JP7057830B2 - 摺動部材及び内燃機関用部材 - Google Patents

摺動部材及び内燃機関用部材 Download PDF

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Publication number
JP7057830B2
JP7057830B2 JP2020534088A JP2020534088A JP7057830B2 JP 7057830 B2 JP7057830 B2 JP 7057830B2 JP 2020534088 A JP2020534088 A JP 2020534088A JP 2020534088 A JP2020534088 A JP 2020534088A JP 7057830 B2 JP7057830 B2 JP 7057830B2
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Prior art keywords
particles
sliding member
coating layer
copper alloy
alloy particles
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JP2020534088A
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JPWO2020026604A1 (ja
Inventor
佳典 伊澤
淳一 荒井
勝則 乙部
信一 西村
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Fukuda Metal Foil and Powder Co Ltd
Nissan Motor Co Ltd
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Fukuda Metal Foil and Powder Co Ltd
Nissan Motor Co Ltd
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/008—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of engine cylinder parts or of piston parts other than piston rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • B22F5/106—Tube or ring forms
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/16—Layered products comprising a layer of metal next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C23C24/00—Coating starting from inorganic powder
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    • 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
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    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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    • 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
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  • Crystallography & Structural Chemistry (AREA)
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  • Other Surface Treatments For Metallic Materials (AREA)
  • Sliding-Contact Bearings (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Shafts, Cranks, Connecting Bars, And Related Bearings (AREA)
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Description

本発明は、摺動部材に係り、更に詳細には、耐摩耗性を向上させた摺動部材に関する。
アルミニウムやアルミニウム合金は、軽量かつ高強度な材料であるため自動車などの軽量化に好適に用いられている。しかし、アルミニウムやアルミニウム合金は耐摩耗性が低いため、摺動部位を有する内燃機関用部材に用いる場合は、アルミニウムを含む基材の表面を被覆して耐摩耗性を向上させることが行われている。
特許文献１には、チタン、ニッケル、鉄、アルミニウム、コバルト、銅などの金属粒子、又はこれらの金属を含む合金粒子を、アルミニウムを含む基材の表面に低温ガスで吹き付け、運動エネルギーによって上記粒子を塑性変形させて基材の表面に結合させ、上記粒子で基材表面を被覆することが開示されている。
日本国特表２００８－５１９１５７号公報
しかしながら、特許文献１に記載の方法にあっては、基材に吹き付ける材料粒子中に吹き付けにより塑性変形が生じる軟らかい金属粒子を含んでいなければ被膜層を形成できない。
そして、炭化タングステンや窒化ケイ素などの硬質粒子を添加した場合は、軟質粒子中に硬質粒子がめり込むだけで粒子同士の化学的な結合が弱いため、被膜層の強度が得られず耐摩耗性が十分でない。
本発明は、このような従来技術の有する課題に鑑みてなされたものであり、その目的とするところは、被膜層の強度が高く、優れた耐摩耗性を有する摺動部材を提供することにある。
本発明者は、上記目的を達成すべく鋭意検討を重ねた結果、組成が異なる２種以上の析出硬化型銅合金粒子で被膜層を形成することで、上記析出硬化型銅合金粒子同士が共に塑性変形して物理的に結合するだけでなく反応層を形成して化学的にも結合することを見出し、本発明を完成するに至った。
即ち、本発明の摺動部材は、基材と、上記基材上に形成された被膜層と、を備える。
そして、上記被膜層が粒子集合体からなり、上記該粒子集合体が、組成が異なる２種の析出硬化型銅合金粒子から成り、
上記粒子集合体を形成する少なくとも１種の析出硬化型銅合金粒子のビッカース硬度が、１５０Ｈｖ～２５０Ｈｖであり、上記２種の析出硬化型銅合金粒子同士の硬さの差が２００Ｈｖ以下であることを特徴とする。
また、本発明の内燃機関用部材は、摺動部位を有する。
そして、上記摺動部位に上記摺動部材を備えることを特徴とする。
本発明によれば、組成が異なる２種の析出硬化型銅合金粒子を含有する粒子集合体で被膜層を形成することとしたため、被膜層の強度が高く優れた耐摩耗性を有する摺動部材を提供することができる。
本発明の摺動部材の断面概略図である。
＜摺動部材＞
本発明の摺動部材について詳細に説明する。
上記摺動部材は、図１に示すように、基材３と該基材上に形成された被膜層２とを備え、上記被膜層２が、組成が異なる２種以上の析出硬化型銅合金粒子２１ａ、２１ｂを含有する粒子集合体からなる。
本発明において、「組成が異なる」とは、銅以外の添加元素が、異種金属であってもよく、また濃度が異なる同種金属であってもよい。
上記析出硬化型銅合金粒子は、過飽和固溶体状態の粒子を、後述するコールドスプレー法により基材表面に吹き付けることで形成でき、固相状態で基材に衝突したときの衝撃による発熱や応力などによって、固溶限を越えて固溶している成分が析出し硬化して析出硬化型銅合金粒子となる。
上記過飽和固溶体状態の粒子は軟らかく変形能が高いため、固相状態で吹き付けて基材表面に衝突させると、塑性変形して局所的な発熱により溶融し原子拡散などが生じて拡散層や金属間化合物などを含む反応層を形成し、析出硬化型銅合金粒子が強固に結合した粒子集合体を形成するため、被膜強度が向上する。
このように、上記過飽和固溶体状態の粒子は、析出硬化により硬度が高くなると共に、析出硬化型銅合金粒子同士が強固に結合した粒子集合体の被膜層を形成するため、耐摩耗性が優れた摺動部材を形成できる。
上記過飽和固溶体状態の粒子としては、銅を主成分とし、変形能が大きく、かつ添加元素として銅の結晶格子中に拡散できる原子半径を有する金属元素を含む合金粒子を使用できる。なお、本発明において主成分とは、８０質量％以上含有する成分をいう。
上記過飽和固溶体状態の粒子としては、例えば、Ｃｕ－Ｎｉ－Ｓｉ系合金粒子、Ｃｕ－Ｃｏ－Ｓｉ系合金粒子、Ｃｕ－Ｃｒ合金粒子、Ｃｕ－Ｚｒ合金粒子、Ｃｕ－Ｔｉ合金粒子などを挙げることができる。
なかでも、Ｓｉを含む合金粒子は、Ｓｉが表面に拡散してＳｉＯ２の膜を形成し、この膜が不動態膜のようにふるまい被膜層の耐腐食性を向上させるため好ましく使用できる。
上記過飽和固溶体状態の粒子の硬度は、その組成にもよるが常温で２００Ｈｖ以下であることが好ましい。
上記添加元素の固溶量が小さく、予め結晶粒子が析出した硬い銅合金粒子であると、析出している結晶粒子が銅合金粒子の変形を阻害し変形能が小さくなるため、衝突時の応力を吸収できず銅合金粒子が割れてしまい被膜層の形成が困難である。
上記過飽和固溶体状態の粒子は、水アトマイズ法により作製することができる。
具体的には、固溶限を超えた添加元素を含む溶融金属を流下させて高圧の水を吹き付け、上記溶融金属を霧化し急冷凝固させて粒子化することで作製できる。
上記過飽和固溶体状態の粒子の平均径（Ｄ５０）は、２０μｍ～４０μｍであることが好ましい。
上記過飽和固溶体状態の粒子の平均粒径を小さくすることで密実な被膜を形成できるが、粒子径が小さすぎると吹き付けの際、上記粒子の運動エネルギーが小さくなって塑性変形し難くなり、上記粒子同士の密着性が低下して被膜層の強度が低下することがある。
上記粒子集合体は、少なくとも１種の析出硬化型銅合金粒子のビッカース硬度が、１５０Ｈｖ～２５０Ｈｖであることが好ましい。硬度が上記範囲の析出硬化型銅合金粒子を含むことで、該粒子が塑性変形して粒子集合体を形成できる。
また、上記比較的軟らかい析出硬化型銅合金粒子を多く含むことで、気孔率が小さくなり被膜強度が向上する。
上記２種以上の析出硬化型銅合金粒子の硬さの差は、２００Ｈｖ以下であることが好ましく、６０Ｈｖ以下であることがより好ましい。
析出硬化型銅合金粒子の硬さの差が２００Ｈｖを超えると軟らかい析出硬化型銅合金粒子のみが塑性変形し、硬い析出硬化型銅合金粒子が塑性変形しないため、硬い析出硬化型銅合金粒子の表面温度が上がらず原子拡散が起こり難くなり、粒子集合体の結合力が低下して耐摩耗性が低下することがある。
上記析出硬化型銅合金粒子中の結晶粒子は、平均粒径が１μｍ未満のナノ結晶であることが好ましい。上記析出硬化型銅合金粒子中の結晶粒子が微細であることで、被膜層の強度が向上する。
上記被膜層は、断面の気孔率が３面積％以下であることが好ましく、１面積％以下であることが好ましい。気孔が少なく密実であることで被膜層の強度が向上し、耐摩耗性が向上する。
上記被膜層の断面における気孔率や、析出硬化型銅合金粒子の平均粒径（円相当径：粒子像の投影面積と同じ面積を持つ円の直径）は、走査型電子顕微鏡像（ＳＥＭ像）を画像処理により２値化し、画像解析により算出することができる。
上記被膜層の厚さは、摺動部材が用いられる箇所の温度や摺動環境にもよるが、例えば、０．０５～５．０ｍｍとすることが好ましく、０．１～０．５ｍｍとすることがより好ましい。
０．０５ｍｍ未満であると、被膜層自体の強度が不足し、基材の強度が低い場合に塑性変形を起こすことがある。また、５．０ｍｍを超えると、成膜時に発生する残留応力と界面密着力の関係により被膜層が剥離し易くなることがある。
上記基材としては、特に制限はなく、内燃機関の摺動部材として従来から用いられている金属を使用できるがアルミ合金は熱伝導性が高く好ましく使用できる。
上記アルミ合金としては、例えば、日本工業規格で規定されているＡＣ２Ａ、ＡＣ８Ａ、ＡＤＣ１２などを挙げることができる。
上記摺動部材は、耐摩耗性に優れ、例えば、ピストン、ピストンリング、ピストンピン、シリンダ、クランクシャフト、カムシャフト、及び、バルブリフタなど、摺動部位を有する内燃機関用部材に好適に使用できる。
＜摺動部材の製造方法＞
上記摺動部材は、コールドスプレー法により、銅を主成分とし、組成が異なる２種以上の過飽和固溶体状態の粒子を含む原料粒子を基材表面に吹き付けることで製造できる。
上記コールドスプレー法は、過飽和固溶体状態の粒子を溶融またはガス化させることなく不活性ガスと共に超音速流で固相状態のまま基材に衝突させて被膜層を形成する方法であり、溶射法などの材料の金属粒子を溶融させて被膜層を形成する方法とは異なり、熱による被膜層の酸化を最小限にすることができる。
上記コールドスプレー法により、固相状態の過飽和固溶体状態の粒子が基材に衝突すると上記粒子自体や基材３が塑性変形して塑性変形部２２が形成され、固溶限を超えた添加成分が析出して硬化し析出硬化型銅合金粒子２１になる。
そして、運動エネルギーの一部が熱エネルギーに変換されて上記析出硬化型銅合金粒子２１の表面が局所的な発熱により溶融して固化し、あるいは原子拡散が生じて析出硬化型銅合金粒子同士が結合して被膜層２が形成される。
このとき、基材３及び過飽和固溶体状態の粒子の温度が該固溶体粒子の融点以下であるため、局所的に溶融した過飽和固溶体状態の粒子の表面が急冷され、過飽和固溶体状態の粒子同士の界面２３にはアモルファスやナノ結晶が形成される。
そして、上記アモルファスやナノ結晶は、歪が大きく原子が動きやすいため、拡散が起こり易く結合強度が高くなる。
このように形成された析出硬化型銅合金粒子２１の粒子集合体は、析出硬化型銅合金粒子２１の表面が局所的に溶融して固化し、被膜層全体の粒子集合体が結合して一体化している。しかし、上記析出硬化型銅合金粒子２１同士が渾然一体とはならずに界面２３を形成しており、この界面２３近傍にアモルファスやナノ結晶含む塑性変形部２２を有する。
この点、溶射などにより、材料の金属粒子が完全に溶融又は溶解し固化し、上記塑性変形部を形成せずに渾然一体となった被膜層と異なる。
また、上記基材３と上記被膜層２との間には、拡散層や金属間化合物層を含む中間層４が形成されるが、溶融した過飽和固溶体状態の粒子の表面が急冷されるため、溶射法や焼結によって形成したときの中間層よりも薄く、その膜厚は２μｍ以下となる。
上記析出硬化型銅合金粒子界面のアモルファスや析出硬化型銅合金粒子中の結晶粒子は、走査電子顕微鏡（ＳＥＭ）による電子線後方散乱回折（ＥＢＳＤ）により、回折パターンを検出器面上に投影し、その投影されたパターンから結晶方位を解析することで確認できる。
上記過飽和固溶体状態の粒子を吹き付ける速度は、３００～１２００ｍ／ｓであることが好ましく、５００～１０００ｍ／ｓであることが好ましい。３００ｍ／ｓ未満では、過飽和固溶体状態の粒子を塑性変形させる応力が小さく、析出硬化が充分でないことがあり、また気孔率が大きくなることがある。
また、上記過飽和固溶体状態の粒子を吹き付ける作動ガスの圧力は、２～５ＭＰａであることが好ましく、３．５～５ＭＰａであることがより好ましい。作動ガスの圧力が２ＭＰａ未満であると、上記粒子速度が得られ難くなることがある。
また、作動ガスの温度は、過飽和固溶体状態の粒子の種類にもよるが、４００～８００℃であることが好ましく、５００～７００℃であることがより好ましい。
作動ガスの温度が４００℃未満であると、過飽和固溶体状態の粒子が塑性変形し難く、気孔率が大きくなって被膜強度が低下することがある。また、作動ガスの温度が８００℃を超えると、酸化により、強度が低下する恐れがある。
上記、作動ガスとしては、例えば、窒素ガス、ヘリウムガスなどを挙げることができ、これらは、１種を単独で用いてもよく、混合して用いてもよい。
以下、本発明を実施例により詳細に説明するが、本発明は下記実施例に限定されるものではない。
［実施例１］
シリンダヘッドにおけるエンジンバルブの着座部の加工完了状態で、狙い被膜層厚み０．２ｍｍを想定して、アルミニウム材（Ａ５０５６ＢＥ－Ｈ１１２）を前加工してアルミニウム基材を用意した。
上記アルミニウム基材を回転テーブルに装着し、回転テーブルを回転させながら、水アトマイズ法で作製した過飽和固溶体状態の粒子（組成：（質量％）Ｃｕ－３Ｎｉ－０．７Ｓｉ、平均粒子径（ｄ５０）：２７．７μｍ）と、同様に水アトマイズ法で作製した過飽和固溶体状態の粒子（組成：Ｃｕ－６Ｎｉ－１．４Ｓｉ、平均粒子径（ｄ５０）：２６．８μｍ）とを質量比８０：２０で含む原料粒子を以下の条件でコールドスプレーし、０．４～０．５ｍｍの被膜層を形成した。
上記固溶体粒子の付着率を表１に示す。
高圧型コールドスプレー装置 ：プラズマ技研工業株式会社製、ＰＣＳ－１０００
作動ガス ：窒素
チャンバー内ガス圧力 ：４ＭＰａ
チャンバー内ガス温度 ：６００℃（衝突時の粒子温度は約２００℃）
粒子速度 ：６８０～７２０ｍ／ｓ
粒子供給量 ：７ｇ／ｍｉｎ
上記被膜層を実際のシリンダヘッドにおけるエンジンバルブの着座部の形状に仕上げ、厚み０．２ｍｍの被膜層として摺動部材を得た。
［実施例２］
過飽和固溶体状態の粒子（組成：Ｃｕ－３Ｎｉ－０．７Ｓｉ、平均粒子径（ｄ５０）：２７．７μｍ）と、過飽和固溶体状態の粒子（組成：（質量％）Ｃｕ－１４Ｎｉ－３Ｓｉ－２Ｖ－２．２Ｃｒ－１．４Ｆｅ－１．２Ａｌ、平均粒子径（ｄ５０）：３３．２μｍ）とを、質量比８０：２０で含む原料粒子を用いる他は実施例１と同様にして摺動部材を得た。
［比較例１］
過飽和固溶体状態の粒子（組成：（質量％）Ｃｕ－３Ｎｉ－０．７Ｓｉ、平均粒子径（ｄ５０）：２７．７μｍ）を単独で用いる他は実施例１と同様にして摺動部材を得た。
［比較例２］
過飽和固溶体状態の粒子（組成：（質量％）Ｃｕ－６Ｎｉ－１．４Ｓｉ、平均粒子径（ｄ５０）：２６．８μｍ）を単独で用いる他は実施例１と同様にして摺動部材を得た。
［比較例３］
過飽和固溶体状態の粒子（組成：（質量％）Ｃｕ－１４Ｎｉ－３Ｓｉ－２Ｖ－２．２Ｃｒ－１．４Ｆｅ－１．２Ａｌ、平均粒子径（ｄ５０）：３３．２μｍ）を単独で用いる他は実施例１と同様にして摺動部材を得た。
＜評価＞
上記摺動部材を以下の方法で評価した。評価結果を表１に示す。
（被膜組織の観察）
走査電子顕微鏡（ＳＥＭ）による電子線後方散乱回折（ＥＢＳＤ）を行い被膜層の組織を観察し、析出硬化型銅合金粒子中の析出結晶粒子の組成、気孔率、析出結晶粒子の粒径及びアモルファスの有無から塑性変形部の有無、及び中間層を確認した。
（析出硬化型銅合金粒子の硬度測定）
上記走査電子顕微鏡（ＳＥＭ）の組成像で成分の違いを確認しながら、同一視野でビッカース硬さ試験（ＪＩＳ Ｚ ２２４４）に準拠して測定した。
（耐摩耗性）
高千穂精機株式会社製のバルブシート摩耗試験機を用いて、下記の条件で耐食性試験後の摺動部材の摩耗量を測定した。
具体的には、形状測定装置を用いて試験前と試験後のシリンダヘッドにおけるエンジンバルブの着座部の形状を取得し、４カ所の摩耗量を測定した平均値から比較例１に対する摩耗比を算出した。
相手バルブ材：ＳＵＨ３５
試験温度 ：３２５℃
上下速度 ：３０００回／ｍｉｎ
バルブ回転数：５ｒｐｍ
着座回数 ：５４００００回
Figure 0007057830000001
表１の結果から、組成が異なる２種以上の析出硬化型銅合金粒子を含有する被膜層を形成した実施例の摺動部材は、析出硬化型銅合金粒子が一種類の比較例に比して耐摩耗性が優れることがわかる。
１ 摺動部材
２ 被膜層
２１ａ 析出硬化型銅合金粒子
２１ｂ 析出硬化型銅合金粒子
２２ 塑性変形部
２３ 界面
３ 基材
４ 中間層

Claims (7)

  1. 基材と、上記基材上に形成された被膜層と、を備える摺動部材であって、
    上記被膜層が粒子集合体からなり、
    上記該粒子集合体が、組成が異なる２種の析出硬化型銅合金粒子から成り、
    上記粒子集合体を形成する少なくとも１種の析出硬化型銅合金粒子のビッカース硬度が、１５０Ｈｖ～２５０Ｈｖであり、
    上記２種の析出硬化型銅合金粒子同士の硬さの差が２００Ｈｖ以下であることを特徴とする摺動部材。
  2. 上記２種の析出硬化型銅合金粒子同士の硬さの差が６０Ｈｖ以下であることを特徴とする請求項１に記載の摺動部材。
  3. 上記基材及び上記被膜層の少なくとも一方が、塑性変形部を有することを特徴とする請求項１又は２に記載の摺動部材。
  4. 上記被膜層を構成する粒子同士の界面に、アモルファス及びナノ結晶の少なくともいずれか一方を有することを特徴とする請求項１～３のいずれか１つの項に記載の摺動部材。
  5. 上記基材と上記被膜層との間の少なくとも一部に中間層を備え、
    上記中間層が、拡散層及び金属間化合物層の少なくとも一方を含むことを特徴とする請求項１～４のいずれか１つの項に記載の摺動部材。
  6. 上記中間の膜厚が２μｍ以下であることを特徴とする請求項５に記載の摺動部材。
  7. 請求項１～６のいずれか１つの項に記載の摺動部材を内燃機関の摺動部位に有することを特徴とする内燃機関の摺動部材。
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