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 PDFInfo
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- 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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- particles
- sliding member
- coating layer
- copper alloy
- alloy particles
- Prior art date
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- 238000002485 combustion reaction Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims description 135
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 42
- 239000011247 coating layer Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 29
- 238000004881 precipitation hardening Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 15
- 238000009792 diffusion process Methods 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009692 water atomization Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001887 electron backscatter diffraction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910020711 Co—Si Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Description
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。
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。
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。
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。
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。
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。
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。
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。
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。
上記固溶体粒子の付着率を表1に示す。
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
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。
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。
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。
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。
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。
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。
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。
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。
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
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)
- 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。 - 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。
- 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。
- 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。
- 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。 - 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。
- 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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