JP2011168831A - Method for manufacturing iron-nickel alloy plating film having high hardness and low thermal expansion coefficient - Google Patents
Method for manufacturing iron-nickel alloy plating film having high hardness and low thermal expansion coefficient Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 111
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000010419 fine particle Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000009713 electroplating Methods 0.000 claims abstract description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000872 buffer Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 29
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 such as a brightener Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005323 electroforming Methods 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- REEBJQTUIJTGAL-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1 REEBJQTUIJTGAL-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 229940049703 saccharin sodium dihydrate Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AYGJDUHQRFKLBG-UHFFFAOYSA-M sodium;1,1-dioxo-1,2-benzothiazol-3-olate;dihydrate Chemical compound O.O.[Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 AYGJDUHQRFKLBG-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、高硬度及び低熱膨張係数を有する鉄−ニッケル合金めっき皮膜及びその製造方法に関する。 The present invention relates to an iron-nickel alloy plating film having a high hardness and a low thermal expansion coefficient, and a method for producing the same.
鉄−ニッケル合金は、鉄とニッケルの比率を変えることによって、様々な特性が得られることから工業的に広く利用されている。特に、鉄含有率50〜70％程度の鉄−ニッケル合金は、線膨張係数がFeおよびNi単体に比べ小さいことから、低熱膨張材料として半導体リードフレームや光ファイバーのパッケージ部品などの電子通信機器分野を中心に用いられている。 Iron-nickel alloys are widely used industrially because various properties can be obtained by changing the ratio of iron to nickel. In particular, the iron-nickel alloy with an iron content of about 50 to 70% has a smaller coefficient of linear expansion than Fe and Ni alone. Used in the center.
近年、電子通信機器の小型、高機能化に対応した高密度実装が進み、それらに使用される部品の微細化がさらに要求されている。しかしながら、従来のプレスやエッチングなどによる加工方法では、最終製品に用いられる部品の形状や寸法精度に限界が見えつつある。 In recent years, high-density mounting corresponding to miniaturization and high functionality of electronic communication devices has progressed, and further miniaturization of components used for them has been demanded. However, with conventional processing methods such as pressing and etching, there are limits to the shape and dimensional accuracy of the parts used in the final product.
これに対して、ＬＩＧＡプロセスなどの光リソグラフィー技術と電鋳技術を融合させた微細加工方法によれば、高アスペクト比の形状で寸法精度の高い部品の製造が可能となる。例えば、Ni電鋳法によってメタルマスクや微細成型金型が製造されている。さらに、Ni電鋳製品に代えて、より低い線膨張係数を有する鉄−ニッケル合金の電鋳製品を用いることによって、温度変化に対して寸法安定性がより向上すると考えられる。 On the other hand, according to the microfabrication method in which the photolithography technology such as the LIGA process and the electroforming technology are merged, it is possible to manufacture a part with a high aspect ratio and high dimensional accuracy. For example, metal masks and fine molds are manufactured by Ni electroforming. Furthermore, it is considered that the dimensional stability is improved with respect to the temperature change by using an iron-nickel alloy electroformed product having a lower linear expansion coefficient instead of the Ni electroformed product.
このように低熱膨張性を有する鉄−ニッケル合金の電鋳製品については、幅広い利用分野が期待されるが、電気めっきによって形成された鉄−ニッケル合金皮膜は、合金相が溶製合金とは異なるため、そのままでは溶製合金と同等の低熱膨張特性は得られず、低熱膨張特性を発現させるためには、めっき後に600℃程度で熱処理を行うことが必要となる。しかしながら、電気めっきによって形成された鉄−ニッケル合金皮膜については、熱処理を行うと皮膜硬度が大きく低下するために、鉄−ニッケル合金皮膜の有する優れた性能を十分に利用することができない（下記非特許文献１、２参照）。 As described above, a wide application field is expected for the iron-nickel alloy electroformed product having low thermal expansion, but the iron-nickel alloy film formed by electroplating has an alloy phase different from that of the melted alloy. Therefore, the low thermal expansion characteristics equivalent to those of the molten alloy cannot be obtained as they are, and in order to develop the low thermal expansion characteristics, it is necessary to perform heat treatment at about 600 ° C. after plating. However, the iron-nickel alloy film formed by electroplating cannot sufficiently utilize the superior performance of the iron-nickel alloy film because the film hardness greatly decreases when heat treatment is carried out (the following non-characteristic). (See Patent Documents 1 and 2).
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、電気めっき方法で形成される鉄−ニッケル合金めっき皮膜について、熱処理後においても皮膜性能の低下、特に、皮膜硬度の低下が生じ難い新規な鉄−ニッケル合金めっき皮膜の形成方法を提供することである。 The present invention has been made in view of the current state of the prior art described above, and the main purpose of the iron-nickel alloy plating film formed by the electroplating method is to reduce the film performance even after heat treatment. An object of the present invention is to provide a novel method for forming an iron-nickel alloy plating film in which a decrease in film hardness hardly occurs.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、鉄−ニッケル合金めっき液中に平均粒径３μｍ程度以下の微粒子を分散させためっき液を用いて形成された複合鉄−ニッケル合金めっき皮膜は、熱処理を行った場合にも結晶粒の成長が抑制されて、皮膜硬度の低下を抑制できることを見出した。その結果、熱処理後の鉄−ニッケル合金皮膜は、溶製鉄−ニッケル合金と同様の低熱膨張係数を有すると共に、高硬度を有する皮膜となり、温度変化に対する安定性に優れ、高硬度を有する鉄−ニッケル合金として、各種の用途に有効に利用できることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, the composite iron-nickel alloy plating film formed by using a plating solution in which fine particles having an average particle size of about 3 μm or less are dispersed in the iron-nickel alloy plating solution has a crystal grain size even when heat treatment is performed. It has been found that the growth is suppressed and the decrease in film hardness can be suppressed. As a result, the heat-treated iron-nickel alloy film has a low thermal expansion coefficient similar to that of the molten iron-nickel alloy, and has a high hardness, and is excellent in stability against temperature changes and has a high hardness. As an alloy, it has been found that it can be effectively used for various applications, and the present invention has been completed here.
即ち、本発明は、下記の高硬度及び低熱膨張係数を有する鉄−ニッケル合金めっき皮膜及びその製造方法を提供するものである。
１． ニッケル塩、第一鉄塩、錯化剤及び緩衝剤を含む水溶液中に平均粒径３μｍ以下の微粒子を分散させた鉄−ニッケル合金めっき液中で、電気めっき法によって該微粒子が共析した鉄−ニッケル合金めっき皮膜を形成した後、形成されためっき皮膜を４００℃以上の温度で熱処理することを特徴とする、低膨張特性及び高硬度を有する鉄−ニッケル合金めっき皮膜の製造方法。
２． 形成される鉄−ニッケル合金めっき皮膜における鉄とニッケルの比率が、両者の合計量を１００質量％として、鉄が６０〜６８質量％及びニッケルが３２〜４０質量％である上記項１に記載の鉄−ニッケル合金めっき皮膜の製造方法。
３． 形成される鉄−ニッケル合金めっき皮膜における微粒子の含有量が、鉄、ニッケル及び微粒子の合計量を１００質量％として、０．１〜１５質量％である上記項１又は２に記載の鉄−ニッケル合金めっき皮膜の製造方法。
４． 上記項１〜３のいずれかの方法によって形成される低膨張特性及び高硬度を有する鉄−ニッケル合金めっき皮膜。
５． 鉄とニッケルの比率が、両者の合計量を１００質量％として、鉄が６０〜６８質量％及びニッケルが３２〜４０質量％であり、
微粒子の含有量が、鉄、ニッケル及び微粒子の合計量を１００質量％として、０．１〜１５質量％であり、
線膨張係数が６×１０−６／℃以下であり、
ビッカース硬度が１７０ＨＶ以上である、
上記項４に記載の鉄−ニッケル合金めっき皮膜。
６． 微粒子が共析した鉄−ニッケル合金めっき皮膜を４００℃以上の温度で熱処理することを特徴とする、低膨張特性及び高硬度を有する鉄−ニッケル合金めっき皮膜の製造方法であって、
該鉄−ニッケル合金めっき皮膜における鉄とニッケルの比率が、両者の合計量を１００質量％として、鉄が６０〜６８質量％及びニッケルが３２〜４０質量％であり、
該鉄−ニッケル合金めっき皮膜における微粒子の含有量が、鉄、ニッケル及び微粒子の合計量を１００質量％として、０．１〜１５質量％である、
ことを特徴とする方法。
That is, this invention provides the iron-nickel alloy plating film which has the following high hardness and a low thermal expansion coefficient, and its manufacturing method.
1. Iron in which the fine particles are co-deposited by electroplating in an iron-nickel alloy plating solution in which fine particles having an average particle size of 3 μm or less are dispersed in an aqueous solution containing a nickel salt, a ferrous salt, a complexing agent and a buffer. A method for producing an iron-nickel alloy plating film having low expansion characteristics and high hardness, characterized in that after the nickel alloy plating film is formed, the formed plating film is heat-treated at a temperature of 400 ° C or higher.
2. Item 2. The ratio of iron to nickel in the formed iron-nickel alloy plating film, wherein the total amount of both is 100% by mass, iron is 60 to 68% by mass, and nickel is 32 to 40% by mass. A method for producing an iron-nickel alloy plating film.
3. The iron-nickel according to item 1 or 2, wherein the content of fine particles in the formed iron-nickel alloy plating film is 0.1 to 15% by mass, where the total amount of iron, nickel and fine particles is 100% by mass. A method for producing an alloy plating film.
4). The iron-nickel alloy plating film which has the low expansion characteristic and high hardness formed by the method in any one of said item | item 1-3.
5. The ratio of iron and nickel is 60 to 68% by mass of iron and 32 to 40% by mass of nickel, with the total amount of both being 100% by mass,
The content of fine particles is 0.1 to 15% by mass, where the total amount of iron, nickel and fine particles is 100% by mass,
The linear expansion coefficient is 6 × 10 −6 / ° C. or less,
Vickers hardness is 170HV or more,
Item 5. The iron-nickel alloy plating film according to Item 4.
6). A method for producing an iron-nickel alloy plating film having low expansion characteristics and high hardness, characterized by heat-treating an iron-nickel alloy plating film in which fine particles are co-deposited at a temperature of 400 ° C. or more,
The ratio of iron and nickel in the iron-nickel alloy plating film is 60 to 68% by mass of iron and 32 to 40% by mass of nickel, with the total amount of both being 100% by mass,
The content of fine particles in the iron-nickel alloy plating film is 0.1 to 15% by mass, where the total amount of iron, nickel and fine particles is 100% by mass,
A method characterized by that.
鉄−ニッケル合金めっき浴
本発明では、基本となる鉄−ニッケル合金めっき浴としては、特に限定はなく、公知の鉄−ニッケル合金めっき浴を用いることができる。このようなめっき浴は、通常、第一鉄塩、ニッケル塩、錯化剤及び緩衝剤を含むものである。
Iron-Nickel Alloy Plating Bath In the present invention, the basic iron-nickel alloy plating bath is not particularly limited, and a known iron-nickel alloy plating bath can be used. Such plating baths usually contain ferrous salts, nickel salts, complexing agents and buffering agents.
第一鉄塩の具体例としては、硫酸第一鉄、塩化第一鉄，スルファミン酸第一鉄等を例示できる。ニッケル塩の具体例としては、硫酸ニッケル、塩化ニッケル、炭酸ニッケル、酢酸ニッケル、スルファミン酸ニッケル、メタンスルフォン酸ニッケル等を挙げることができる。錯化剤の具体例としては、マロン酸、酒石酸、コハク酸、クエン酸、リンゴ酸等の有機酸、これらの有機酸の水溶性塩、例えば、ナトリウム塩、カリウム塩、アンモニウム塩等を挙げることができる。これらの内で、特に、マロン酸、酒石酸、これらの水溶性塩を用いることが特に好ましい。緩衝剤の具体例としては、ホウ酸、酢酸、クエン酸等を挙げることができる。 Specific examples of the ferrous salt include ferrous sulfate, ferrous chloride, ferrous sulfamate and the like. Specific examples of the nickel salt include nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, nickel sulfamate, nickel methanesulfonate, and the like. Specific examples of complexing agents include organic acids such as malonic acid, tartaric acid, succinic acid, citric acid, malic acid, and water-soluble salts of these organic acids, such as sodium salts, potassium salts, ammonium salts, etc. Can do. Of these, it is particularly preferable to use malonic acid, tartaric acid, and water-soluble salts thereof. Specific examples of the buffer include boric acid, acetic acid, citric acid and the like.
鉄−ニッケル合金めっき浴における各成分の具体的な配合量については、使用する成分の種類によって異なるが、後述する目的とする組成の鉄−ニッケルめっき皮膜が形成されるように公知の配合量に基づいて決めればよい。 About the specific compounding quantity of each component in an iron-nickel alloy plating bath, although it changes with kinds of component to be used, it becomes a well-known compounding quantity so that the iron-nickel plating film of the target composition mentioned later may be formed. You can decide based on it.
更に、鉄−ニッケル合金めっき浴には、必要に応じて、光沢剤、界面活性剤、酸化防止剤等の公知の添加剤を加えることができる。これらの内で、光沢剤としては、サッカリンナトリウム、ナフタレンスルホン酸ナトリウム、アリルスルホン酸ナトリウム、ビニルスルホン酸ナトリウム、ブチンジオール、プロパギルアルコール、アセチレン系化合物、ピリジニウムプロピルスルホベタイン等を例示できる。界面活性剤としては、硫酸エステル系、アルキルスルホン酸系、スルホコハク酸エステル系等の界面活性剤を例示できる。酸化防止剤としては、アスコルビン酸、イソアスコルビン酸等を例示できる。 Furthermore, well-known additives, such as a brightener, surfactant, antioxidant, can be added to an iron-nickel alloy plating bath as needed. Among these, examples of the brightener include saccharin sodium, sodium naphthalene sulfonate, sodium allyl sulfonate, sodium vinyl sulfonate, butynediol, propargyl alcohol, acetylene compounds, pyridinium propyl sulfobetaine and the like. Examples of the surfactant include sulfate ester-based, alkyl sulfonate-based, sulfosuccinate-based surfactants and the like. Examples of the antioxidant include ascorbic acid and isoascorbic acid.
以下、本発明に適用できる鉄−ニッケル合金めっき浴の好ましい組成範囲及びめっき条件を記載する。 Hereinafter, the preferable composition range and plating conditions of the iron-nickel alloy plating bath applicable to the present invention will be described.
硫酸ニッケル〔NiSO4・6H2O〕 150〜300g/L
塩化ニッケル〔NiCl2・6H2O〕 30〜70g/L
ホウ酸 〔H3BO3〕 30〜45g/L
硫酸第一鉄 〔FeSO4・7H2O〕 3.4〜139g/L
サッカリンナトリウム2水和物 0.5〜6g/L
マロン酸 1〜10g/L
pH 2〜3
浴温 40〜60℃
陰極電流密度 2〜8A/dm2
本発明では、上記した鉄−ニッケル合金めっき浴に対して、平均粒径３μｍ以下、好ましくは平均粒径１μｍ以下の微粒子を分散させためっき浴を用いて、該微粒子が共析した鉄−ニッケル合金めっき皮膜を形成することが必要である。微粒子の平均粒径の下限値については特に限定的ではないが、例えば、０．００５μｍ程度以上の粒径のものを用いることができる。
Nickel sulfate (NiSO 4・ 6H 2 O) 150 ~ 300g / L
Nickel chloride [NiCl 2・ 6H 2 O] 30 ~ 70g / L
Boric acid [H 3 BO 3 ] 30-45 g / L
Ferrous sulfate [FeSO 4・ 7H 2 O] 3.4 ~ 139g / L
Saccharin sodium dihydrate 0.5-6g / L
Malonic acid 1-10g / L
pH 2-3
Bath temperature 40-60 ° C
Cathode current density 2 ~ 8A / dm 2
In the present invention, an iron-nickel alloy in which the fine particles are co-deposited by using a plating bath in which fine particles having an average particle size of 3 μm or less, preferably an average particle size of 1 μm or less, are dispersed with respect to the iron-nickel alloy plating bath described above. It is necessary to form an alloy plating film. The lower limit value of the average particle size of the fine particles is not particularly limited, but for example, particles having a particle size of about 0.005 μm or more can be used.
平均粒径３μｍ以下の微粒子としては、後述する熱処理の際に、分解、溶解などが生じることなく、その形状を維持できるものであればよい。例えば、ダイヤモンド、窒化ホウ素、窒化ケイ素、炭化ケイ素、シリカ、アルミナなどを用いることができる。これらの内で、例えば、炭化ケイ素は、後述する熱処理後の鉄−ニッケル合金めっき皮膜の熱膨張率に近い熱膨張率を有するので、温度変化に対して寸法安定性に優れた鉄−ニッケル合金めっき皮膜を形成するためには、特に有効である。 The fine particles having an average particle size of 3 μm or less may be any fine particles that can maintain their shapes without being decomposed or dissolved during the heat treatment described later. For example, diamond, boron nitride, silicon nitride, silicon carbide, silica, alumina, or the like can be used. Among these, for example, silicon carbide has a thermal expansion coefficient close to that of an iron-nickel alloy plating film after heat treatment, which will be described later. Therefore, an iron-nickel alloy having excellent dimensional stability against temperature changes. This is particularly effective for forming a plating film.
尚、該微粒子の平均粒径は、倍率５０００倍の顕微鏡で複数の視野を観察して、視野範囲内の任意に選択した１００個の微粒子の粒径の平均値である。この場合、非球形の粒子については、長径の長さを粒径とする。 The average particle diameter of the fine particles is an average value of the particle diameters of 100 fine particles arbitrarily selected within a visual field range by observing a plurality of visual fields with a microscope having a magnification of 5000 times. In this case, for the non-spherical particles, the length of the major axis is defined as the particle size.
鉄−ニッケル合金めっき浴中の微粒子の配合量は、形成される鉄−ニッケル合金めっき皮膜中に共析する微粒子量によって決めればよく、通常、１〜４０g/L程度の範囲内とすればよい。 The blending amount of the fine particles in the iron-nickel alloy plating bath may be determined by the amount of fine particles co-deposited in the formed iron-nickel alloy plating film, and is usually within a range of about 1 to 40 g / L. .
鉄−ニッケル合金めっき皮膜の形成方法
上記した微粒子を分散させた鉄−ニッケル合金めっき浴を用いて、微粒子が共析した複合めっき皮膜を形成する方法としては、該合金めっき浴を撹拌して該微粒子を均一に分散させた状態において通電して、電気めっきを行えばよい。具体的なめっき条件については、使用する鉄−ニッケル合金めっき浴の種類に応じて、通常のめっき条件の範囲内から適宜決めればよい。めっき浴を撹拌する方法については、特に限定はなく、例えば、機械的撹拌法、空気撹拌法などを採用して、めっき浴中に添加した微粒子が均一に分散されるように撹拌すればよく、特に、第一鉄塩の酸化を防止するために、機械撹拌法が好ましい。
Method of forming iron-nickel alloy plating film As a method of forming a composite plating film in which fine particles are co-deposited using the iron-nickel alloy plating bath in which the fine particles are dispersed, the alloy plating bath is stirred to Electroplating may be performed by energizing in a state where fine particles are uniformly dispersed. Specific plating conditions may be appropriately determined from the range of normal plating conditions depending on the type of iron-nickel alloy plating bath to be used. The method for stirring the plating bath is not particularly limited. For example, a mechanical stirring method, an air stirring method, or the like may be adopted, and stirring may be performed so that the fine particles added in the plating bath are uniformly dispersed. In particular, a mechanical stirring method is preferable in order to prevent oxidation of the ferrous salt.
本発明の高硬度及び低熱膨張係数を有する鉄−ニッケル合金めっき皮膜の製造方法では、上記した方法で微粒子が共析した鉄−ニッケル合金めっき皮膜を形成した後、熱処理を行うことが必要である。一般に、電気めっき法によって形成される鉄−ニッケル合金めっき皮膜は、めっき直後には、ｆｃｃ相とｂｃｃ相が存在する2相合金であり、十分な低熱膨張特性を発現できないが、熱処理を施すことによって、ｆｃｃ相の単相合金となり、熱膨張係数が大きく低下する。この際、通常の鉄−ニッケル合金めっき皮膜では、結晶粒が粗大化して皮膜の軟化が起こり溶製合金より低い硬度となる。これに対して、本発明方法によって形成される微粒子が共析した鉄−ニッケル合金めっき皮膜では、熱処理を行う際に、硬度の低下が大きく抑制される。この理由については明確ではないが、本発明の方法で形成される鉄−ニッケル合金めっき皮膜では、皮膜中に微粒子が点在しており、これによって熱処理の際に結晶粒の粗大化が抑制されるため、硬度低下が起こり難くなると考えられる。 In the method for producing an iron-nickel alloy plating film having a high hardness and a low thermal expansion coefficient according to the present invention, it is necessary to perform a heat treatment after forming the iron-nickel alloy plating film in which fine particles are co-deposited by the above-described method. . Generally, an iron-nickel alloy plating film formed by an electroplating method is a two-phase alloy in which an fcc phase and a bcc phase exist immediately after plating, and cannot exhibit sufficient low thermal expansion characteristics, but is subjected to heat treatment. Thus, an fcc phase single-phase alloy is obtained, and the thermal expansion coefficient is greatly reduced. At this time, in an ordinary iron-nickel alloy plating film, the crystal grains become coarse and the film softens, resulting in a lower hardness than that of the melted alloy. On the other hand, in the iron-nickel alloy plating film in which fine particles formed by the method of the present invention are co-deposited, a decrease in hardness is greatly suppressed when heat treatment is performed. Although the reason for this is not clear, in the iron-nickel alloy plating film formed by the method of the present invention, fine particles are scattered in the film, which suppresses the coarsening of crystal grains during heat treatment. For this reason, it is considered that the hardness is unlikely to decrease.
熱処理温度については、通常、４００℃程度以上とすればよく、６００℃以上とすることが好ましい。熱処理温度の上限については特に限定的ではなく、めっき皮膜中に含まれる微粒子が分解、溶融などを生じない温度であればよいが、過度に高温とすることは経済的に不利である。通常、８００℃程度以下とすればよい。 About heat processing temperature, what is necessary is just normally about 400 degreeC or more, and it is preferable to set it as 600 degreeC or more. The upper limit of the heat treatment temperature is not particularly limited as long as the fine particles contained in the plating film do not decompose or melt, but it is economically disadvantageous to have an excessively high temperature. Usually, the temperature may be about 800 ° C. or lower.
熱処理の雰囲気については、特に限定的ではないが、めっき皮膜の酸化による変質を避けるためには、不活性ガス雰囲気、還元性雰囲気などの非酸化性雰囲気とすることが好ましい。 The atmosphere for the heat treatment is not particularly limited, but in order to avoid alteration due to oxidation of the plating film, a non-oxidizing atmosphere such as an inert gas atmosphere or a reducing atmosphere is preferable.
熱処理時間については特に限定的ではなく、めっき皮膜の膜厚などによって異なるが、通常、３分〜１時間程度の範囲とすればよい。 The heat treatment time is not particularly limited, and varies depending on the film thickness of the plating film, but is usually in the range of about 3 minutes to 1 hour.
鉄−ニッケル合金めっき皮膜
上記した方法で熱処理を行って得られる鉄−ニッケル合金めっき皮膜は、熱処理によって膨張係数が低下して低膨張特性を有するものとなる。更に、熱処理の際に、硬度の低下が抑制されており、高硬度及び低熱膨張係数を有する鉄−ニッケル合金めっき皮膜となる。
Iron-nickel alloy plating film The iron-nickel alloy plating film obtained by performing the heat treatment by the above-described method has a low expansion characteristic due to a decrease in expansion coefficient due to the heat treatment. Further, during the heat treatment, a decrease in hardness is suppressed, and an iron-nickel alloy plating film having a high hardness and a low thermal expansion coefficient is obtained.
鉄−ニッケル合金めっき皮膜の組成については、特に限定的ではないが、特に、鉄とニッケルの合計を１００質量％として、鉄６０〜６８質量％及びニッケル３２〜４０質量％程度の範囲の組成の鉄−ニッケル合金は、熱処理によって膨張係数が大きく低下する点で好ましい。 The composition of the iron-nickel alloy plating film is not particularly limited. Particularly, the composition is in the range of about 60 to 68% by mass of iron and 32 to 40% by mass of nickel, where the total of iron and nickel is 100% by mass. An iron-nickel alloy is preferable in that the expansion coefficient is greatly reduced by heat treatment.
鉄−ニッケル合金めっき皮膜中に共析する微粒子の比率についても特に限定的ではないが、熱処理による硬度の低下を抑制するためには、鉄、ニッケル及び微粒子の合計量を１００質量％として、微粒子量を０．１〜１５質量％程度とすることが好ましく、１〜１２質量％程度とすることがより好ましい。微粒子の量が少なすぎる場合には、硬度低下を抑制する効果が十分には発現されず、一方、微粒子の量が多すぎると、めっき皮膜自体の性能の低下が生じることがあるので、好ましくない。 The ratio of fine particles that are eutectoid in the iron-nickel alloy plating film is not particularly limited, but in order to suppress a decrease in hardness due to heat treatment, the total amount of iron, nickel, and fine particles is set to 100% by mass. The amount is preferably about 0.1 to 15% by mass, and more preferably about 1 to 12% by mass. If the amount of the fine particles is too small, the effect of suppressing the decrease in hardness is not sufficiently exhibited. On the other hand, if the amount of the fine particles is too large, the performance of the plating film itself may be deteriorated, which is not preferable. .
熱処理後の鉄−ニッケル合金めっき皮膜の熱膨張係数については、形成されるめっき皮膜の組成、熱処理温度等によって異なるが、好ましい組成範囲であるＦｅ：Ｎｉ（質量％）＝６０〜６８：３２：４０の範囲の鉄−ニッケル合金を４００℃程度以上の温度で熱処理した場合には、６×１０−６／℃程度以下という低い線膨張係数を有するものとなる。 The thermal expansion coefficient of the iron-nickel alloy plating film after the heat treatment varies depending on the composition of the plating film to be formed, the heat treatment temperature, and the like, but a preferable composition range is Fe: Ni (mass%) = 60 to 68:32: When an iron-nickel alloy in the range of 40 is heat-treated at a temperature of about 400 ° C. or higher, it has a low linear expansion coefficient of about 6 × 10 −6 / ° C. or lower.
また、熱処理後のめっき皮膜の硬度については、熱処理の際の硬度の低下が大きく抑制されており、ビッカース硬度として１７０ＨＶ程度以上の高い硬度を有するものとなる。 Moreover, about the hardness of the plating film after heat processing, the fall of the hardness in the case of heat processing is suppressed greatly, and it has a high hardness about 170HV or more as Vickers hardness.
鉄−ニッケル合金めっき皮膜の膜厚については特に限定的ではなく、通電時間を調整することによって任意の膜厚のめっき皮膜を形成できる。例えば、２００μｍ程度以上の厚膜の鉄−ニッケル合金めっき皮膜であっても、クラックなどの異常を生じることなく、容易に形成することができる。 The film thickness of the iron-nickel alloy plating film is not particularly limited, and a plating film having an arbitrary film thickness can be formed by adjusting the energization time. For example, even a thick iron-nickel alloy plating film having a thickness of about 200 μm or more can be easily formed without causing abnormalities such as cracks.
本発明の鉄−ニッケル合金めっき皮膜の製造方法によれば、電気めっき法によって形成された鉄−ニッケル合金めっき皮膜について、熱膨張係数を低下させるための熱処理を行う場合にも、硬度の低下が大きく抑制されて、実用上望ましい高硬度を維持することができる。 According to the method for producing an iron-nickel alloy plating film of the present invention, even when a heat treatment for reducing the thermal expansion coefficient is performed on an iron-nickel alloy plating film formed by electroplating, the hardness is reduced. It is greatly suppressed and the high hardness desirable in practice can be maintained.
このため、本発明方法を適用することによって、温度変化に対して寸法安定性がよく、高硬度を有する鉄−ニッケル合金めっき皮膜を形成することが可能となる。 For this reason, by applying the method of the present invention, it is possible to form an iron-nickel alloy plating film having good dimensional stability against temperature changes and high hardness.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
硫酸ニッケル250g/L、塩化ニッケル40g/L、ホウ酸30g/L、硫酸第一鉄97.3g/L、サッカリンナトリウム2水和物2g/L、及びマロン酸5.2g/Lを含有するｐＨ2．5の水溶液からなる鉄−ニッケル合金めっき浴に、平均粒径0.5μmの炭化ケイ素15g/Lを添加しためっき浴を用い、被めっき物としてステンレス板を用いて、機械撹拌下で、浴温50℃、陰極電流密度4A/dm2で5時間のめっきを行った。
Example 1
PH 2.5 containing nickel sulfate 250 g / L, nickel chloride 40 g / L, boric acid 30 g / L, ferrous sulfate 97.3 g / L, sodium saccharin dihydrate 2 g / L, and malonic acid 5.2 g / L An iron-nickel alloy plating bath made of an aqueous solution, using a plating bath to which 15 g / L of silicon carbide having an average particle size of 0.5 μm is added, using a stainless steel plate as the object to be plated, under mechanical stirring, a bath temperature of 50 ° C., Plating was performed at a cathode current density of 4 A / dm 2 for 5 hours.
形成されためっき皮膜は、膜厚が約200μmであり、線膨張係数が10.7×10-6／℃、硬度がHV245であった。 The formed plating film had a film thickness of about 200 μm, a linear expansion coefficient of 10.7 × 10 −6 / ° C., and a hardness of HV245.
このめっき皮膜について、約５ｍＰａの真空雰囲気下において、600℃、1時間の熱処理を行った。熱処理後のめっき皮膜の線膨張係数は、1.1×10-6／℃と大きく減少しており、溶製（６４質量％鉄−３６質量％ニッケル）合金の値とほぼ同等となった。また、熱処理後のめっき皮膜の硬度はHV196であり、高硬度が維持されていた。 This plating film was heat-treated at 600 ° C. for 1 hour in a vacuum atmosphere of about 5 mPa. The linear expansion coefficient of the plated film after the heat treatment was greatly reduced to 1.1 × 10 −6 / ° C., which was almost the same as that of the melted (64 mass% iron-36 mass% nickel) alloy. Further, the hardness of the plating film after the heat treatment was HV196, and high hardness was maintained.
尚、めっき皮膜の組成は、蛍光Ｘ線分析法によって測定し、めっき皮膜の硬度は、マイクロビッカース硬度計（荷重０．４９N）を用いて室温で測定した。また、線膨張係数については、短冊形状（５ｍｍ×２０ｍｍ×０．１ｍｍ）の試料を用いて測定した熱膨張曲線から３０〜１００℃の範囲で求めた。熱膨張測定は、試料の伸びの検出に差動トランスを用いた示差熱膨張計を用い、Ｎ２雰囲気、昇温速度５℃／ｍｉｎで行った。 The composition of the plating film was measured by fluorescent X-ray analysis, and the hardness of the plating film was measured at room temperature using a micro Vickers hardness meter (load 0.49 N). Moreover, about the linear expansion coefficient, it calculated | required in the range of 30-100 degreeC from the thermal expansion curve measured using the strip-shaped (5 mm x 20 mmx0.1mm) sample. The thermal expansion was measured by using a differential thermal dilatometer using a differential transformer for detecting the elongation of the sample, in an N 2 atmosphere and at a heating rate of 5 ° C./min.
実施例２〜１０及び比較例１
下記表１に示す浴Ｉ又は浴IIの鉄−ニッケル合金めっき浴を用い、これに、微粒子として、炭化ケイ素（ＳｉＣ）又は酸化ケイ素（ＳｉＯ２）を添加して、微粒子を分散した鉄−ニッケル合金めっき浴を調製した。
Examples 2 to 10 and Comparative Example 1
The iron-nickel alloy plating bath of bath I or bath II shown in Table 1 below is used, and silicon carbide (SiC) or silicon oxide (SiO 2 ) is added as fine particles to the iron-nickel in which the fine particles are dispersed. An alloy plating bath was prepared.
これらのめっき浴を用い、被めっき物としてステンレス板を用いて、下記表２に示す微粒子の添加量及び電解条件で、微粒子が共析した鉄−ニッケル合金めっき皮膜を形成した。その後、実施例１と同様にして、600℃で１時間の熱処理を行った。 Using these plating baths, an iron-nickel alloy plating film in which fine particles were co-deposited was formed using a stainless steel plate as an object to be plated with the addition amount of fine particles and electrolytic conditions shown in Table 2 below. Thereafter, in the same manner as in Example 1, heat treatment was performed at 600 ° C. for 1 hour.
下記表３に、形成されためっき皮膜の膜厚、合金比及び微粒子の共析量を示し、更に、熱処理前と熱処理後の硬度と線膨張係数を示す。 Table 3 below shows the film thickness of the formed plating film, the alloy ratio, and the amount of eutectoid of fine particles, and further shows the hardness and linear expansion coefficient before and after heat treatment.
以上の結果から明らかなように、微粒子を分散させた鉄−ニッケル合金めっき浴から形成されるめっき皮膜は、熱処理を行うことによって、高硬度を維持したままで、線膨張係数を大きく低減することができる。これに対して、微粒子を含まないめっき皮膜から形成された比較例１の鉄−ニッケル合金めっき皮膜については、熱処理によって熱膨張係数が低下するが、めっき皮膜の硬度も大きく低下することが判る。 As is clear from the above results, the plating film formed from the iron-nickel alloy plating bath in which fine particles are dispersed greatly reduces the linear expansion coefficient while maintaining high hardness by performing heat treatment. Can do. On the other hand, it can be seen that the thermal expansion coefficient of the iron-nickel alloy plating film of Comparative Example 1 formed from a plating film containing no fine particles is reduced by heat treatment, but the hardness of the plating film is also greatly reduced.
Claims (6)
微粒子の含有量が、鉄、ニッケル及び微粒子の合計量を１００質量％として、０．１〜１５質量％であり、
線膨張係数が６×１０−６／℃以下であり、
ビッカース硬度が１７０ＨＶ以上である、
請求項４に記載の鉄−ニッケル合金めっき皮膜。 The ratio of iron and nickel is 60 to 68% by mass of iron and 32 to 40% by mass of nickel, with the total amount of both being 100% by mass,
The content of fine particles is 0.1 to 15% by mass, where the total amount of iron, nickel and fine particles is 100% by mass,
The linear expansion coefficient is 6 × 10 −6 / ° C. or less,
Vickers hardness is 170HV or more,
The iron-nickel alloy plating film according to claim 4.
該鉄−ニッケル合金めっき皮膜における鉄とニッケルの比率が、両者の合計量を１００質量％として、鉄が６０〜６８質量％及びニッケルが３２〜４０質量％であり、
該鉄−ニッケル合金めっき皮膜における微粒子の含有量が、鉄、ニッケル及び微粒子の合計量を１００質量％として、０．１〜１５質量％である、
ことを特徴とする方法。 A method for producing an iron-nickel alloy plating film having low expansion characteristics and high hardness, characterized by heat-treating an iron-nickel alloy plating film in which fine particles are co-deposited at a temperature of 400 ° C. or more,
The ratio of iron and nickel in the iron-nickel alloy plating film is 60 to 68% by mass of iron and 32 to 40% by mass of nickel, with the total amount of both being 100% by mass,
The content of fine particles in the iron-nickel alloy plating film is 0.1 to 15% by mass, where the total amount of iron, nickel and fine particles is 100% by mass,
A method characterized by that.
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