JP7030199B2 - 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
- Publication number
- JP7030199B2 JP7030199B2 JP2020534098A JP2020534098A JP7030199B2 JP 7030199 B2 JP7030199 B2 JP 7030199B2 JP 2020534098 A JP2020534098 A JP 2020534098A JP 2020534098 A JP2020534098 A JP 2020534098A JP 7030199 B2 JP7030199 B2 JP 7030199B2
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- Prior art keywords
- particles
- coating layer
- sliding member
- copper alloy
- base material
- Prior art date
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- 238000002485 combustion reaction Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims description 122
- 239000011247 coating layer Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 35
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 32
- 239000010941 cobalt Substances 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 22
- 238000004881 precipitation hardening Methods 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000002159 nanocrystal Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000007921 spray Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 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
- 230000035882 stress Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- 229910020711 Co—Si Inorganic materials 0.000 description 1
- 229910017868 Cu—Ni—Co Inorganic materials 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
- 238000005299 abrasion Methods 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 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
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/06—Sliding surface mainly made of metal
- F16C33/12—Structural composition; Use of special materials or surface treatments, e.g. for rust-proofing
-
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- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- F01L1/047—Camshafts
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01L2800/00—Methods of operation using a variable valve timing mechanism
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L2820/00—Details on specific features characterising valve gear arrangements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
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Description
そして、上記被膜層が、析出硬化型銅合金粒子を含有する粒子集合体で形成され、
上記析出硬化型銅合金粒子が、0.8質量%~4質量%のコバルト(Co)とケイ素(Si)と、を含み、ケイ化コバルト(Co 2 Si)を含む析出相を有し、粒子中の結晶粒子の平均粒径が1μm未満であり、
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。
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、コバルト(Co)及びケイ素(Si)を含む析出硬化型銅合金粒子21を含有する粒子集合体を含む。
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。
添加元素の固溶量が小さく、結晶粒子が予め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するため、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、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強度が低下することがある。
上記摺動部材は、コールドスプレー法により、コバルト(Co)及びケイ素(Si)を含み、銅を主成分とする過飽和固溶体状態の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。
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、強度が低下することがある。
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。
上記過飽和固溶体状態の粒子の付着率を表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:(質量%)Cu-0.8Ni-2.2Co-0.7Si、平均粒子径(d50):26.1μm)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-1.5Ni-1.5Co-0.7Si、平均粒子径(d50):26.2μm)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-2.2Ni-0.8Co-0.7Si、平均粒子径(d50):26.3μm)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-3.0Ni-0.7Si、平均粒子径(d50):27.7μm)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-14Ni-3Si-2V-2.2Cr-1.4Fe-1.2Al、平均粒子径(d50):33.2μm)を用いる他は実施例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。
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 被覆層
21 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 (5)
- 基材と、該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、析出硬化型銅合金粒子を含有する粒子集合体で形成され、
上記析出硬化型銅合金粒子が、0.8質量%~4質量%のコバルト(Co)とケイ素(Si)と、を含み、ケイ化コバルト(Co 2 Si)を含む析出相を有し、粒子中の結晶粒子の平均粒径が1μm未満であり、
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摺動部材。 - 上記析出硬化型銅合金粒子が、ニッケル(Ni)、鉄(Fe)、及びマンガン(Mn)から成る群から選択される少なくとも1種を含み、コバルトとの合計含有量が2質量%~4質量%であることを特徴とする請求項1に記載の摺動部材。
- 上記被膜層の断面における気孔率が、3面積%以下であ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1~3のいずれか1つの項に記載の摺動部材。 - 摺動部位を有する内燃機関用部材であって、
上記摺動部位に上記請求項1~4のいずれか1つの項に記載の摺動部材を備えることを特徴とする内燃機関用部材。
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JP2507931B2 (ja) * | 1987-03-25 | 1996-06-19 | 三菱マテリアル株式会社 | Cu系合金製変速機用同期リング |
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WO2001004373A1 (fr) * | 1999-07-09 | 2001-01-18 | Taiho Kogyo Co., Ltd. | Materiau composite cuivre-aluminium projete et procede de fabrication associe |
JP2001240925A (ja) * | 2000-02-29 | 2001-09-04 | Daido Metal Co Ltd | 銅系摺動材料 |
US20060093736A1 (en) | 2004-10-29 | 2006-05-04 | Derek Raybould | Aluminum articles with wear-resistant coatings and methods for applying the coatings onto the articles |
JP5713073B2 (ja) * | 2013-09-27 | 2015-05-07 | 千住金属工業株式会社 | 摺動部材及び摺動部材の製造方法 |
JP6246666B2 (ja) * | 2014-06-11 | 2017-12-13 | 日本発條株式会社 | 積層体の製造方法 |
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JP2006097134A (ja) | 2004-09-17 | 2006-04-13 | Sulzer Metco Ag | スプレー粉 |
JP2008144253A (ja) | 2006-12-13 | 2008-06-26 | Daido Metal Co Ltd | 銅系摺動材料及びその製造方法 |
JP2011219860A (ja) | 2011-02-09 | 2011-11-04 | Jx Nippon Mining & Metals Corp | 電子材料用Cu−Si−Co系合金及びその製造方法 |
JP2018123388A (ja) | 2017-02-02 | 2018-08-09 | トヨタ自動車株式会社 | 耐摩耗部材及びその製造方法 |
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