加し、このめっき液を用いて動翼２３に無電解めっきすることにより作製する。この無電解めっきは、例えば、次に説明する、周期律表の第８属金属（Ｎｉ）の自己触媒作用を利用する方法が用いられる。まず、Ｎｉの中間めっき皮膜１１を成膜した動翼２３の表面を、アルカリ脱脂する（ステップＳ１０２）。次に、動翼２３の表面を酸洗いして、その後、電解洗浄する（ステップＳ１０３）。酸洗い、及び電解洗浄は、第１フッ素樹脂含有めっき皮膜１２を成膜する中間めっき皮膜１１の表面を活性化させるために行われる。   Next, a first fluororesin-containing plating film 12 is formed on the intermediate plating film 11. The first fluororesin-containing plating film 12 is produced by adding the first fluororesin particles 13P to the plating solution and electrolessly plating the moving blade 23 using this plating solution. For this electroless plating, for example, a method that utilizes the autocatalytic action of a group 8 metal (Ni) in the periodic table, which will be described below, is used. First, the surface of the rotor blade 23 on which the Ni intermediate plating film 11 is formed is alkali degreased (step S102). Next, the surface of the moving blade 23 is pickled and then electrolytically washed (step S103). The pickling and electrolytic cleaning are performed to activate the surface of the intermediate plating film 11 on which the first fluororesin-containing plating film 12 is formed.

次に、動翼２３の表面に成膜された中間めっき皮膜１１上に、第１フッ素樹脂含有めっき皮膜１２を成膜する（ステップＳ１０４）。このめっきにおいては、めっき液中の次亜燐酸陰イオンが、周期律表の第８族金属（この実施例では中間めっき皮膜１１であり、Ｎｉ）にある特定条件で接触すると、その金属が触媒となって、式（１）のように脱水素分解を起こさせる。なお、このメッキ液中には、直径が１μｍ以上２０μｍ以下に調整された第１フッ素樹脂粒子１３Ｐが添加されている。
［Ｈ2ＰＯ2］-＋Ｈ2Ｏ→Ｈ［ＨＰＯ3］-＋２Ｈ・・・（１） Next, the first fluororesin-containing plating film 12 is formed on the intermediate plating film 11 formed on the surface of the rotor blade 23 (step S104). In this plating, when the hypophosphite anion in the plating solution comes into contact with a group 8 metal in the periodic table (in this embodiment, the intermediate plating film 11 is Ni) under a specific condition, the metal becomes a catalyst. Thus, dehydrogenative decomposition is caused as shown in Formula (1). In addition, in this plating solution, the 1st fluororesin particle 13P adjusted in diameter to 1 to 20 micrometers is added.
[H 2 PO 2 ] − + H 2 O → H [HPO 3 ] − + 2H (1)

式（１）に示す反応によって生成した水素原子は、触媒金属（この実施例では中間めっき皮膜１１）表面に吸着されて、いわゆるCondensed Layerとなって活性化し、これがめっき液中のＮｉ陽イオンに接触すると、式（２）に示す反応によって、Ｎｉを金属に還元して触媒金属（この実施例では中間めっき皮膜１１）表面に析出させる。
Ｎｉ++＋２Ｈ→ＮｉO＋２Ｈ+・・・（２） The hydrogen atoms generated by the reaction shown in the formula (1) are adsorbed on the surface of the catalytic metal (in this embodiment, the intermediate plating film 11) and activated as a so-called condensed layer, which becomes Ni cations in the plating solution. When contacted, Ni is reduced to a metal by the reaction shown in Formula (2) and deposited on the surface of the catalytic metal (intermediate plating film 11 in this embodiment).
Ni ++ + 2H → Ni O + 2H + (2)

また触媒金属表面の活性化した水素原子は、めっき液中の次亜燐酸陰イオンと反応して、次亜燐酸陰イオンの含有するＰを還元してＮｉと合金を作る。これによって析出したニッケルが触媒となって、式（１）、式（２）で示した反応と同様なニッケルの還元めっき反応が継続して進行する。すなわちニッケルの自己触媒作用によりめっきが継続進行する。めっき液中のＮｉが上記反応によって析出する過程で、めっき液中に添加されている第１フッ素樹脂粒子１３Ｐは中間めっき皮膜１１上に付着し、析出したＮｉによって保持される。   The activated hydrogen atoms on the surface of the catalytic metal react with the hypophosphite anion in the plating solution to reduce P contained in the hypophosphite anion to form an alloy with Ni. The nickel thus deposited serves as a catalyst, and the nickel reduction plating reaction similar to the reaction represented by the formulas (1) and (2) proceeds continuously. That is, the plating proceeds continuously by the autocatalytic action of nickel. In the process in which Ni in the plating solution is precipitated by the above reaction, the first fluororesin particles 13P added in the plating solution adhere to the intermediate plating film 11 and are retained by the deposited Ni.

この実施例では、周期律表の第８属金属の自己触媒作用を利用する方法によって第１フッ素樹脂含有めっき皮膜１２を成膜するが、電気めっきによって第１フッ素樹脂含有めっき皮膜１２を成膜してもよい。なお、周期律表の第８属金属の自己触媒作用を利用する方法によって第１フッ素樹脂含有めっき皮膜１２を成膜すると、３次元形状に対しても、均一に第１フッ素樹脂含有めっき皮膜１２を形成できる。また、この実施例において、フッ素樹脂含有めっき皮膜１２の厚さは特に限定されるものではないが、１μｍ以上５０μｍ以下程度が適当である。   In this embodiment, the first fluororesin-containing plating film 12 is formed by a method using the autocatalytic action of the eighth group metal in the periodic table, but the first fluororesin-containing plating film 12 is formed by electroplating. May be. In addition, when the 1st fluororesin containing plating film 12 is formed into a film by the method of utilizing the autocatalytic action of the 8th group metal of a periodic table, the 1st fluororesin containing plating film 12 is also uniformly with respect to a three-dimensional shape. Can be formed. In this embodiment, the thickness of the fluororesin-containing plating film 12 is not particularly limited, but about 1 μm or more and 50 μm or less is appropriate.

次に、第１フッ素樹脂含有めっき皮膜１２上に、第２フッ素樹脂含有めっき皮膜１４を成膜する。第２フッ素樹脂含有めっき皮膜１４は、めっき液中に第２フッ素樹脂粒子１４Ｐを添加し、このめっき液を用いて第１フッ素樹脂含有めっき皮膜１２上に無電解めっきすることにより作製する。この無電解めっきは、例えば、上述した、周期律表の第８属金属（Ｎｉ）の自己触媒作用を利用する方法を用いる。まず、めっきマトリックス１３ＭがＮｉ‐Ｐの第１フッ素樹脂含有めっき皮膜１２の表面を、アルカリ脱脂する（ステップＳ１０５）。次に、第１フッ素樹脂含有めっき皮膜１２の表面を酸洗いして、その後、電解洗浄する（ステップＳ１０６）。酸洗い、及び電解洗浄は、第２フッ素樹脂含有めっき皮膜１４を成膜する第１フッ素樹脂含有めっき皮膜１２の表面を活性化させるために行われる。   Next, a second fluororesin-containing plating film 14 is formed on the first fluororesin-containing plating film 12. The second fluororesin-containing plating film 14 is prepared by adding the second fluororesin particles 14P to the plating solution and electrolessly plating the first fluororesin-containing plating film 12 using this plating solution. This electroless plating uses, for example, the above-described method utilizing the autocatalytic action of the group 8 metal (Ni) in the periodic table. First, the surface of the first fluororesin-containing plating film 12 in which the plating matrix 13M is Ni—P is alkaline degreased (step S105). Next, the surface of the first fluororesin-containing plating film 12 is pickled and then electrolytically washed (step S106). The pickling and electrolytic cleaning are performed to activate the surface of the first fluororesin-containing plating film 12 on which the second fluororesin-containing plating film 14 is formed.

次に、動翼２３の表面に成膜された第１フッ素樹脂含有めっき皮膜１２上に、第２フッ素樹脂含有めっき皮膜１４を成膜する（ステップＳ１０７）。この実施例では、上述した周期律表の第８属金属（この実施例では第１フッ素樹脂含有めっき皮膜１２であり、Ｎｉ‐Ｐ合金）の自己触媒作用を利用する方法を用いる。このＮｉ‐Ｐめっき液中には、直径が１μｍ未満に調整された第２フッ素樹脂粒子１４Ｐが添加されている。Ｎｉの自己触媒作用によりめっきが継続進行する過程で、めっき液中のＮｉが析出する。その過程で、めっき液中に添加されている第２フッ素樹脂粒子１４Ｐは第１フッ素樹脂含有めっき皮膜１２上に付着し、析出したＮｉによって保持される。   Next, the second fluorine resin-containing plating film 14 is formed on the first fluorine resin-containing plating film 12 formed on the surface of the rotor blade 23 (step S107). In this example, a method using the autocatalytic action of the eighth group metal (in this example, the first fluororesin-containing plating film 12 and Ni-P alloy) in the periodic table is used. In the Ni-P plating solution, second fluororesin particles 14P having a diameter adjusted to less than 1 μm are added. Ni in the plating solution is deposited in the process of continuous plating by the autocatalytic action of Ni. In the process, the second fluororesin particles 14P added to the plating solution adhere to the first fluororesin-containing plating film 12 and are retained by the deposited Ni.

この実施例では、周期律表の第８属金属の自己触媒作用を利用する方法によって第２フッ素樹脂含有めっき皮膜１４を成膜するが、電気めっきによって第２フッ素樹脂含有めっき皮膜１４を成膜してもよい。なお、周期律表の第８属金属の自己触媒作用を利用する方法によって第２フッ素樹脂含有めっき皮膜１４を成膜すると、３次元形状に対しても、均一に第１フッ素樹脂含有めっき皮膜１２を形成できる。   In this embodiment, the second fluororesin-containing plating film 14 is formed by a method utilizing the autocatalytic action of the eighth group metal in the periodic table, but the second fluororesin-containing plating film 14 is formed by electroplating. May be. When the second fluororesin-containing plating film 14 is formed by a method utilizing the autocatalytic action of the eighth group metal in the periodic table, the first fluororesin-containing plating film 12 is evenly formed even for a three-dimensional shape. Can be formed.

上記手順によって、被めっき部材である動翼２３に、中間めっき皮膜１１及びフッ素樹脂含有めっき皮膜１２を備えるめっき皮膜１０が成膜される。なお、めっき皮膜１０を成膜したら（ステップＳ１０７）、めっき皮膜１０を成膜した動翼２３を、３００℃〜３５０℃に所定時間保持する熱処理を施す（ステップＳ１０８）。この熱処理により、第１及び第２フッ素樹脂含有めっき皮膜１２、１４中のフッ素樹脂分を軟化・固着させる。これによって、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐの脱落が抑制でき、粒子の付着性抑制効果が長期にわたって維持できる。   By the above procedure, the plating film 10 including the intermediate plating film 11 and the fluororesin-containing plating film 12 is formed on the rotor blade 23 which is a member to be plated. In addition, if the plating film 10 is formed (step S107), the moving blade 23 on which the plating film 10 is formed is subjected to heat treatment for holding at 300 ° C. to 350 ° C. for a predetermined time (step S108). By this heat treatment, the fluororesin content in the first and second fluororesin-containing plating films 12 and 14 is softened and fixed. Thereby, the first and second fluororesin particles 13P and 14P can be prevented from falling off, and the effect of suppressing the adhesion of the particles can be maintained over a long period of time.

このように、フッ素樹脂含有するめっき皮膜１０を蒸気と接する動翼２３の表面２３Ｓに設けることにより、前記表面２３Ｓに付着する、蒸気に含まれるＳｉＯ2や酸化鉄（Ｆｅ3Ｏ4）等の微粒子の量を低減できる。 Thus, by providing the plating film 10 containing the fluororesin on the surface 23S of the moving blade 23 in contact with the steam, the SiO 2 or iron oxide (Fe 3 O 4 ) contained in the steam adheres to the surface 23S. The amount of fine particles can be reduced.

ここで、平面視において、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐの露出部分が、第２フッ素樹脂含有めっき皮膜１４の表面を占有する割合（表面占有率）は、１０％以上とすることが好ましい。表面占有率が１０％よりも小さいと、動翼２３の表面２３Ｓに付着する、蒸気に含まれるＳｉＯ2や酸化鉄（Ｆｅ3Ｏ4）等の微粒子の量が多くなるが、前記範囲であれば、前記微粒子の付着量を効果的に低減できる。前記微粒子の付着量を低減させる観点から、表面占有率は、２０％以上とすることがより好ましい。サブミクロンオーダーのフッ素樹脂粒子を含むめっき液を用いる場合、表面占有率は最大で２０％程度である。しかし、上述した、この実施例に係るめっき皮膜１０の構成によれば、第１フッ素樹脂粒子１３Ｐの間に、第２フッ素樹脂粒子１４Ｐを含む第２フッ素樹脂含有めっき皮膜１４が析出するので、表面占有率を４０％以上まで容易に引き上げることができる。 Here, in plan view, the ratio of the exposed portions of the first and second fluororesin particles 13P and 14P occupying the surface of the second fluororesin-containing plating film 14 (surface occupancy) is 10% or more. Is preferred. If the surface occupancy is smaller than 10%, the amount of fine particles such as SiO 2 and iron oxide (Fe 3 O 4 ) contained in the vapor adhering to the surface 23S of the rotor blade 23 increases. Thus, the amount of the fine particles attached can be effectively reduced. From the viewpoint of reducing the adhesion amount of the fine particles, the surface occupation ratio is more preferably 20% or more. In the case of using a plating solution containing submicron order fluororesin particles, the surface occupancy is about 20% at the maximum. However, according to the configuration of the plating film 10 according to this embodiment described above, the second fluororesin-containing plating film 14 including the second fluororesin particles 14P is deposited between the first fluororesin particles 13P. The surface occupancy can be easily increased to 40% or more.

上述したように、前記微粒子の付着量を低減させる観点からは、表面占有率はできるだけ大きい方がよい。しかし、表面占有率が大きくなりすぎると、めっきマトリックス１３Ｍ、１４Ｍによる第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐの保持能力が低下して、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐが脱落するおそれがある。かかる観点から、表面占有率は６０％以下とすることが好ましい。このようにすれば、第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐを、第１及び第２フッ素樹脂含有めっき皮膜１２、１４のめっきマトリックス１３Ｍ、１４Ｍで確実に保持できる。   As described above, the surface occupancy is preferably as large as possible from the viewpoint of reducing the adhesion amount of the fine particles. However, if the surface occupancy becomes too large, the holding ability of the first and second fluororesin particles 13P and 14P by the plating matrices 13M and 14M decreases, and the first and second fluororesin particles 13P and 14P fall off. There is a fear. From this viewpoint, the surface occupancy is preferably 60% or less. In this way, the first and second fluororesin particles 13P, 14P can be reliably held by the plating matrices 13M, 14M of the first and second fluororesin-containing plating films 12, 14.

第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐは、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリビリニデンフルオライド（ＰＶＤＦ）、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）のうち少なくとも１種類を含んで構成される。   The first and second fluororesin particles 13P and 14P are made of polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), It is configured to include at least one of polyvinylidene fluoride (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and ethylene-tetrafluoroethylene copolymer (ETFE).

（変形例１）
図６は、この実施例の第１変形例に係る動翼の表面を示す模式図である。この変形例は、上記実施例と略同様の構成であるが、第２フッ素樹脂含有めっき皮膜の表面に、さらにフッ素樹脂の皮膜を設ける点が異なる。他の構成は上記実施例と同様なので、説明を省略する。なお、上記実施例の構成は、適宜この変形例に適用できる。 (Modification 1)
FIG. 6 is a schematic view showing the surface of a rotor blade according to a first modification of this embodiment. This modified example has substantially the same configuration as the above example, except that a fluororesin film is further provided on the surface of the second fluororesin-containing plating film. Since other configurations are the same as those in the above embodiment, description thereof is omitted. In addition, the structure of the said Example is applicable to this modification suitably.

この動翼２３ａが備えるめっき皮膜１０ａは、第２フッ素樹脂含有めっき皮膜１４の表面に、さらにフッ素樹脂皮膜１５が形成される。このフッ素樹脂皮膜１５は、直径がサブミクロンオーダーのフッ素樹脂からなる。フッ素樹脂皮膜１５は、直径がサブミクロンオーダーのフッ素樹脂を界面活性剤で分散させた塗工液を、第１フッ素樹脂含有めっき皮膜１４の表面に塗布することにより形成される。これにより、めっき皮膜１０ａにおけるフッ素樹脂の表面占有率をさらに向上させることができるので、蒸気や圧縮対象の気体に含まれるＳｉＯ2等の微粒子の付着をより効果的に抑制できる。ここで、フッ素樹脂皮膜１５を構成するフッ素樹脂は、前記第１あるいは第２フッ素樹脂粒子１３Ｐ、１４Ｐと同じ材料を用いることができる。 As for the plating film 10a with which this moving blade 23a is provided, the fluororesin film | membrane 15 is further formed in the surface of the 2nd fluororesin containing plating film | membrane 14. FIG. The fluororesin film 15 is made of a fluororesin having a diameter of submicron order. The fluororesin film 15 is formed by applying a coating liquid in which a fluororesin having a diameter of submicron order is dispersed with a surfactant onto the surface of the first fluororesin-containing plating film 14. Thereby, since the surface occupation rate of the fluororesin in the plating film 10a can be further improved, adhesion of fine particles such as SiO 2 contained in vapor or gas to be compressed can be more effectively suppressed. Here, the fluororesin constituting the fluororesin film 15 may be made of the same material as the first or second fluororesin particles 13P and 14P.

（変形例２）
図７−１、図７−２は、この実施例の第２変形例に係る動翼の表面を示す模式図である。この変形例は、上記実施例と略同様の構成であるが、めっき皮膜を成膜する動翼の表面に、疲労強度を向上させる表面改質処理を施した点が異なる。他の構成は上記実施例と同様なので、説明を省略する。なお、上記実施例の構成は、適宜この変形例に適用できる。 (Modification 2)
FIGS. 7-1 and FIGS. 7-2 are schematic diagrams which show the surface of the moving blade which concerns on the 2nd modification of this Example. This modified example has substantially the same configuration as the above example, except that the surface of the rotor blade on which the plating film is formed is subjected to a surface modification treatment that improves fatigue strength. Since other configurations are the same as those in the above embodiment, description thereof is omitted. In addition, the structure of the said Example is applicable to this modification suitably.

中間めっき皮膜１１、第１及び第２フッ素樹脂含有めっき皮膜１２、１４により構成されるめっき皮膜１０を成膜した動翼は、めっき皮膜１０の成膜過程で基材の疲労強度が低下する。図７−１に示すように、蒸気中に含まれる粒子の衝突によりめっき皮膜１０が割れ、めっき皮膜１０にはクラック３が生ずることがある。クラック３が基材１ａまで到達した場合、クラック３の先端部３ｔが接する基材１ａの部分に大きな応力が作用する。この部分が破壊の起点となって、基材１ａの疲労を進行させてしまう。   In the moving blade on which the plating film 10 composed of the intermediate plating film 11 and the first and second fluororesin-containing plating films 12 and 14 is formed, the fatigue strength of the base material is lowered during the film formation process of the plating film 10. As shown in FIG. 7A, the plating film 10 may be cracked by the collision of particles contained in the vapor, and the plating film 10 may have a crack 3. When the crack 3 reaches the substrate 1a, a large stress acts on the portion of the substrate 1a with which the tip 3t of the crack 3 is in contact. This part becomes a starting point of destruction, and fatigue of the base material 1a is advanced.

図７−１、図７−２に示す動翼２３ｂ、２３ｃは、基材１ｂ、１ｃの疲労強度を向上させるため、基材１ｂ、１ｃの表面に中間めっき皮膜１１を形成する前に、基材１ｂ（動翼２３ｂ）等の表面に、予め疲労強度を向上させる表面改質処理を施す。図７−１に示す動翼２３ｂでは、基材１ｂの表面に窒化処理を施すことにより、窒化層２を形成する。これによって、基材１ｂの疲労強度を予め向上させる。そして、窒化層２の上に、中間めっき皮膜１１、第１フッ素樹脂含有めっき皮膜１２、第２フッ素樹脂含有めっき皮膜１４の順に成膜して、めっき皮膜１０を形成する。   In order to improve the fatigue strength of the base materials 1b and 1c, the rotor blades 23b and 23c shown in FIGS. 7-1 and 7-2 are formed before the intermediate plating film 11 is formed on the surfaces of the base materials 1b and 1c. A surface modification treatment for improving the fatigue strength is performed on the surface of the material 1b (the moving blade 23b) or the like in advance. In the moving blade 23b shown in FIG. 7A, the nitrided layer 2 is formed by nitriding the surface of the substrate 1b. Thereby, the fatigue strength of the substrate 1b is improved in advance. Then, on the nitride layer 2, the intermediate plating film 11, the first fluororesin-containing plating film 12, and the second fluororesin-containing plating film 14 are formed in this order to form the plating film 10.

また、図７−２に示す動翼２３ｃでは、基材１ｃの表面にショットピーニング加工を施す。これによって、基材１ｃの疲労強度を予め向上させる。そして、ショットピーニング加工した基材１ｃの表面に、中間めっき皮膜１１、第１フッ素樹脂含有めっき皮膜１２、第２フッ素樹脂含有めっき皮膜１４の順に成膜して、めっき皮膜１０を形成する。このように、動翼を構成する基材の表面に中間めっき皮膜を形成する前に、基材の表面に、予め疲労強度を向上させる表面改質処理を施すので、めっき皮膜に生じたクラックが基材１ｂ、１ｃまで到達した場合であっても、基材の疲労進行を抑制できる。また、窒化は基材の耐食性がやや低下するが、ショットピーニングによれば、窒化と比較して、基材１ｂの耐食性低下は少ないという利点もある。   Moreover, in the moving blade 23c shown to FIGS. 7-2, the shot peening process is given to the surface of the base material 1c. Thereby, the fatigue strength of the base material 1c is improved in advance. Then, the plating film 10 is formed by forming the intermediate plating film 11, the first fluororesin-containing plating film 12, and the second fluororesin-containing plating film 14 in this order on the surface of the base material 1 c subjected to the shot peening process. Thus, before the intermediate plating film is formed on the surface of the base material constituting the rotor blade, the surface of the base material is subjected to a surface modification treatment that improves the fatigue strength in advance, so that cracks generated in the plating film are generated. Even when the base materials 1b and 1c are reached, the progress of fatigue of the base material can be suppressed. In addition, nitriding slightly lowers the corrosion resistance of the base material, but shot peening has an advantage that the corrosion resistance of the base material 1b is less reduced than nitriding.

このように、基材に疲労強度を改善するための表面改質を施すと、めっきによる基材の疲労強度低下の影響を抑制できるので、特に疲労強度の要求される蒸気タービンの動翼やローター等に本発明は好ましく適用できる。この変形例では、基材の疲労強度を向上させる表面改質処理として、窒化及びショットピーニングを説明したが、基材の疲労強度を向上させる表面改質処理として、例えば浸炭や表面焼入れ等を適用してもよい。なお、窒化やショットピーニングを用いると、基材１ａ、１ｂと、中間めっき皮膜１１やフッ素樹脂含有めっき皮膜１２との密着性を向上できるので好ましい。   In this way, if surface modification is performed to improve the fatigue strength of the base material, the influence of the decrease in the fatigue strength of the base material due to plating can be suppressed. For example, the present invention is preferably applicable. In this modification, nitriding and shot peening have been described as the surface modification treatment for improving the fatigue strength of the base material. However, as the surface modification treatment for improving the fatigue strength of the base material, for example, carburization or surface quenching is applied. May be. In addition, it is preferable to use nitriding or shot peening because adhesion between the base materials 1a and 1b and the intermediate plating film 11 or the fluororesin-containing plating film 12 can be improved.

（変形例３）
図８、図９は、この実施例の第３変形例に係る動翼の表面を示す模式図である。この変形例は、上記実施例と略同様の構成であるが、基材の上に中間皮膜を介在させずに、直接フッ素樹脂含有めっき皮膜を成膜した点が異なる。他の構成は上記実施例と同様なので、説明を省略する。なお、上記実施例及びその変形例の構成は、適宜この変形例に適用できる。 (Modification 3)
8 and 9 are schematic views showing the surface of a rotor blade according to a third modification of this embodiment. This modified example has substantially the same configuration as the above example, except that a fluororesin-containing plating film is directly formed on the substrate without interposing an intermediate film. Since other configurations are the same as those in the above embodiment, description thereof is omitted. In addition, the structure of the said Example and its modification is applicable to this modification suitably.

図８に示す動翼２３ｄが備えるめっき皮膜１０ｄは、基材１の表面に、直接第１フッ素樹脂含有めっき皮膜１２を成膜し、その表面に第２フッ素樹脂含有めっき皮膜１４を成膜して構成される。このようにしても、めっき皮膜１０ｄの表面に露出する第１及び第２フッ素樹脂粒子１３Ｐ、１４Ｐによって、蒸気や圧縮対象の気体に含まれるＳｉＯ2等の微粒子の付着をより効果的に抑制できる。第１フッ素樹脂含有めっき皮膜１２を、周期律表の第８属金属の自己触媒作用を利用する方法により作製する場合、基材１の表面をアルカリ脱脂し、その後、基材１の表面１Ｓを酸洗い、電解洗浄することによって活性化させる。その後、前記方法により第１フッ素樹脂含有めっき皮膜１２を成膜する。なお、フッ素樹脂含有めっき皮膜１２は、ワット浴等の電気めっきによっても成膜することができる。 8 has a first fluororesin-containing plating film 12 formed directly on the surface of the substrate 1, and a second fluororesin-containing plating film 14 formed on the surface thereof. Configured. Even in this case, the first and second fluororesin particles 13P and 14P exposed on the surface of the plating film 10d can more effectively suppress adhesion of fine particles such as SiO 2 contained in vapor or gas to be compressed. . When producing the 1st fluororesin containing plating film 12 by the method of utilizing the autocatalytic action of the 8th group metal of a periodic table, the surface of the base material 1 is alkali-degritted, Then, the surface 1S of the base material 1 is formed. It is activated by pickling and electrolytic cleaning. Then, the 1st fluororesin containing plating film 12 is formed into a film by the said method. The fluororesin-containing plating film 12 can also be formed by electroplating such as a Watt bath.

図９に示す動翼２３ｅが備えるめっき皮膜１０ｅは、基材１の表面に、直接第１フッ素樹脂含有めっき皮膜１２を成膜する。そして、第１フッ素樹脂含有めっき皮膜１２の表面に第２フッ素樹脂含有めっき皮膜１４を成膜する。さらに第２フッ素樹脂含有めっき皮膜の表面に、上記変形例１で説明した、サブミクロンオーダーのフッ素樹脂からなるフッ素樹脂皮膜１５が形成される。これにより、めっき皮膜１０ｅにおけるフッ素樹脂の面積占有率をさらに向上させることができるので、蒸気や圧縮対象の気体に含まれるＳｉＯ2等の微粒子の付着をより効果的に抑制できる。 A plating film 10e included in the moving blade 23e shown in FIG. 9 directly forms the first fluororesin-containing plating film 12 on the surface of the base material 1. Then, the second fluororesin-containing plating film 14 is formed on the surface of the first fluororesin-containing plating film 12. Further, the fluororesin film 15 made of a submicron-order fluororesin described in Modification 1 is formed on the surface of the second fluororesin-containing plating film. Thereby, since the area occupation rate of the fluororesin in the plating film 10e can be further improved, adhesion of fine particles such as SiO 2 contained in vapor or gas to be compressed can be more effectively suppressed.

（評価例）
本発明に係るめっき皮膜を成膜した試験片を作製し、粒子付着を評価した。本発明に係る第１、第２フッ素樹脂含有めっき皮膜を成膜するにあたり、フッ素樹脂粒子として、ＰＴＦＥ及びＰＦＡを使用し、マトリックスの材料としてＮｉ‐Ｐ、Ｎｉ‐Ｂ、Ｎｉを用いたフッ素樹脂含有めっき皮膜を、基材（ＳＵＳ４１０Ｊ１）上に成膜した試験片を作製した。それぞれのフッ素樹脂含有めっき皮膜は、Ｎｉ‐Ｐの無電解めっき、Ｎｉ‐Ｂの無電解めっき、Ｎｉの電解めっきにより成膜した。また、基材の上に、フッ素樹脂を含有しない中間めっき皮膜を成膜して、その表面にフッ素樹脂含有めっき皮膜を成膜した試験片も作製した。さらに、第２フッ素樹脂含有めっき皮膜の表面にフッ素樹脂皮膜を成膜しためっき皮膜も作製した。いずれの試験片が備えるフッ素樹脂含有めっき皮膜においても、フッ素樹脂粒子表面占有率は１０％以上とした。なお、フッ素樹脂粒子表面占有率は、フッ素樹脂含有めっき皮膜の表面拡大写真から求めた。 (Evaluation example)
A test piece on which the plating film according to the present invention was formed was prepared, and particle adhesion was evaluated. In forming the first and second fluororesin-containing plating films according to the present invention, PTFE and PFA are used as the fluororesin particles, and the fluororesin using Ni-P, Ni-B, and Ni as the matrix material The test piece which formed the containing plating film into a film on the base material (SUS410J1) was produced. Each of the fluororesin-containing plating films was formed by Ni-P electroless plating, Ni-B electroless plating, or Ni electroplating. Moreover, the test piece which formed the intermediate plating film which does not contain a fluororesin on the base material, and formed the fluororesin containing plating film on the surface was also produced. Furthermore, a plating film in which a fluororesin film was formed on the surface of the second fluororesin-containing plating film was also produced. In any fluororesin-containing plating film provided in any test piece, the surface occupation ratio of the fluororesin particles was set to 10% or more. In addition, the fluorine resin particle surface occupation rate was calculated | required from the surface enlarged photograph of the fluororesin containing plating film.

比較例として、フッ素樹脂含有めっき層のフッ素樹脂粒子の直径が０．５μｍの試験片を作製した。また、従来例としてフッ素樹脂含有有機塗料を前記ステンレス鋼の基材にコーティングした試験片、及び前記ステンレス鋼の基材のみ（いずれのめっき皮膜なし）の試験片を作製した。そして、作製した試験片を用いて、それぞれのめっき皮膜の粒子付着を評価した。本発明に係るフッ素樹脂含有めっき皮膜を成膜した試験片、及び比較例に係る試験片皮膜構成、及び評価結果を表１に示す。   As a comparative example, a test piece having a fluororesin particle diameter of 0.5 μm of the fluororesin-containing plating layer was prepared. In addition, as a conventional example, a test piece in which a fluororesin-containing organic paint was coated on a stainless steel substrate and a test piece of only the stainless steel substrate (without any plating film) were prepared. And using the produced test piece, the particle adhesion of each plating film was evaluated. Table 1 shows the test piece on which the fluororesin-containing plating film according to the present invention was formed, the test piece film configuration according to the comparative example, and the evaluation results.

Figure 0004358803
Figure 0004358803

（めっき皮膜の成膜方法）
表１中のＮｏ．１〜Ｎｏ．４の試験片は、次の手順によりめっき皮膜が成膜された。
（１）２０ｍｍ×２０ｍｍ×５ｍｍのＳＵＳ４１０Ｊ１基材上に、本発明に係る第１及び第２フッ素樹脂含有めっき皮膜を成膜した。
（２）第１フッ素樹脂含有めっき皮膜は、日本カニゼン（株）製カニフロン（登録商標）液をベースとした中リンタイプの無電解Ｎｉ‐Ｐめっき液を使用し、その中にＰＴＦＥ,ＰＦＡの弗素粒子を界面活性剤により均一に分散させた。この場合のフッ素樹脂粒子径は１〜２０μｍである。皮膜の厚さは、粒子径に応じて次に示すように変化させた。なお、めっき温度は９０℃とした。
（ａ）粒子径が１μｍの場合、皮膜の厚さは２μｍ
（ｂ）粒子径が８μｍの場合、皮膜の厚さは５μｍ
（ｃ）粒子径が２０μｍの場合、皮膜の厚さは１５μｍ
（３）第２フッ素樹脂含有めっき皮膜は、日本カニゼン（株）製カニフロン（登録商標）液をベースとした中リンタイプの無電解Ｎｉ-Ｐめっき液を使用し、その中にＰＴＦＥ,ＰＦＡのフッ素樹脂粒子を界面活性剤により均一に分散させた。フッ素樹脂粒子径は０．３μｍである。皮膜の厚さは１０μｍとした。なお、めっき温度は９０℃とした。
（４）上記めっき後、いずれの試験片も３５０℃で１時間熱処理を施した。 (Plating film deposition method)
No. in Table 1 1-No. In the test piece No. 4, a plating film was formed by the following procedure.
(1) On the 20 mm × 20 mm × 5 mm SUS410J1 substrate, the first and second fluororesin-containing plating films according to the present invention were formed.
(2) The first fluororesin-containing plating film uses a medium phosphorus type electroless Ni-P plating solution based on the Kaniflon (registered trademark) solution manufactured by Nippon Kanisen Co., Ltd., and contains PTFE and PFA. Fluorine particles were uniformly dispersed with a surfactant. In this case, the fluororesin particle diameter is 1 to 20 μm. The thickness of the film was changed as follows according to the particle diameter. The plating temperature was 90 ° C.
(A) When the particle diameter is 1 μm, the film thickness is 2 μm
(B) When the particle diameter is 8 μm, the film thickness is 5 μm.
(C) When the particle diameter is 20 μm, the film thickness is 15 μm.
(3) The second fluororesin-containing plating film uses a medium phosphorus type electroless Ni-P plating solution based on Kaniflon (registered trademark) solution manufactured by Nippon Kanisen Co., Ltd., and contains PTFE and PFA. The fluororesin particles were uniformly dispersed with a surfactant. The fluororesin particle diameter is 0.3 μm. The thickness of the film was 10 μm. The plating temperature was 90 ° C.
(4) After the plating, all the test pieces were heat-treated at 350 ° C. for 1 hour.

表１中のＮｏ．５、Ｎｏ．６の試験片は、次の手順によりめっき皮膜が成膜された。
（１）２０ｍｍ×２０ｍｍ×５ｍｍのＳＵＳ４１０Ｊ１基材上に、本発明に係る中間めっき皮膜、第１及び第２フッ素樹脂含有めっき皮膜を成膜した。
（２）中間めっき皮膜（フッ素樹脂粒子を含有しないめっき皮膜）は、めっき液に中リンタイプの無電解Ｎｉ-Ｐめっき液及びワット浴用の電気めっき液を使用し、無電解めっきの場合は温度９０℃で、電気めっきの場合は温度５０℃、かつ電流密度５Ａ／ｄｍ2で、皮膜厚さ５μｍにめっきした。
（３）第１フッ素樹脂含有めっき皮膜は、中リンタイプの無電解Ｎｉ‐Ｐめっき液を使用し、その中にＰＴＦＥ、ＰＦＡの弗素粒子を界面活性剤により均一に分散させた。この場合のフッ素樹脂粒子径は８μｍである。皮膜の厚さは５μｍとした。
（４）第２フッ素樹脂含有めっき皮膜は、中リンタイプの無電解Ｎｉ-Ｐめっき液を使用し、その中にＰＴＦＥ,ＰＦＡのフッ素樹脂粒子を界面活性剤により均一に分散させた。この場合のフッ素樹脂粒子径は０．３μｍである。皮膜の厚さは１０μｍとした。なお、めっき温度は９０℃とした。
（５）上記めっき後、いずれの試験片も３５０℃で１時間熱処理を施した。 No. in Table 1 5, no. As for the test piece of 6, the plating film was formed in the following procedure.
(1) The intermediate plating film and the first and second fluororesin-containing plating films according to the present invention were formed on a SUS410J1 substrate of 20 mm × 20 mm × 5 mm.
(2) Intermediate plating film (plating film that does not contain fluororesin particles) uses medium phosphorus type electroless Ni-P plating solution and electroplating solution for watt bath as plating solution. In the case of electroplating at 90 ° C., plating was performed at a temperature of 50 ° C., a current density of 5 A / dm 2 , and a film thickness of 5 μm.
(3) As the first fluororesin-containing plating film, a medium phosphorous type electroless Ni-P plating solution was used, and PTFE and PFA fluorine particles were uniformly dispersed therein with a surfactant. In this case, the fluororesin particle diameter is 8 μm. The thickness of the film was 5 μm.
(4) For the second fluororesin-containing plating film, a medium phosphorus type electroless Ni—P plating solution was used, in which PTFE and PFA fluororesin particles were uniformly dispersed by a surfactant. In this case, the fluororesin particle diameter is 0.3 μm. The thickness of the film was 10 μm. The plating temperature was 90 ° C.
(5) After the plating, each test piece was heat-treated at 350 ° C. for 1 hour.

表１中のＮｏ．７、Ｎｏ．８の試験片は、次の手順によりめっき皮膜が成膜された。
（１）２０ｍｍ×２０ｍｍ×５ｍｍのＳＵＳ４１０Ｊ１基材上に、本発明に係る中間めっき皮膜、第１及び第２フッ素樹脂含有めっき皮膜、並びにフッ素樹脂皮膜を成膜した。
（２）第１フッ素樹脂含有めっき皮膜は、めっき液に中リンタイプの無電解Ｎｉ-Ｐめっき液及びワット浴用の電気めっき液を使用し、めっき液中にＰＴＦＥのフッ素樹脂粒子を界面活性剤により均一に分散させた。無電解めっきの場合は温度９０℃で、電気めっきの場合は温度５０℃、かつ電流密度５Ａ／ｄｍ2で、皮膜厚さ５μｍにめっきした。なお、フッ素樹脂粒子径は８μｍである。
（３）第２フッ素樹脂含有めっき皮膜は、中リンタイプの無電解Ｎｉ‐Ｐめっき液を使用し、その中にＰＴＦＥ,ＰＦＡの弗素粒子を界面活性剤により均一に分散させた。この場合のフッ素樹脂粒子径は８μｍである。皮膜の厚さは５μｍとした。
（４）第２フッ素樹脂含有めっき皮膜は、中リンタイプの無電解Ｎｉ-Ｐめっき液を使用し、その中にＰＴＦＥ,ＰＦＡのフッ素樹脂粒子を界面活性剤により均一に分散させた。無電解めっきの場合は温度９０℃で、電気めっきの場合は温度５０℃、かつ電流密度５Ａ／ｄｍ2で、皮膜厚さ１０μｍにめっきした。なお、フッ素樹脂粒子径は０．３μｍである。
（５）フッ素樹脂皮膜は、直径０．３μｍのＰＴＦＥを界面活性剤によりイオン交換水中に均一分散し（例えば、日本カニゼン（株）カニフロン（登録商標）用フッ素粒子分散液を使用）、前記手順によって第１及び第２フッ素樹脂含有めっき皮膜を成膜した試験片をその中に浸漬し、引き上げ成膜した。
（６）上記めっき後、いずれの試験片も３５０℃で１時間熱処理を施した。 No. in Table 1 7, no. As for the test piece of 8, the plating film was formed into a film with the following procedure.
(1) On the 20 mm × 20 mm × 5 mm SUS410J1 base material, the intermediate plating film, the first and second fluororesin-containing plating films, and the fluororesin film according to the present invention were formed.
(2) The first fluororesin-containing plating film uses a medium phosphorus type electroless Ni-P plating solution and a watt bath electroplating solution as the plating solution, and PTFE fluororesin particles in the plating solution as a surfactant. To make it evenly dispersed. In the case of electroless plating, plating was performed at a temperature of 90 ° C., in the case of electroplating, the temperature was 50 ° C., and the current density was 5 A / dm 2 , and the film thickness was 5 μm. The fluororesin particle diameter is 8 μm.
(3) As the second fluororesin-containing plating film, a medium phosphorous type electroless Ni-P plating solution was used, and PTFE and PFA fluorine particles were uniformly dispersed therein with a surfactant. In this case, the fluororesin particle diameter is 8 μm. The thickness of the film was 5 μm.
(4) For the second fluororesin-containing plating film, a medium phosphorus type electroless Ni—P plating solution was used, in which PTFE and PFA fluororesin particles were uniformly dispersed by a surfactant. In the case of electroless plating, plating was performed at a temperature of 90 ° C., in the case of electroplating, the temperature was 50 ° C., and the current density was 5 A / dm 2 , and the film thickness was 10 μm. The fluororesin particle diameter is 0.3 μm.
(5) The fluororesin film is prepared by uniformly dispersing PTFE having a diameter of 0.3 μm in ion-exchanged water using a surfactant (for example, using a fluorine particle dispersion for Kaniflon (registered trademark), Nippon Kanisen Co., Ltd.) The test piece on which the first and second fluororesin-containing plating films were formed was immersed in the film and pulled up to form a film.
(6) After the plating, each test piece was heat-treated at 350 ° C. for 1 hour.

表１中のＮｏ．９、Ｎｏ．１０の試験片は、次の手順によりめっき皮膜が成膜された。
（１）２０ｍｍ×２０ｍｍ×５ｍｍのＳＵＳ４１０Ｊ１基材上に、本発明に係る中間めっき皮膜、第１及び第２フッ素樹脂含有めっき皮膜、並びにフッ素樹脂皮膜を成膜した。
（２）中間めっき皮膜（フッ素樹脂粒子を含有しないめっき皮膜）は、めっき液に中リンタイプの無電解Ｎｉ-Ｐめっき液を使用し、温度９０℃で皮膜厚さ５μｍにめっきした。
（３）第１フッ素樹脂含有めっき皮膜は、めっき液に中リンタイプの無電解Ｎｉ-Ｐめっき液を使用し、めっき液中にＰＴＦＥのフッ素樹脂粒子を界面活性剤により均一に分散させた。そして、温度９０℃で、皮膜厚さ５μｍにめっきした。フッ素樹脂粒子径は８μｍである。
（４）第２フッ素樹脂含有めっき皮膜は、中リンタイプの無電解Ｎｉ‐Ｐめっき液を使用し、その中にＰＴＦＥ,ＰＦＡの弗素粒子を界面活性剤により均一に分散させた。無電解めっきは温度９０℃で、皮膜厚さ１０μｍにめっきした。なお、フッ素樹脂粒子径は０．３μｍである。
（５）フッ素樹脂皮膜は、直径０．３μｍのＰＴＦＥを界面活性剤によりイオン交換水中に均一分散し、前記手順によって第１及び第２フッ素樹脂含有めっき皮膜を成膜した試験片をその中に浸漬し、引き上げ成膜した。
（６）上記めっき後、いずれの試験片も３５０℃で１時間熱処理を施した。 No. in Table 1 9, no. Ten test pieces were formed with a plating film by the following procedure.
(1) On the 20 mm × 20 mm × 5 mm SUS410J1 base material, the intermediate plating film, the first and second fluororesin-containing plating films, and the fluororesin film according to the present invention were formed.
(2) The intermediate plating film (plating film containing no fluororesin particles) was plated at a temperature of 90 ° C. to a film thickness of 5 μm using a medium phosphorus type electroless Ni—P plating solution as the plating solution.
(3) For the first fluororesin-containing plating film, a medium phosphorus type electroless Ni-P plating solution was used as the plating solution, and PTFE fluororesin particles were uniformly dispersed in the plating solution by a surfactant. Then, the film was plated at a temperature of 90 ° C. to a film thickness of 5 μm. The fluororesin particle diameter is 8 μm.
(4) For the second fluororesin-containing plating film, a medium phosphorous type electroless Ni-P plating solution was used, and PTFE and PFA fluorine particles were uniformly dispersed therein with a surfactant. Electroless plating was performed at a temperature of 90 ° C. and a film thickness of 10 μm. The fluororesin particle diameter is 0.3 μm.
(5) The fluororesin film has a test piece in which PTFE having a diameter of 0.3 μm is uniformly dispersed in ion-exchanged water using a surfactant, and the first and second fluororesin-containing plating films are formed by the above procedure. It was immersed and pulled up to form a film.
(6) After the plating, each test piece was heat-treated at 350 ° C. for 1 hour.

（粒子付着評価試験方法）
図１０は、粒子付着評価試験に用いる試験装置を示す装置構成図である。この試験装置３０は、上記手順によって作製した試験片３６を、ドラム３１に嵌め込んで、粒子付着評価試験に供する。粒子付着評価試験は、ドラム３１を回転させながら、窒素（Ｎ2）ガスにより搬送されたシリカ（ＳｉＯ2）の超微粒子を試験片３６の表面に吹き付け、付着させる試験である。窒素ガスは、ノズル３３を通って噴射され、シリカ粒子は、粒子供給装置３２からノズル３３の出口近傍に供給される。ドラム３１の下方には、水タンク３４が設置されている。水タンク３４内の水は、１００℃で沸騰させられており、前記試験片３６に水分が供給される。また、試験片３６はドラム３１の内側に設置したヒーター３５により加熱される。 (Particle adhesion evaluation test method)
FIG. 10 is an apparatus configuration diagram showing a test apparatus used for the particle adhesion evaluation test. This test apparatus 30 is used for a particle adhesion evaluation test by fitting the test piece 36 produced by the above procedure into the drum 31. The particle adhesion evaluation test is a test in which ultrafine particles of silica (SiO 2 ) conveyed by nitrogen (N 2 ) gas are sprayed onto the surface of the test piece 36 while rotating the drum 31. Nitrogen gas is injected through the nozzle 33, and silica particles are supplied from the particle supply device 32 to the vicinity of the outlet of the nozzle 33. A water tank 34 is installed below the drum 31. The water in the water tank 34 is boiled at 100 ° C., and moisture is supplied to the test piece 36. The test piece 36 is heated by a heater 35 installed inside the drum 31.

（試験条件）
ドラム３１の回転数は１０ｒｐｍとし、試験片３６も、ドラム３１と同じ回転数で回転する。シリカ粒子は、日本アエロジル製のフュームドシリカ（グレード５０）を用いた。試験片３６の加熱温度は８０℃とした。また、シリカ粒子の衝突速度は３００ｍ／ｓｅｃ．とし、試験時間は８０時間とした。 (Test conditions)
The rotational speed of the drum 31 is 10 rpm, and the test piece 36 also rotates at the same rotational speed as the drum 31. As the silica particles, fumed silica (grade 50) manufactured by Nippon Aerosil Co., Ltd. was used. The heating temperature of the test piece 36 was 80 ° C. Further, the collision speed of the silica particles is 300 m / sec. The test time was 80 hours.

（評価方法）
試験前後における試験片３６の質量差から、シリカ粒子の付着量を測定した。それぞれの試験片の表面に付着したシリカ粒子の付着量Ｙ（ｇ）と、試験片の基材（ＳＵＳ４１０Ｊ１）そのものの表面（表面粗さＲｚ＝３．５μｍ）に付着したシリカ粒子の付着量Ｘ（ｇ）との比を、シリカ粒子付着倍率Ｚとして式（３）により算出した。
Ｚ＝Ｙ／Ｘ・・・（３） (Evaluation methods)
From the mass difference between the test pieces 36 before and after the test, the adhesion amount of the silica particles was measured. The amount Y (g) of silica particles adhering to the surface of each test piece and the amount X of silica particles adhering to the surface (surface roughness Rz = 3.5 μm) of the base material (SUS410J1) itself of the test piece The ratio with (g) was calculated by the formula (3) as the silica particle adhesion magnification Z.
Z = Y / X (3)

上記試験の結果を表１に示す。なお、次の説明におけるＮｏ．は、表１中の試験片Ｎｏ．に対応する。表１に示すように、本発明に係るフッ素樹脂含有めっき皮膜を成膜した試験片（Ｎｏ．１〜Ｎｏ．１０）のシリカ粒子付着倍率は、最も大きいもので０．２２である（Ｎｏ．１）。この結果からわかるように、本発明に係るフッ素樹脂含有めっき皮膜は、従来例の基材そのもの（Ｎｏ．１２）に対して、シリカ粒子付着量がおよそ１／５以下である。従来例のフッ素樹脂含有有機塗料（Ｎｏ．１３）に対しては、シリカ粒子付着量がおよそ１／４以下である。このように、本発明は、従来のものに対して格段に優れた粒子付着量低減効果を奏する。また、基材表面にフッ素樹脂含有めっき皮膜を形成したもの（Ｎｏ．１１）に対しても、シリカ粒子付着量を低減できる。   The results of the above test are shown in Table 1. In the following description, No. Is the test piece No. in Table 1. Corresponding to As shown in Table 1, the silica particle adhesion magnification of the test pieces (No. 1 to No. 10) on which the fluororesin-containing plating film according to the present invention was formed is the largest and is 0.22 (No. 1). 1). As can be seen from the results, the fluororesin-containing plating film according to the present invention has a silica particle adhesion amount of about 1/5 or less with respect to the conventional base material itself (No. 12). For the conventional fluororesin-containing organic paint (No. 13), the silica particle adhesion amount is about 1/4 or less. As described above, the present invention has a particle adhesion amount reducing effect that is remarkably superior to the conventional one. Moreover, the silica particle adhesion amount can also be reduced with respect to what formed the fluororesin containing plating film on the base-material surface (No. 11).

第２フッ素樹脂含有めっき皮膜の表面に、フッ素樹脂皮膜を形成した方が（Ｎｏ．７〜Ｎｏ．１０）、第２フッ素樹脂含有めっき皮膜の表面のみの場合（Ｎｏ．１〜Ｎｏ．６）よりもシリカ粒子付着倍率は小さくなる。   When the fluororesin film is formed on the surface of the second fluororesin-containing plating film (No. 7 to No. 10), only the surface of the second fluororesin-containing plating film is (No. 1 to No. 6). The silica particle adhesion magnification is smaller than that.

中間めっき皮膜の有無により、シリカ粒子付着倍率は影響を受けない。また、フッ素樹脂は、ＰＦＡ（Ｎｏ．４、Ｎｏ．１０）よりも、ＰＴＦＥ（Ｎｏ．１〜Ｎｏ．３、Ｎｏ．５〜Ｎｏ．９）の方が、シリカ粒子付着倍率はやや小さくなる。さらに、フッ素樹脂含有めっき皮膜の成膜方法（無電解めっきか電気めっき）の違いによるシリカ粒子付着倍率の違いは、ほとんどない。ただし、電気Ｎｉめっきでの硬度はＨｖで１５０〜３００であるのに対し、無電解Ｎｉ−Ｐめっき（フッ素樹脂含有無電解Ｎｉ−Ｐめっき）での硬度は、Ｈｖで２５０〜３００（非晶質）、めっき後、３５０℃〜４００℃で加熱処理をした場合には、Ｈｖで４５０〜５００（結晶質）である。割れ感受性は硬度に強い相関があり、電気Ｎｉめっきの方が無電解Ｎｉ−Ｐめっきよりも軟らかく、割れにくい。次に、窒化の有無が疲労強度に与える影響について説明する。   The silica particle adhesion magnification is not affected by the presence or absence of the intermediate plating film. Moreover, as for a fluororesin, the silica particle adhesion magnification becomes somewhat small in PTFE (No.1-No.3, No.5-No.9) rather than PFA (No.4, No.10). Furthermore, there is almost no difference in the silica particle adhesion magnification due to the difference in the film formation method (electroless plating or electroplating) of the fluororesin-containing plating film. However, the hardness in electro Ni plating is 150 to 300 in Hv, whereas the hardness in electroless Ni—P plating (fluororesin-containing electroless Ni—P plating) is 250 to 300 in Hv (amorphous). Quality), after plating, when the heat treatment is performed at 350 ° C. to 400 ° C., the Hv is 450 to 500 (crystalline). Cracking susceptibility has a strong correlation with hardness, and electric Ni plating is softer and more difficult to crack than electroless Ni-P plating. Next, the influence of the presence or absence of nitriding on the fatigue strength will be described.

図１１は、応力振幅と破断繰り返し数との関係を示す説明図である。試験片の基材の材料はＳＵＳ４１０Ｊ１、試験片は平滑試験片を用い、疲労強度を向上させる表面改質処理として窒化処理をした試験片、及び窒化処理をしない試験片にフッ素樹脂含有めっき皮膜（Ｎｉ−Ｐ）を形成した。窒化はラジカル窒化を用いた。そして、回転曲げ疲労試験により試験片の破断繰り返し数を求めた。繰り返し速度は３６００ｒｐｍ（Revolution Per Minute）、試験温度は室温とした。比較対象として、ＳＵＳ４１０Ｊ１のみの試験片（めっきなし）も試験した。   FIG. 11 is an explanatory diagram showing the relationship between the stress amplitude and the number of repetitions of fracture. The material of the base material of the test piece is SUS410J1, the test piece is a smooth test piece, a test piece subjected to nitriding treatment as a surface modification treatment for improving fatigue strength, and a test piece not subjected to nitriding treatment to a fluororesin-containing plating film ( Ni-P) was formed. Nitridation was radical nitriding. And the fracture | rupture repetition number of the test piece was calculated | required by the rotation bending fatigue test. The repetition rate was 3600 rpm (Revolution Per Minute), and the test temperature was room temperature. As a comparison object, a test piece (without plating) of only SUS410J1 was also tested.

図１１に示すように、窒化処理をしない試験片にフッ素樹脂含有めっき皮膜（Ｎｉ−Ｐ）を形成した試験片は、１０5程度の繰り返し数で試験片が破断している。一方、窒化処理をした試験片にフッ素樹脂含有めっき皮膜（Ｎｉ−Ｐ）を形成した試験片は、１０7程度の繰り返し数を経過した後でも試験片の破断はない。このように、基材に疲労強度を向上させる表面改質処理を施すと、めっき皮膜を形成した基材の疲労強度が向上し、単に基材のみの場合よりも大きな応力振幅に耐えられることがわかる。なお、疲労強度を向上させる表面改質処理は、ショットピーニングでも窒化の場合と同様の結果を示す。 As shown in FIG. 11, the test piece in which the fluororesin-containing plating film (Ni-P) is formed on the test piece not subjected to nitriding treatment has the test piece broken at a repetition rate of about 10 5 . On the other hand, the test piece in which the fluororesin-containing plating film (Ni-P) is formed on the nitriding-treated test piece does not break the test piece even after the number of repetitions of about 10 7 has elapsed. As described above, when the surface modification treatment for improving the fatigue strength is performed on the base material, the fatigue strength of the base material on which the plating film is formed is improved, and it can withstand a larger stress amplitude than the case of the base material alone. Recognize. Note that the surface modification treatment for improving the fatigue strength shows the same result as in nitriding in shot peening.

図１２は、めっき皮膜が単層の場合と複層の場合とにおけるフッ素樹脂粒子の表面占有面積率を示す説明図である。めっき皮膜を単層で構成する場合、粒子径が０．３μｍ及び６μｍのフッ素樹脂粒子を用いてフッ素樹脂含有めっき皮膜を形成した。めっき皮膜を複層で構成する場合、粒子径が６μｍのフッ素樹脂粒子を用いた第１フッ素樹脂含有めっき皮膜の表面に、粒子径が０．３μｍのフッ素樹脂粒子を用いた第２フッ素樹脂含有めっき皮膜を形成した。図１２の結果からわかるように、フッ素樹脂含有めっき皮膜を複層（この例では２層）で形成したものが、最もフッ素樹脂粒子の表面占有面積率は大ききなることがわかる。なお、フッ素樹脂含有めっき皮膜を複層とする場合、基材の表面に現れる第２フッ素樹脂含有めっき皮膜に含まれるフッ素樹脂粒子の粒子径は、第１フッ素樹脂含有めっき皮膜のフッ素粒子よりも直径が小さい。   FIG. 12 is an explanatory diagram showing the surface area ratio of the fluororesin particles when the plating film is a single layer and when it is a multilayer. When the plating film is composed of a single layer, the fluororesin-containing plating film was formed using fluororesin particles having particle diameters of 0.3 μm and 6 μm. When the plating film is composed of two or more layers, the second fluororesin is contained on the surface of the first fluororesin-containing plating film using the fluororesin particles having a particle diameter of 6 μm and the fluororesin particles having a particle diameter of 0.3 μm. A plating film was formed. As can be seen from the results in FIG. 12, it can be understood that the surface occupation area ratio of the fluororesin particles is the largest when the fluororesin-containing plating film is formed of multiple layers (in this example, two layers). When the fluororesin-containing plating film is a multilayer, the particle diameter of the fluororesin particles contained in the second fluororesin-containing plating film appearing on the surface of the substrate is larger than the fluorine particles of the first fluororesin-containing plating film. Small diameter.

以上のように、本発明に係る回転機械の部品及び回転機械は、蒸気タービンや圧縮機等の回転機械が備える部品に有用であり、特に、蒸気や圧縮対象の気体に含まれる微粒子が前記回転機械の部品に付着する量を低減することに適している。   As described above, the rotating machine component and the rotating machine according to the present invention are useful for a component provided in a rotating machine such as a steam turbine or a compressor, and in particular, fine particles contained in steam or a gas to be compressed are in the rotation. It is suitable for reducing the amount attached to machine parts.

この実施例に係るフッ素樹脂粒子含有めっき皮膜で表面を被覆した動翼を備える蒸気タービンのタービン室周辺を示す断面図である。It is sectional drawing which shows the turbine chamber periphery of a steam turbine provided with the moving blade which coat | covered the surface with the fluororesin particle containing plating film which concerns on this Example. この実施例に係るフッ素樹脂粒子含有めっき皮膜で表面を被覆した、蒸気タービンの動翼を示す斜視図である。It is a perspective view which shows the moving blade of a steam turbine which coat | covered the surface with the fluororesin particle containing plating film which concerns on this Example. 図２のＡ−Ａ断面図である。It is AA sectional drawing of FIG. この実施例に係る動翼の表面を示す模式図である。It is a schematic diagram which shows the surface of the moving blade which concerns on this Example. この実施例に係るめっき皮膜を生成する手順を示すフローチャートである。It is a flowchart which shows the procedure which produces | generates the plating film which concerns on this Example. この実施例の第１変形例に係る動翼の表面を示す模式図である。It is a schematic diagram which shows the surface of the moving blade which concerns on the 1st modification of this Example. この実施例の第２変形例に係る動翼の表面を示す模式図である。It is a schematic diagram which shows the surface of the moving blade which concerns on the 2nd modification of this Example. この実施例の第２変形例に係る動翼の表面を示す模式図である。It is a schematic diagram which shows the surface of the moving blade which concerns on the 2nd modification of this Example. この実施例の第３変形例に係る動翼の表面を示す模式図である。It is a schematic diagram which shows the surface of the moving blade which concerns on the 3rd modification of this Example. この実施例の第３変形例に係る動翼の表面を示す模式図である。It is a schematic diagram which shows the surface of the moving blade which concerns on the 3rd modification of this Example. 粒子付着評価試験に用いる試験装置を示す装置構成図である。It is an apparatus block diagram which shows the test apparatus used for a particle adhesion evaluation test. 応力振幅と破断繰り返し数との関係を示す説明図である。It is explanatory drawing which shows the relationship between a stress amplitude and the fracture | rupture repetition number. めっき皮膜が単層の場合と複層の場合とにおけるフッ素樹脂粒子の表面占有面積率を示す説明図である。It is explanatory drawing which shows the surface occupation area rate of the fluororesin particle in the case where a plating film is a single layer and the case where it is a multilayer.

符号の説明Explanation of symbols

１、１ａ、１ｂ、１ｃ 基材
２ 窒化層
３ クラック
３ｔ 先端部
１０、１０ａ、１０ｄ、１０ｅ めっき皮膜
１１ 中間めっき皮膜
１２ 第１フッ素樹脂含有めっき皮膜
１３Ｍ 第１めっきマトリックス
１３Ｐ 第１フッ素樹脂粒子
１４ 第２フッ素樹脂含有めっき皮膜
１４Ｐ 第２フッ素樹脂粒子
１４Ｍ 第２めっきマトリックス
１５ フッ素樹脂皮膜
２３、２３ａ、２３ｂ、２３ｃ、２３ｄ、２３ｅ 動翼 DESCRIPTION OF SYMBOLS 1, 1a, 1b, 1c Base material 2 Nitride layer 3 Crack 3t Tip part 10, 10a, 10d, 10e Plating film 11 Intermediate plating film 12 1st fluororesin containing plating film 13M 1st plating matrix 13P 1st fluororesin particle 14 Second fluororesin-containing plating film 14P Second fluorine resin particles 14M Second plating matrix 15 Fluorine resin film 23, 23a, 23b, 23c, 23d, 23e

Claims (12)

微粒子を含む気体を取り扱う回転体に用いられ、かつ微粒子を含む気体が接触する構造体であって、
第１のフッ素樹脂粒子が第１のめっきマトリックスに含有され、かつ前記第１のフッ素樹脂粒子の一部は、前記第１のめっきマトリックスの表面から露出する第１フッ素樹脂含有めっき皮膜と、
前記第１フッ素樹脂含有めっき皮膜の表面に形成され、かつ前記第１のフッ素樹脂粒子よりも直径が小さい第２のフッ素樹脂粒子が第２のめっきマトリックスに含有され、かつ前記第２のフッ素樹脂粒子及び前記第１のフッ素樹脂粒子の一部は、前記第２のめっきマトリックスの表面から露出する第２フッ素樹脂含有めっき皮膜と、
を含むめっき皮膜が表面に設けられることを特徴とする回転機械の部品。 A structure that is used in a rotating body that handles gas containing fine particles, and that is in contact with gas containing fine particles,
A first fluororesin particle is contained in the first plating matrix, and a part of the first fluororesin particle is exposed from a surface of the first plating matrix;
Second fluororesin particles formed on the surface of the first fluororesin-containing plating film and having a diameter smaller than that of the first fluororesin particles are contained in the second plating matrix, and the second fluororesin Particles and a part of the first fluororesin particles, a second fluororesin-containing plating film exposed from the surface of the second plating matrix;
A part of a rotating machine, characterized in that a plating film containing is provided on the surface. 前記めっき皮膜は、前記第１のフッ素樹脂含有めっき皮膜と前記構造体の表面との間に設けられる、金属の中間めっき皮膜を備えることを特徴とする請求項１に記載の回転機械の部品。   2. The rotating machine component according to claim 1, wherein the plating film includes a metal intermediate plating film provided between the first fluororesin-containing plating film and the surface of the structure. 前記中間めっき皮膜は、電気めっきにより成膜されることを特徴とする請求項２に記載の回転機械の部品。   The rotating machine part according to claim 2, wherein the intermediate plating film is formed by electroplating. 前記中間めっき皮膜は、Ｎｉであることを特徴とする請求項２又は３に記載の回転機械の部品。   4. The rotating machine component according to claim 2, wherein the intermediate plating film is Ni. 前記回転機械の部品の表面には、前記中間めっき皮膜が形成される部分の疲労強度を向上させる表面改質処理が施されることを特徴とする請求項１〜４のいずれか１項に記載の回転機械の部品。   The surface of the part of the rotating machine is subjected to a surface modification treatment for improving fatigue strength of a portion where the intermediate plating film is formed. Rotating machine parts. 前記第１のフッ素樹脂粒子の直径は１μｍ以上２０μｍ以下であることを特徴とする請求項１〜５のいずれか１項に記載の回転機械の部品。   6. The rotating machine component according to claim 1, wherein a diameter of the first fluororesin particle is 1 μm or more and 20 μm or less. 前記第１のフッ素樹脂粒子又は前記第２のフッ素樹脂粒子は、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリビリニデンフルオライド（ＰＶＤＦ）、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）の少なくとも１種類であることを特徴とする請求項１〜６のいずれか１項に記載の回転機械の部品。   The first fluororesin particles or the second fluororesin particles are made of polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. (PFA), poly (vinylidene fluoride) (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and ethylene-tetrafluoroethylene copolymer (ETFE). Item 7. A rotating machine component according to any one of Items 1 to 6. 前記第２フッ素樹脂含有めっき皮膜の表面に、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリビリニデンフルオライド（ＰＶＤＦ）、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）の少なくとも１種類からなるフッ素樹脂皮膜が形成されることを特徴とする請求項１〜７のいずれか１項に記載の回転機械の部品。   On the surface of the second fluororesin-containing plating film, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), poly A fluororesin film composed of at least one of vinylidene fluoride (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and ethylene-tetrafluoroethylene copolymer (ETFE) is formed. The component of the rotary machine of any one of Claims 1-7 to do. 前記第１のめっきマトリックス及び前記第２のめっきマトリックスは、Ｎｉ又はＮｉ基の金属であることを特徴とする請求項１〜８のいずれか１項に記載の回転機械の部品。   9. The rotating machine component according to claim 1, wherein the first plating matrix and the second plating matrix are Ni or a Ni-based metal. 平面視において、前記第１のフッ素樹脂粒子及び前記第２のフッ素樹脂粒子の露出した部分が、前記第２フッ素樹脂含有めっき皮膜の表面を占める面積の割合が１０％以上であることを特徴とする請求項１〜９のいずれか１項に記載の回転機械の部品。   In plan view, the ratio of the area of the exposed portion of the first fluororesin particles and the second fluororesin particles occupying the surface of the second fluororesin-containing plating film is 10% or more. The component of the rotary machine of any one of Claims 1-9 to do. 前記第１フッ素樹脂粒子含有めっき皮膜又は前記第２フッ素樹脂粒子含有めっき皮膜のうち少なくとも一方は、無電解めっきにより成膜されることを特徴とする請求項１〜１０のいずれか１項に記載の回転機械の部品。   11. The method according to claim 1, wherein at least one of the first fluororesin particle-containing plating film and the second fluororesin particle-containing plating film is formed by electroless plating. Rotating machine parts. 請求項１〜１１のいずれか１項に記載の回転機械の部品を、微粒子を含む気体が接触する部分に備えることを特徴とする回転機械。   A rotating machine comprising the rotating machine component according to any one of claims 1 to 11 in a portion in contact with a gas containing fine particles.
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