JP5561920B2 - Al-containing copper alloy coated steel and method for producing the same - Google Patents
Al-containing copper alloy coated steel and method for producing the same Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims description 65
- 239000010959 steel Substances 0.000 title claims description 65
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000463 material Substances 0.000 claims description 71
- 239000010949 copper Substances 0.000 claims description 60
- 238000007747 plating Methods 0.000 claims description 56
- 238000009792 diffusion process Methods 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000002436 steel type Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910017767 Cu—Al Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Description
本発明は、表面にＡｌ含有銅合金被覆層を有する鋼材およびその製造方法に関する。 The present invention relates to a steel material having an Al-containing copper alloy coating layer on the surface and a method for producing the same.
Ａｌを含有する銅合金は従来よりアルミニウム青銅として知られており、例えばＪＩＳ Ｈ３１００には合金番号Ｃ６１４０、Ｃ６１６１、Ｃ６２８０、Ｃ６３０１の各種Ｃｕ−Ａｌ系合金が規定されている。Ａｌ含有銅合金は耐食性、耐海水性、耐高温酸化性、耐摩耗性等に優れることから、車両用、機械用、化学工業用、船舶用等のギヤーピニオン、シャフト、ブッシュといった様々な用途に使用されている。 A copper alloy containing Al is conventionally known as aluminum bronze. For example, JIS H3100 defines various Cu-Al alloys of alloy numbers C6140, C6161, C6280, and C6301. Al-containing copper alloy is excellent in corrosion resistance, seawater resistance, high temperature oxidation resistance, wear resistance, etc., so it can be used in various applications such as gear pinions, shafts, bushes for vehicles, machinery, chemical industry, and ships. It is used.
しかし近年、銅原料価格の高騰が銅合金の価格上昇を招いており、相場の変動に伴う銅合金価格の不安定さも問題となっている。また銅合金は一般的に強靱性の点で鋼材に劣り、機械部品などでは更なる高強度化が望まれる場合も多い。このような状況において、Ａｌ含有銅合金の上記長所を具備したまま、より強靱性に優れ、かつ安価な材料の出現が望まれるところである。 However, in recent years, the rise in the price of copper raw materials has led to an increase in the price of copper alloys, and the instability of copper alloy prices accompanying fluctuations in market prices has also become a problem. Copper alloys are generally inferior to steel materials in terms of toughness, and mechanical parts are often required to have higher strength. Under such circumstances, it is desired to develop a material that is superior in toughness and inexpensive while maintaining the above-mentioned advantages of the Al-containing copper alloy.
Ａｌ含有銅合金の長所を具備した強靱な材料として、芯材に鋼材を用い、その表層にＣｕ−Ａｌ合金を設けた複合材料を採用することが有効であると考えられる。しかしながら、現状においてそのような複合材料を生産性良く安価に製造する技術は確立されていない。 As a tough material having the advantages of an Al-containing copper alloy, it is considered effective to employ a composite material in which a steel material is used as a core material and a Cu—Al alloy is provided on the surface layer. However, at present, a technique for manufacturing such a composite material with high productivity and low cost has not been established.
例えば特許文献１には、Ａｌを含有する銅合金皮膜を金属やセラミックスの表面に形成する技術が記載されている。しかし、これは真空蒸着法、イオンプレーティング法、スパッタリング法などのドライめっき法によるものであり、成膜速度が遅いことから生産性に劣る。同文献にはＣｕめっき上にＡｌめっき皮膜を形成したのち熱拡散によって合金化する方法も記載されているが、Ａｌは標準電極電位が低いため水溶性電解液からの電気めっきが不可能であり、特殊有機溶媒浴あるいは溶融塩浴を用いる必要がある。このような非水系の浴を使用した電気めっきは厳密な浴管理が必要となりコスト的に大量生産化は難しい。 For example, Patent Document 1 describes a technique for forming a copper alloy film containing Al on a metal or ceramic surface. However, this is due to a dry plating method such as a vacuum deposition method, an ion plating method, or a sputtering method, and is inferior in productivity because the film forming speed is low. The same document also describes a method in which an Al plating film is formed on Cu plating and then alloyed by thermal diffusion. However, since Al has a low standard electrode potential, electroplating from a water-soluble electrolyte is impossible. It is necessary to use a special organic solvent bath or a molten salt bath. Electroplating using such a non-aqueous bath requires strict bath management and is difficult to mass-produce in terms of cost.
特許文献２には、Ａｌ、Ｃｕ、Ｎｉなどの金属層で被覆されたステンレス鋼ストリップを、電子ビーム蒸着法を用いて製造する方法が提案されている。しかし、この手法もドライめっきの欠点である生産性の低さによりコスト上昇は免れない。 Patent Document 2 proposes a method of manufacturing a stainless steel strip coated with a metal layer such as Al, Cu, or Ni by using an electron beam evaporation method. However, this method is also unavoidable due to low productivity, which is a disadvantage of dry plating.
また、従来から一般的に知られている鋼材表面への異種金属の被覆方法として、合金箔を圧延（熱間、温間または冷間）によりクラッディングする方法、合金粉末のペーストを鋼材表面に塗布したのち焼結させる方法、溶融した合金を鋼材表面に溶射する方法などがある。しかし、これらの方法は皮膜密着性や生産性の面で問題があり、品質の良い銅合金被覆鋼材を安定的に低コストで製造することは難しい。 In addition, conventionally known methods for coating dissimilar metals on the surface of steel materials include a method of cladding an alloy foil by rolling (hot, warm or cold), and a paste of alloy powder on the surface of the steel material. There are a method of sintering after coating, a method of spraying a molten alloy on the surface of a steel material, and the like. However, these methods have problems in terms of film adhesion and productivity, and it is difficult to stably produce a high-quality copper alloy-coated steel material at a low cost.
本発明は、Ａｌを含有する銅合金の表面特性（耐食性や耐摩耗性）を有し、工業的に生産性良く製造することができる金属材料を提供しようというものである。 The present invention is intended to provide a metal material that has the surface characteristics (corrosion resistance and wear resistance) of a copper alloy containing Al and can be manufactured industrially with high productivity.
上記目的は、平均厚さ０.５〜１００μｍ、Ａｌ含有量１〜１５質量％の銅合金層を鋼材表面に有するＡｌ含有銅合金被覆鋼材によって達成される。その銅合金層は例えば、Ａｌ含有鋼にＣｕめっきを施したＣｕめっき鋼材において、鋼中に存在するＡｌが、Ｃｕめっき層側に加熱拡散することにより形成されたものである。銅合金層の組成としては、質量％でＡｌ：１〜１５％を含有し、Ｎｉ：７％以下、Ｆｅ：６％以下、Ｃｒ：２％以下、Ｍｎ：２％以下の１種以上を含有し、残部Ｃｕおよび不可避的不純物であるものが挙げられる。 The above object is achieved by an Al-containing copper alloy-coated steel material having a copper alloy layer having an average thickness of 0.5 to 100 μm and an Al content of 1 to 15% by mass on the surface of the steel material. The copper alloy layer is formed by, for example, Cu-plated steel material obtained by performing Cu plating on Al-containing steel by heat diffusion of Al present in the steel to the Cu plating layer side. The composition of the copper alloy layer includes Al: 1 to 15% by mass, Ni: 7% or less, Fe: 6% or less, Cr: 2% or less, and Mn: 2% or less. And the remainder Cu and inevitable impurities.
また本発明では、Ａｌ含有量１〜２０質量％の鋼材を基材として、その表面にＣｕめっき層を形成したＣｕめっき鋼材を、非酸化性雰囲気中６００〜１０５０℃に加熱保持することにより、基材中のＡｌがＣｕめっき層側に拡散する現象を利用して鋼材表面にＡｌ含有量１質量％以上の銅合金層を形成させるＡｌ含有銅合金被覆鋼材の製造方法が提供される。 In the present invention, by using a steel material having an Al content of 1 to 20% by mass as a base material, a Cu plated steel material having a Cu plating layer formed on the surface thereof is heated and held at 600 to 1050 ° C. in a non-oxidizing atmosphere. There is provided a method for producing an Al-containing copper alloy-coated steel material in which a copper alloy layer having an Al content of 1% by mass or more is formed on the steel material surface by utilizing a phenomenon in which Al in the base material diffuses toward the Cu plating layer.
前記の基材としては、質量％で、Ｃ：１％以下、Ａｌ：１〜２０％を含有し、その他の合金成分として、Ｓｉ：３％以下、Ｍｎ：５％以下、Ｐ：０.１％以下、Ｓ：０.０３％以下、Ｃｒ：３５％以下、Ｎｉ：２４％以下、Ｍｏ：５％以下、Ｃｕ：６％以下、Ｔｉ：１％以下、Ｎｂ：１％以下、Ｖ：１％以下、Ｎ：０.５％以下、Ｂ：１％以下、Ｃａ：０.１％以下、Ｍｇ：０.１％以下、Ｙ：０.１％以下、ＲＥＭ（希土類元素）：０.１％以下の１種以上を含有し、残部がＦｅおよび不可避的不純物からなる鋼を採用することができる。 As said base material, it contains C: 1% or less, Al: 1-20% by mass%, As other alloy components, Si: 3% or less, Mn: 5% or less, P: 0.1 %: S: 0.03% or less, Cr: 35% or less, Ni: 24% or less, Mo: 5% or less, Cu: 6% or less, Ti: 1% or less, Nb: 1% or less, V: 1 %: N: 0.5% or less, B: 1% or less, Ca: 0.1% or less, Mg: 0.1% or less, Y: 0.1% or less, REM (rare earth element): 0.1 It is possible to employ steel that contains one or more elements of not more than% and the balance being Fe and inevitable impurities.
特にフェライト系ステンレス鋼等の高Ｃｒフェライト系鋼種を基材として採用する場合には、質量％で、Ｃ：０.１％以下、Ｃｒ：９〜３２％、Ａｌ：１〜６％であり、その他の合金成分として、Ｓｉ：１％以下、Ｍｎ：１％以下、Ｐ：０.０４％以下、Ｓ：０.０３％以下、Ｎｉ：０.６％以下、Ｍｏ：５％以下、Ｃｕ：３.５％以下、Ｔｉ：０.８％以下、Ｎｂ：０.８％以下、Ｖ：１％以下、Ｎ：０.０２５％以下、Ｂ：０.１％以下、Ｃａ：０.１％以下、Ｍｇ：０.１％以下、Ｙ：０.１％以下、ＲＥＭ（希土類元素）：０.１％以下の１種以上を含有し、残部がＦｅおよび不可避的不純物からなるフェライト系鋼種を採用することができる。 In particular, when a high Cr ferritic steel type such as ferritic stainless steel is used as a base material, the mass% is C: 0.1% or less, Cr: 9 to 32%, Al: 1 to 6%, As other alloy components, Si: 1% or less, Mn: 1% or less, P: 0.04% or less, S: 0.03% or less, Ni: 0.6% or less, Mo: 5% or less, Cu: 3.5% or less, Ti: 0.8% or less, Nb: 0.8% or less, V: 1% or less, N: 0.025% or less, B: 0.1% or less, Ca: 0.1% Hereinafter, a ferritic steel type containing at least one of Mg: 0.1% or less, Y: 0.1% or less, REM (rare earth element): 0.1% or less, with the balance being Fe and inevitable impurities. Can be adopted.
基材表面のＣｕめっき層としては、例えば平均厚さ０.５μｍ以上の電気Ｃｕめっき層を採用することができる。その電気Ｃｕめっき層は、基材鋼材の表面に形成させたＮｉストライクめっき層の上に形成させても構わない。 As the Cu plating layer on the substrate surface, for example, an electric Cu plating layer having an average thickness of 0.5 μm or more can be employed. The electric Cu plating layer may be formed on the Ni strike plating layer formed on the surface of the base steel material.
本発明は以下のようなメリットを有する。
（１）電気Ｃｕめっき法を採用することで高生産性、低コストでの製造が可能である。
（２）本発明の鋼材表面を被覆するＡｌ含有銅合金層の構成元素であるＡｌは、基材側からの拡散により供給されるため、ドライめっきや非水系浴を用いたＡｌめっきによってＡｌを供給する必要がなく、簡便な方法で均一性の高いＡｌ含有銅合金層が形成可能である。
（３）Ａｌ含有銅合金層は加熱拡散処理により形成されたものであるため基材との密着性に優れる。
（４）本発明の手法により形成されたＡｌ含有銅合金層は優れた耐酸化性、耐食性、耐高温酸化性および耐摩耗性を有し、ギヤーピニオン、シャフトなどの機械部品、船舶用スクリューなど、従来Ｃｕ−Ａｌ系合金が使用されていた用途の他、ＳＯＦＣ（固体酸化物形燃料電池）のインターコネクタ（金属セパレータ）等への適用が期待される。
The present invention has the following merits.
(1) High electric productivity and low cost are possible by adopting the electric Cu plating method.
(2) Since Al, which is a constituent element of the Al-containing copper alloy layer covering the surface of the steel material of the present invention, is supplied by diffusion from the base material side, Al is applied by dry plating or Al plating using a non-aqueous bath. There is no need to supply, and a highly uniform Al-containing copper alloy layer can be formed by a simple method.
(3) Since the Al-containing copper alloy layer is formed by heat diffusion treatment, it has excellent adhesion to the substrate.
(4) The Al-containing copper alloy layer formed by the method of the present invention has excellent oxidation resistance, corrosion resistance, high temperature oxidation resistance, and wear resistance, and mechanical parts such as gear pinions and shafts, marine screws, etc. In addition to applications in which Cu—Al based alloys have been conventionally used, application to SOFC (solid oxide fuel cell) interconnectors (metal separators) and the like is expected.
〔Ａｌ含有銅合金層〕
本発明によって提供されるＡｌ含有銅合金被覆鋼材は、表面に、平均厚さ０.５μｍ以上、Ａｌ含有量１〜１５質量％のＡｌ含有銅合金層を有するものである。Ａｌ含有銅合金層の平均厚さが０.５μｍ未満では銅にＡｌを添加することによる耐食性や耐摩耗性などの向上作用を効果的に発揮させることが難しい。１μｍ以上を確保することがより望ましい。Ａｌ含有銅合金層の厚さ上限については特に制限しなくてもよいが、用途に応じて平均厚さ１００μｍ以下の範囲で調整すればよい。Ａｌ含有銅合金層の厚さは拡散処理前のＣｕめっき層の形成厚さに依存する。過剰な膜厚とすることは不経済となるので、Ａｌ含有銅合金層の平均厚さは例えば１０μｍ以下に管理しても構わない。
[Al-containing copper alloy layer]
The Al-containing copper alloy-coated steel material provided by the present invention has an Al-containing copper alloy layer having an average thickness of 0.5 μm or more and an Al content of 1 to 15% by mass on the surface. When the average thickness of the Al-containing copper alloy layer is less than 0.5 μm, it is difficult to effectively exhibit the improving action such as corrosion resistance and wear resistance by adding Al to copper. It is more desirable to ensure 1 μm or more. The upper limit of the thickness of the Al-containing copper alloy layer is not particularly limited, but may be adjusted within a range of an average thickness of 100 μm or less depending on the application. The thickness of the Al-containing copper alloy layer depends on the formation thickness of the Cu plating layer before the diffusion treatment. Since it is uneconomical to use an excessive film thickness, the average thickness of the Al-containing copper alloy layer may be controlled to 10 μm or less, for example.
Ａｌ含有銅合金層の組成は、当該合金層の厚さ中央部で測定すればよい。Ａｌ含有銅合金層中のＡｌ含有量は１質量％以上とすることが望ましい。それよりＡｌ含有量が少ないとＣｕ−Ａｌ系合金の特長を発揮させる効果が薄い。ただし、拡散処理による基材側からのＡｌの供給においては、１５質量％を超えるＡｌ含有量を実現させることは難しい。通常、Ａｌ含有銅合金層中のＡｌ含有量は１２質量％以下とすればよく、１０質量以下、あるいは８質量％以下としても構わない。 What is necessary is just to measure the composition of Al containing copper alloy layer in the thickness center part of the said alloy layer. The Al content in the Al-containing copper alloy layer is preferably 1% by mass or more. If the Al content is less than that, the effect of exhibiting the characteristics of the Cu-Al alloy is thin. However, in the supply of Al from the base material side by the diffusion treatment, it is difficult to realize an Al content exceeding 15% by mass. Usually, the Al content in the Al-containing copper alloy layer may be 12 mass% or less, and may be 10 mass% or less, or 8 mass% or less.
Ａｌ含有銅合金層を構成するＡｌ以外の残部元素は、質量％で例えばＮｉ：７％以下、Ｆｅ：６％以下、Ｃｒ：２％以下、Ｍｎ：２％以下の１種以上を含有し、残部Ｃｕおよび不可避的不純物とすることができる。これらの元素は後述のＮｉストライクめっき層や基材の鋼からの拡散により混入し得る。また、これらの元素がＣｕめっき層中に含まれる場合も、Ａｌ含有銅合金層の構成成分となる。Ｃｕ、Ａｌ、Ｎｉ、Ｆｅ、Ｃｒ、Ｍｎ以外の混入元素の含有量は合計１質量％以下であることが望ましい。 The remaining elements other than Al constituting the Al-containing copper alloy layer contain, by mass%, for example, one or more of Ni: 7% or less, Fe: 6% or less, Cr: 2% or less, Mn: 2% or less, The remaining Cu and inevitable impurities can be used. These elements can be mixed by diffusion from the Ni strike plating layer described later or the steel of the base material. Moreover, also when these elements are contained in a Cu plating layer, it becomes a structural component of an Al containing copper alloy layer. The total content of mixed elements other than Cu, Al, Ni, Fe, Cr, and Mn is desirably 1% by mass or less.
〔基材〕
本発明のＡｌ含有銅合金被覆鋼材は、後述のようにＣｕめっき鋼材を加熱拡散処理に供することにより好適に製造することができる。そのＣｕめっき鋼材の基材となる鋼としては、Ａｌを１〜２０質量％含有するものが適用される。基材のＡｌ含有量が１質量％未満だと拡散処理によって表層Ｃｕ皮膜中のＡｌ濃度を十分に増大させることが難しくなる。一方、鋼中のＡｌ含有量が多くなると鋼の金属組織においてＦｅ−Ａｌ系金属間化合物相の存在量が増大し、鋼材の製造が難しくなるので、基材中のＡｌ含有量は２０質量％以下の範囲とする。製造性を重視する場合はＦｅ−Ａｌ系金属間化合物相がほとんど生成しないＡｌ含有量１０質量％以下の範囲とすることが望ましく、８質量％以下あるいは６質量％以下に管理しても構わない。
〔Base material〕
The Al-containing copper alloy-coated steel material of the present invention can be suitably manufactured by subjecting a Cu-plated steel material to a heat diffusion treatment as will be described later. As steel used as the base material of the Cu plated steel material, one containing 1 to 20% by mass of Al is applied. When the Al content of the substrate is less than 1% by mass, it is difficult to sufficiently increase the Al concentration in the surface layer Cu film by the diffusion treatment. On the other hand, when the Al content in the steel increases, the abundance of the Fe-Al intermetallic compound phase increases in the steel microstructure, making it difficult to produce the steel material, so the Al content in the base material is 20% by mass. The following range. When emphasizing manufacturability, it is desirable that the Al content is within a range of 10% by mass or less, in which almost no Fe—Al intermetallic phase is generated, and it may be controlled to 8% by mass or less or 6% by mass or less. .
基材の鋼は、Ａｌ含有量が上記の範囲にある鋼であれば、種々の鋼種が適用可能である。例えば鋼板素材に加工して使用することを想定すると、以下のような成分組成を例示することができる。
質量％で、Ｃ：０.５％以下、Ａｌ：１〜２０％を含有し、その他の合金成分として、Ｓｉ：３％以下、Ｍｎ：５％以下、Ｐ：０.１％以下、Ｓ：０.０３％以下、Ｃｒ：３５％以下、Ｎｉ：２４％以下、Ｍｏ：５％以下、Ｃｕ：６％以下、Ｔｉ：１％以下、Ｎｂ：１％以下、Ｖ：１％以下、Ｎ：０.５％以下、Ｂ：１％以下、Ｃａ：０.１％以下、Ｍｇ：０.１％以下、Ｙ：０.１％以下、ＲＥＭ（希土類元素）：０.１％以下の１種以上を含有し、残部Ｆｅおよび不可避的不純物
As the base steel, various steel types can be applied as long as the Al content is in the above range. For example, assuming that it is processed into a steel plate material, the following component composition can be exemplified.
In mass%, C: 0.5% or less, Al: 1-20%, and other alloy components, Si: 3% or less, Mn: 5% or less, P: 0.1% or less, S: 0.03% or less, Cr: 35% or less, Ni: 24% or less, Mo: 5% or less, Cu: 6% or less, Ti: 1% or less, Nb: 1% or less, V: 1% or less, N: 0.5% or less, B: 1% or less, Ca: 0.1% or less, Mg: 0.1% or less, Y: 0.1% or less, REM (rare earth element): 0.1% or less Contains the remainder, Fe and unavoidable impurities
また、耐食性が要求される用途ではステンレス鋼を採用することが望まれる。特にＳＯＦＣのインターコネクタなどの用途には熱膨張係数が比較的小さく、応力腐食割れの問題も生じないフェライト系ステンレス鋼の採用が有利となる。フェライト系ステンレス鋼としては、鋼板素材に加工して使用することを想定すると、以下のような成分組成を例示することができる。
質量％で、Ｃ：０.１％以下、Ｃｒ：９〜３２％、Ａｌ：１〜６％であり、その他の合金成分として、Ｓｉ：１％以下、Ｍｎ：１％以下、Ｐ：０.０４％以下、Ｓ：０.０３％以下、Ｎｉ：０.６％以下、Ｍｏ：５％以下、Ｃｕ：３.５％以下、Ｔｉ：０.８％以下、Ｎｂ：０.８％以下、Ｖ：１％以下、Ｎ：０.０２５％以下、Ｂ：０.１％以下、Ｃａ：０.１％以下、Ｍｇ：０.１％以下、Ｙ：０.１％以下、ＲＥＭ（希土類元素）：０.１％以下の１種以上を含有し、残部Ｆｅおよび不可避的不純物
In applications where corrosion resistance is required, it is desirable to use stainless steel. In particular, for applications such as SOFC interconnectors, it is advantageous to use ferritic stainless steel that has a relatively low thermal expansion coefficient and does not cause the problem of stress corrosion cracking. As a ferritic stainless steel, the following component composition can be illustrated assuming that it is processed into a steel plate material.
In mass%, C: 0.1% or less, Cr: 9 to 32%, Al: 1 to 6%. As other alloy components, Si: 1% or less, Mn: 1% or less, P: 0.00%. 04% or less, S: 0.03% or less, Ni: 0.6% or less, Mo: 5% or less, Cu: 3.5% or less, Ti: 0.8% or less, Nb: 0.8% or less, V: 1% or less, N: 0.025% or less, B: 0.1% or less, Ca: 0.1% or less, Mg: 0.1% or less, Y: 0.1% or less, REM (rare earth element) ): Contains one or more of 0.1% or less, the balance Fe and inevitable impurities
〔Ｃｕめっき層の形成〕
上記の基材の表面にＣｕめっきを施す。めっき方法としては大量生産に適する電気Ｃｕめっき法を採用することができる。電気めっき浴は例えば従来一般的な硫酸銅浴、シアン化銅浴、ピロりん酸銅浴などを使用すればよい。Ｃｕめっき層の平均厚さは０.５μｍ以上とすることが望ましい。それより薄いと拡散処理後に十分な厚さのＡｌ含有銅合金層を安定して形成させることが難しくなる場合ある。Ｃｕめっき層の厚さは用途に応じて例えば１００μｍ以下の範囲で調整すればよい。１０μｍ以下の範囲に管理しても構わない。
[Formation of Cu plating layer]
Cu plating is performed on the surface of the substrate. As a plating method, an electric Cu plating method suitable for mass production can be employed. For example, a conventional copper sulfate bath, copper cyanide bath, copper pyrophosphate bath, or the like may be used as the electroplating bath. The average thickness of the Cu plating layer is preferably 0.5 μm or more. If it is thinner than that, it may be difficult to stably form an Al-containing copper alloy layer having a sufficient thickness after the diffusion treatment. What is necessary is just to adjust the thickness of Cu plating layer in the range of 100 micrometers or less, for example according to a use. You may manage in the range of 10 micrometers or less.
Ｃｕめっきに先立ち、鋼材表面には下地処理としてＮｉストライクめっき、あるいはＣｕストライクめっきを施しても構わない。Ｃｕストライクめっきを施した場合は、上記Ｃｕめっき層の厚さとしてストライクめっき層の厚さが含まれる。Ｎｉストライクめっきの場合は膜厚０.０５〜０.３μｍ程度のＮｉ薄膜層を形成させることが望ましい。ＮｉストライクめっきによるＮｉ薄膜層は拡散処理を行うことでほとんど消失し、Ａｌ含有銅合金層中には拡散してきたＮｉストライクめっき由来のＮｉが観測される。 Prior to Cu plating, Ni strike plating or Cu strike plating may be applied to the steel surface as a base treatment. When Cu strike plating is performed, the thickness of the strike plating layer is included as the thickness of the Cu plating layer. In the case of Ni strike plating, it is desirable to form a Ni thin film layer having a thickness of about 0.05 to 0.3 μm. The Ni thin film layer formed by Ni strike plating almost disappears by performing a diffusion treatment, and diffused Ni derived from Ni strike plating is observed in the Al-containing copper alloy layer.
以下に、Ｎｉストライクめっきを施す場合を例に挙げて、Ｃｕめっき層を形成させる一般的な手順を例示する。
（１）基材（めっき原板）となる鋼材（鋼板）を脱脂、酸洗処理する。
（２）Ｎｉストライクめっきを施す。条件は例えば、塩化ニッケル２００〜３００ｇ／Ｌ、塩酸１００〜１５０ｍＬ／Ｌを含有する水溶液をめっき浴として、浴温３０〜４０℃、電流密度５〜１０Ａ／ｄｍ2にて、平均膜厚０.０５〜０.３μｍ程度のＮｉ薄膜層を形成させる。
（３）Ｃｕめっきを施す。条件は例えば、硫酸銅１５０〜２５０ｇ／Ｌ、硫酸３０〜８０ｇ／Ｌを含有する水溶液をめっき浴（硫酸銅浴）として、浴温２０〜６０℃、電流密度３〜１０Ａ／ｄｍ2にて、平均膜厚０.５〜１００μｍ、好ましくは１〜１０μｍ程度のＣｕめっき層を形成させる。
Below, the case where Ni strike plating is given is mentioned as an example, and the general procedure which forms Cu plating layer is illustrated.
(1) A steel material (steel plate) to be a base material (plating original plate) is degreased and pickled.
(2) Ni strike plating is performed. The conditions are, for example, an aqueous solution containing nickel chloride 200 to 300 g / L and hydrochloric acid 100 to 150 mL / L as a plating bath, a bath temperature of 30 to 40 ° C., a current density of 5 to 10 A / dm 2 , and an average film thickness of 0. A Ni thin film layer of about 05 to 0.3 μm is formed.
(3) Apply Cu plating. The conditions are, for example, an aqueous solution containing copper sulfate 150 to 250 g / L and sulfuric acid 30 to 80 g / L as a plating bath (copper sulfate bath) at a bath temperature of 20 to 60 ° C. and a current density of 3 to 10 A / dm 2 . A Cu plating layer having an average film thickness of 0.5 to 100 μm, preferably about 1 to 10 μm is formed.
〔Ａｌ含有銅合金層の形成〕
基材表面にＣｕめっき層を形成した「Ｃｕめっき鋼材」を高温に加熱すると、基材中に存在するＡｌがＣｕめっき層の内部に拡散し、鋼材表層部にはＡｌ含有銅合金層が形成される。加熱温度は６００〜１０５０℃とすることが望ましく、７００℃〜１０２０℃とすることがより好ましい。加熱時間は０〜２４ｈの範囲で最適条件を設定すればよい。ここで加熱時間０ｈとは、上記温度範囲に設定した所定の加熱温度に材料温度が到達した後、直ちに降温過程に移行させるヒートパターンを採用する場合を意味する。加熱温度および加熱時間は、Ｃｕめっき層の厚さ、基材中のＡｌ含有量などに応じて、Ａｌ含有銅合金層の膜厚およびＡｌ含有量が目的の範囲となるように条件を設定すればよい。
[Formation of Al-containing copper alloy layer]
When "Cu-plated steel" with a Cu-plated layer formed on the substrate surface is heated to a high temperature, Al present in the substrate diffuses into the Cu-plated layer, and an Al-containing copper alloy layer is formed on the steel surface layer. Is done. The heating temperature is preferably 600 to 1050 ° C, more preferably 700 to 1020 ° C. What is necessary is just to set optimal conditions for the heating time in the range of 0-24h. Here, the heating time 0h means a case in which a heat pattern is adopted in which the material temperature immediately reaches the predetermined heating temperature set in the above temperature range and is immediately shifted to the temperature lowering process. The heating temperature and heating time should be set so that the film thickness and Al content of the Al-containing copper alloy layer are within the target range depending on the thickness of the Cu plating layer and the Al content in the substrate. That's fine.
この拡散処理の加熱は非酸化性雰囲気で行う。例えば、真空雰囲気、窒素ガスやアルゴンガスなどの不活性ガス雰囲気、水素ガスなどの還元性ガス雰囲気などが例示できる。さらに露点を−２０℃以下好ましくは−３０℃以下に低く保つことが表面酸化を抑制する上で特に効果的である。 The diffusion treatment is heated in a non-oxidizing atmosphere. Examples thereof include a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas and argon gas, and a reducing gas atmosphere such as hydrogen gas. Furthermore, keeping the dew point at -20 ° C or lower, preferably -30 ° C or lower, is particularly effective in suppressing surface oxidation.
表１に示す鋼種Ａからなる板厚１ｍｍの鋼板を用意した。この鋼板の表面を＃１０００耐水研磨紙で研磨したのち、６０℃の５質量％オルソ珪酸ナトリウム水溶液中で電解脱脂し、次いで５質量％塩酸水溶液で中和処理することにより基材（めっき原板）とした。
この基材に、硫酸銅２００ｇ／Ｌ、硫酸５０ｇ／Ｌを含有する硫酸銅浴を用いて、浴温４０℃、電流密度１０Ａ／ｄｍ2にて電気Ｃｕめっきを施し、平均厚さ１μｍのＣｕめっき層を表面に有するＣｕめっき鋼材を得た。
このＣｕめっき鋼材を、露点−６０℃の１００％窒素ガス雰囲気中にて、加熱温度１０００℃、加熱時間５ｍｉｎの拡散処理に供した。
A steel plate having a thickness of 1 mm made of steel type A shown in Table 1 was prepared. After polishing the surface of this steel plate with # 1000 water-resistant abrasive paper, it is electrolytically degreased in a 5% by mass sodium orthosilicate aqueous solution at 60 ° C., and then neutralized with a 5% by mass hydrochloric acid aqueous solution to form a base material (plating original plate) It was.
This substrate was subjected to electro Cu plating at a bath temperature of 40 ° C. and a current density of 10 A / dm 2 using a copper sulfate bath containing 200 g / L of copper sulfate and 50 g / L of sulfuric acid, and Cu having an average thickness of 1 μm. A Cu plated steel material having a plating layer on the surface was obtained.
This Cu plated steel material was subjected to a diffusion treatment at a heating temperature of 1000 ° C. and a heating time of 5 minutes in a 100% nitrogen gas atmosphere having a dew point of −60 ° C.
拡散処理後の材料について、表面付近の断面をＳＥＭ−ＥＤＸで観察・分析したところ、鋼材表面に平均厚さ約１μｍのＡｌ含有銅合金層が形成されていた。その組成は、Ｃｕ、Ａｌ、Ｎｉ、Ｆｅの分析値によると、厚さ中央部１０箇所の測定結果の平均値で、Ａｌ：２.１質量％、Ｎｉ：０.０２質量％、Ｆｅ：０.６質量％であり、残部はＣｕであった。
このＡｌ含有銅合金層は厚さ変動および組成変動が少なく、均一性の高いものであった。
When the cross section near the surface was observed and analyzed for the material after the diffusion treatment by SEM-EDX, an Al-containing copper alloy layer having an average thickness of about 1 μm was formed on the steel material surface. According to the analysis values of Cu, Al, Ni, and Fe, the composition is the average value of the measurement results at 10 locations in the thickness center, Al: 2.1 mass%, Ni: 0.02 mass%, Fe: 0 0.6% by mass, and the balance was Cu.
This Al-containing copper alloy layer had little variation in thickness and composition, and was highly uniform.
表１に示す鋼種Ｂからなる板厚１ｍｍの鋼板を用意した。この鋼板の表面を＃１０００耐水研磨紙で研磨したのち、６０℃の５質量％オルソ珪酸ナトリウム水溶液中で電解脱脂し、次いで５質量％塩酸水溶液で中和処理することにより基材（めっき原板）とした。
この基材に、塩化ニッケル２４０ｇ／Ｌ、塩酸１２０ｍＬ／Ｌを含有する塩化ニッケル浴を用いて、浴温３０℃、電流密度５Ａ／ｄｍ2にてＮｉストライクめっきを施し、平均厚さ０.３μｍのＮｉ薄膜層を表面に有する鋼材を得た。
このＮｉ薄膜層の上に、硫酸銅２００ｇ／Ｌ、硫酸５０ｇ／Ｌを含有する硫酸銅浴を用いて、浴温４０℃、電流密度１０Ａ／ｄｍ2にて電気Ｃｕめっきを施し、平均厚さ３μｍのＣｕめっき層を表面に有するＣｕめっき鋼材を得た。
このＣｕめっき鋼材を、露点−３０℃の１００％水素ガス雰囲気中にて、加熱温度８００℃、加熱時間２ｈの拡散処理に供した。
A steel plate having a thickness of 1 mm made of steel type B shown in Table 1 was prepared. After polishing the surface of this steel plate with # 1000 water-resistant abrasive paper, it is electrolytically degreased in a 5% by mass sodium orthosilicate aqueous solution at 60 ° C., and then neutralized with a 5% by mass hydrochloric acid aqueous solution to form a base material (plating original plate) It was.
This substrate was subjected to Ni strike plating at a bath temperature of 30 ° C. and a current density of 5 A / dm 2 using a nickel chloride bath containing 240 g / L of nickel chloride and 120 mL / L of hydrochloric acid, and an average thickness of 0.3 μm. A steel material having a Ni thin film layer on its surface was obtained.
On this Ni thin film layer, using a copper sulfate bath containing 200 g / L of copper sulfate and 50 g / L of sulfuric acid, electro Cu plating was performed at a bath temperature of 40 ° C. and a current density of 10 A / dm 2 to obtain an average thickness. A Cu plated steel material having a 3 μm Cu plated layer on the surface was obtained.
This Cu plated steel material was subjected to a diffusion treatment at a heating temperature of 800 ° C. and a heating time of 2 hours in a 100% hydrogen gas atmosphere having a dew point of −30 ° C.
拡散処理後の材料について、表面付近の断面をＳＥＭ−ＥＤＸで観察・分析したところ、鋼材表面に平均厚さ約３μｍのＡｌ含有銅合金層が形成されていた。その組成は、Ｃｕ、Ａｌ、Ｎｉ、Ｆｅの分析値によると、厚さ中央部１０箇所の測定結果の平均値で、Ａｌ：６.２質量％、Ｎｉ：０.６質量％、Ｆｅ：１.２質量％であり、残部はＣｕであった。 When the cross section near the surface of the material after the diffusion treatment was observed and analyzed by SEM-EDX, an Al-containing copper alloy layer having an average thickness of about 3 μm was formed on the steel surface. According to the analysis values of Cu, Al, Ni, and Fe, the composition is the average value of the measurement results at 10 locations in the central portion of the thickness, Al: 6.2% by mass, Ni: 0.6% by mass, Fe: 1 0.2% by mass, and the balance was Cu.
図１に、拡散処理後の材料の表面付近の断面ＳＥＭ写真を示す。図２に、拡散処理前のＣｕめっき鋼材および拡散処理後のＡｌ含有銅合金被覆鋼材について、高周波グロー放電分光分析（ＧＤＳ）による表面から深さ方向への元素濃度分布の測定結果を示す。拡散処理により基材の鋼中に存在していたＡｌがＣｕめっき層側に拡散し、厚さ方向の濃度変動が少ない均質性の高いＡｌ含有銅合金層が形成されていることがわかる。 FIG. 1 shows a cross-sectional SEM photograph near the surface of the material after the diffusion treatment. FIG. 2 shows the measurement results of the element concentration distribution from the surface to the depth direction by high frequency glow discharge spectroscopic analysis (GDS) for the Cu-plated steel material before the diffusion treatment and the Al-containing copper alloy coated steel material after the diffusion treatment. It can be seen that Al present in the steel of the base material diffuses to the Cu plating layer side by the diffusion treatment, and a highly homogeneous Al-containing copper alloy layer with little concentration fluctuation in the thickness direction is formed.
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