JP3942505B2 - Titanium copper alloy material and manufacturing method thereof - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、曲げ加工性及び応力緩和特性等の機械的特性の均一性が優れたチタン銅合金材及びその製造方法に関する。
【０００２】
【従来の技術】
従来より、ばね性、応力緩和特性及び曲げ加工性等の機械的特性並びに導電性が要求される部材、例えば、電子部品用ばね材等には、チタン銅合金材が使用されている。このようなチタン銅合金は、例えば、ＪＩＳ Ｈ３１３０の合金Ｃ１９９０において規定されている。そして近時、より良好且つ均質な機械的特性を有するチタン銅合金材の開発が進められている。
【０００３】
例えば、特公昭６２−３９２１５号公報には、Ｔｉの含有量を２乃至６質量％とし、マトリックス（母相）であるα相中に第二相であるＣｕ３Ｔｉ析出物を微細且つ均一に分散させ、平均結晶粒径を２５μｍ以下としたチタン銅合金が開示されている。特公昭６２−３９２１５号公報には、これにより、機械的特性のばらつきが小さいチタン銅合金が得られると記載されている。
【０００４】
また、特開平７−２５８８０３号公報には、Ｔｉを０．０１乃至４．０質量％含有する銅合金に、８００℃以上の温度で２４０秒間以内の熱処理を行う１回目の溶体化処理を施し、８０％未満の加工度で１回目の冷間圧延を施し、８００℃以上の温度で２４０秒間以内の熱処理を行う２回目の溶体化処理を施し、５０％未満の加工度で２回目の冷間圧延を施し、３００乃至７００℃の温度で１時間以上１５時間未満の熱処理を行う時効処理を施して、チタン銅合金を製造する方法が開示されている。特開平７−２５８８０３号公報には、これにより、曲げ性及び応力緩和特性が優れたチタン銅合金が得られると記載されている。
【０００５】
【発明が解決しようとする課題】
しかしながら、上述の従来の技術には、以下に示すような問題点がある。特公昭６２−３９２１５号公報及び特開平７−２５８８０３号公報に記載されているチタン銅合金により板材を形成すると、この板材の幅方向における位置により、また、測定方向が圧延方向か圧延直交方向かにより、曲げ加工性及び応力緩和特性等の機械的特性がばらついてしまい、良好な機械的特性を安定して得ることができないという問題点がある。
【０００６】
本発明はかかる問題点に鑑みてなされたものであって、曲げ加工性及び応力緩和特性等の機械的特性が均一且つ良好であるチタン銅合金及びその製造方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明に係るチタン銅合金材は、Ｔｉを１．０乃至５．０質量％含有し残部がＣｕ及び不可避的不純物からなる組成を有し、（結晶粒径の偏差／平均結晶粒径）比の値が０．６０以下であることを特徴とする。
【０００８】
本発明においては、チタン銅合金材にＴｉを１．０乃至５．０質量％含有させ、（結晶粒径の偏差／平均結晶粒径）比の値を０．６０以下とすることにより、溶体化処理中にβ相が析出することを抑制し、結晶粒の大きさのばらつきを抑制することにより、機械的特性を均一且つ良好にすることができる。
【０００９】
本発明に係るチタン銅合金材の製造方法は、Ｔｉを１．０乃至５．０質量％含有し残部がＣｕ及び不可避的不純物からなる組成を有するチタン銅合金からなる部材に対して、８２０℃以上の温度に１００秒間以上保持する第１の溶体化処理を施して前記部材の平均結晶粒径を１５μｍ以上とする工程と、５０％以上の加工率で第１の冷間圧延を施す工程と、１０００℃／分以上の昇温速度で８２０℃以上の温度に加熱する第２の溶体化処理を施す工程と、５乃至８５％の加工率で第２の冷間圧延を施す工程と、３５０乃至４８０℃の温度に２乃至１０時間保持する時効処理を施す工程と、を有することを特徴とする。
【００１０】
本発明においては、第２の溶体化処理工程において、１０００℃／分以上の昇温速度で８２０℃以上の温度に加熱することにより、昇温中にβ相が析出せず、８２０℃以上の温度に達したときに、チタン銅合金材がα単相となる。これにより、β相の析出によるＴｉの偏析及び結晶粒径のばらつきが発生せず、チタン銅合金材の組織が均一になり、均一且つ良好な機械的特性が得られる。
【００１１】
また、第１の溶体化処理工程における温度を８２０℃以上とし、保持時間を１００秒間以上とすることにより、マトリックスにＴｉを十分に固溶させると共に、再結晶を促進し、平均結晶粒径が１５μｍ以上の組織とすることができる。これにより、第１の溶体化処理後のチタン銅合金において、組織及びＴｉの固溶状態を均一化することができる。また、第１の冷間圧延工程における加工率を５０％以上とすることにより、第２の溶体化処理工程において、核発生を促進し、十分に再結晶させることができる。これにより、第２の溶体化処理工程において、均一な組織を得ることができる。
【００１２】
【発明の実施の形態】
以下、本発明の実施形態について添付の図面を参照して具体的に説明する。本発明の実施形態に係るチタン銅合金は、Ｔｉを１．０乃至５．０質量％含有し残部がＣｕ及び不可避的不純物からなる組成を有している。また、（結晶粒径の偏差／平均結晶粒径）比の値が０．６０以下である。
【００１３】
本実施形態に係るチタン銅合金材の製造方法について説明する。図１は本実施形態に係るチタン銅合金材の製造方法を示すフローチャートである。先ず、図１のステップＳ１に示すように、溶解により、Ｔｉを１．０乃至５．０質量％含有し残部がＣｕ及び不可避的不純物からなる組成を有するインゴットを作製する。そして、図１のステップＳ２乃至Ｓ４に示すように、このインゴットに鍛造、熱間圧延及び冷間圧延を施し、例えば板材に加工する。次に、ステップＳ５に示すように、この板材を８２０℃以上の温度に１００秒間以上保持して第１の溶体化処理を行う。このとき、前記温度は例えばこの板材の固溶線よりも３０℃以上高い温度とする。これにより、Ｔｉがマトリックス中に十分固溶すると共に、再結晶が起こり、平均結晶粒径が１５μｍ以上の組織となる。その後、この板材を室温まで冷却する。次に、ステップＳ６に示すように、この板材に対して、５０％以上の加工率で第１の冷間圧延を施す。これにより、次の工程である第２の溶体化処理において、核発生を促進することができる。
【００１４】
次に、ステップＳ７に示すように、この板材を１０００℃／分以上の昇温速度で室温から８２０℃以上の温度まで加熱し、８２０℃以上の温度に５秒間以上、例えば１００秒間以上保持して第２の溶体化処理を行う。このとき、前記温度は例えばこの板材の固溶線よりも３０℃以上高い温度とする。その後、室温まで冷却する。そして、ステップＳ８に示すように、この板材に対して、５乃至８５％の加工率で第２の冷間圧延を施す。このとき、加工率は目標とする材質及び最終板厚に応じて決定する。次に、ステップＳ９に示すように、板材を３５０乃至４８０℃の温度に２乃至１０時間保持して時効処理を施す。これにより、前記板材が析出硬化する。このようにして、本実施形態に係るチタン銅合金材が作製される。
【００１５】
以下、本発明の各構成要件における数値限定理由について説明する。
【００１６】
Ｔｉ含有量：１．０乃至５．０質量％
Ｔｉは銅合金を析出硬化させるために添加する。Ｔｉの含有量が１．０質量％未満では、析出硬化の効果が小さく、チタン銅合金材の強度が不足する。一方、Ｔｉの含有量が５．０質量％を超えると、チタン銅合金材の加工性が低下する。
従って、Ｔｉの含有量は１．０乃至５．０質量％とする。より好適には、２．５乃至４．０質量％である。
【００１７】
（結晶粒径の偏差／平均結晶粒径）比の値：０．６０以下
（結晶粒径の偏差／平均結晶粒径）比の値が０．６０より大きいと、結晶のばらつきが大きく、チタン銅合金材の曲げ加工性のばらつきが大きくなる。従って、（結晶粒径の偏差／平均結晶粒径）比の値は０．６０以下とする。
【００１８】
第１の溶体化処理における加熱温度：８２０℃以上
前記加熱温度が８２０℃未満であると、Ｔｉの固溶が不十分となると共に、再結晶が不十分となり、平均結晶粒径が１５μｍ以上の再結晶粒が生成しない。このため、時効処理後のチタン銅合金の組織が不均一となる。従って、第１の溶体化処理における加熱温度は８２０℃以上とする。より好ましくは、チタン銅合金材の固溶線よりも３０℃以上高い温度である。
【００１９】
第１の溶体化処理における加熱時間：１００秒間以上
前記加熱時間が１００秒間未満であると、Ｔｉの固溶が不十分となると共に、再結晶が不十分となり、平均結晶粒径が１５μｍ以上の再結晶粒が生成しない。
このため、時効処理後のチタン銅合金の組織が不均一となる。従って、第１の溶体化処理における加熱時間は１００秒間以上とする。
【００２０】
第１の溶体化処理を行った後の平均結晶粒径：１５μｍ以上
平均結晶粒径が１５μｍ未満であると、結晶組織は結晶の大きさがばらついた混粒となる。この状態の組織を顕微鏡により観察すると、粒径が１乃至１０μｍ程度の結晶粒が混在した状態となっている。このような状態では、固溶したＴｉが偏析する。これに対して、平均結晶粒径を１５μｍ以上とすると、結晶の粒径がほぼ揃った状態となり、Ｔｉの偏析を抑制することができる。このため、第１溶体化処理後のチタン銅合金材の組織を、第２の溶体化処理の開始条件として好適なＴｉの偏析が抑制された状態とすることができる。
【００２１】
第１の冷間圧延における加工率：５０％以上
第１の冷間圧延における加工率が５０％未満であると、チタン銅合金材に付与する加工歪みが不十分となり、第２の溶体化処理において、十分な核発生が起こらない。このため、再結晶が十分に進行しない。従って、第１の冷間加工における加工率は５０％以上とする。
【００２２】
第２の溶体化処理における昇温速度：１０００℃／分以上
第２の溶体化処理における昇温速度が１０００℃／分未満であると、昇温中にβ相の粒界析出反応が進行する。このため、チタンの偏析及び結晶粒のばらつきが発生し、チタン銅合金材の組織が不均一になり、（結晶粒径の偏差／平均結晶粒径）比の値が０．６０より大きくなる。この結果、時効処理後のチタン銅合金材の機械的特性が不均一になる。従って、第２の溶体化処理における昇温速度は１０００℃／分以上とする。
【００２３】
第２の溶体化処理における加熱温度：８２０℃以上
前記加熱温度が８２０℃未満であると、Ｔｉの固溶が不十分となると共に、再結晶が十分に進行しない。また、この溶体化処理中にβ相が生成してしまう。これにより、時効処理後のチタン銅合金の組織が不均一となる。従って、第２の溶体化処理における加熱温度は８２０℃以上とする。より好ましくは、チタン銅合金材の固溶線よりも３０℃以上高い温度である。
【００２４】
第２の冷間圧延における加工率：５乃至８５％
加工率が５％未満の冷間圧延は技術的に困難である。一方、加工率を８５％より大きくしても、加工率を増加させることによる効果が飽和し、特性がそれ以上向上しないため無意味である。従って、第２の冷間圧延における加工率は５乃至８５％とする。
【００２５】
時効処理における加熱温度：３５０乃至４８０℃
時効処理における加熱温度が３５０℃未満であると、Ｔｉを析出させるために長時間の加熱が必要となり、製造コストが増大する。一方、前記加熱温度が４８０℃を超えると、Ｔｉの析出が過剰となり、材料強度の低下を招く。即ち、チタン銅合金材を効率的に固溶強化及び析出強化させるために、時効処理における加熱温度を３５０乃至４８０℃とする。
【００２６】
時効処理における加熱時間：２乃至１０時間
時効処理における加熱時間が２時間未満であると、Ｔｉの析出が不十分となり、チタン銅合金材が十分に析出硬化しない。一方、前記加熱時間が１０時間を超えると、過時効によりチタン銅合金材の強度が却って低下する。従って、時効処理における加熱時間は２乃至１０時間とする。
【００２７】
次に、第２の溶体化処理における昇温速度と組織との関係について、より詳細に説明する。図２は横軸にチタン銅合金におけるＴｉ含有量をとり、縦軸に温度をとって、チタン銅合金の相状態を示すＣｕ−Ｔｉ状態図である。また、図３は、横軸に昇温開始時点からの時間をとり、縦軸に温度をとって、チタン銅合金の昇温に伴う組織変化を示す恒温変態線図（ＴＴＴ曲線：time-temperature-transformation diagram）である。なお、図３において、線Ａ、Ｂ、Ｃ及びＤは、一定の昇温速度で室温から例えば８２０℃まで加熱し、その後、８２０℃の温度に保持する処理における温度変化を示し、線Ａは昇温速度が例えば２０００℃／分の場合を示し、線Ｂは昇温速度が例えば１０００℃／分の場合を示し、線Ｃは昇温速度が例えば６７０℃／分の場合を示し、線Ｄは昇温速度が例えば６７０℃／分未満、例えば３３０℃／分の場合を示す。
【００２８】
図２に示すように、実用的なＣｕ−３質量％Ｔｉ合金、例えばＴｉ濃度が３．２質量％である合金は、７９０℃以上の温度に加熱すると、Ｃｕからなるマトリックス（母相）にＴｉが固溶してα相となる。但し、図２は安定状態を示しており、時間の要素は無視されている。実際には、固溶状態に到る昇温過程及び７９０℃以上の温度に達した後の保持時間により、組織に違いが生じる。
【００２９】
チタン銅合金材を室温から昇温させることにより、チタン銅合金材の温度が二相分離領域（図２に示す（α＋β）領域）に入ると、マトリックスであるα相中にＣｕ及びＴｉからなるβ相が析出する。但し、β相が析出するためには、マトリックス内で固溶しているＴｉ原子が移動し凝集することが必要であり、従って、Ｔｉ原子がβ相の析出に必要な距離を移動する間、チタン銅合金材の温度が二相分離領域に留まることが必要である。そして、Ｔｉ原子の移動距離は移動速度及び時間によって決定され、Ｔｉ原子の移動速度は温度によって決定される。従って、Ｔｉ原子の移動距離は温度及び時間に依存する。
【００３０】
このため、図３の線Ａ及びＢに示すように、チタン銅合金材の昇温速度が十分に速いと、チタン銅合金材の温度が二相分離領域にある時間内に、Ｔｉ原子が十分な距離を移動することができず、β相が析出しない。この結果、７９０℃以上に加熱されたチタン銅合金材の組織はα単相となる。
【００３１】
これに対して、図３の線Ｃ及びＤに示すように、チタン銅合金材の昇温速度が遅いと、チタン銅合金材の温度が二相分離領域にある時間内に、Ｔｉ原子が十分な距離を移動して凝集し、β相が析出する。この場合、チタン銅合金材の温度が二相分離領域を通過してα単相領域に達すると、生成したβ相は再固溶する。しかしながら、一旦析出した相の再固溶には、凝集時に必要とされる熱エネルギー以上の熱エネルギーが必要とされるため、再固溶は簡単には進行しない。実際には、チタン銅合金材の温度が８２０℃に達した時点においても、まだβ相は残っている。第２の溶体化処理時において、β相が残留していると、チタン銅合金材中の固溶Ｔｉがこのβ相中に析出してしまい、Ｔｉが均一に固溶しなくなる。また、β相が析出することにより、チタン銅合金材の結晶粒径のばらつきが大きくなり、組織が不均一になる。この結果、チタン銅合金材の機械的特性が不均一になる。
【００３２】
なお、昇温過程において析出したβ相は、チタン銅合金材を８２０℃の温度に長時間保持するか、チタン銅合金材の加熱温度を高くすることにより、消滅させることができる。しかし、保持時間を長くすると、実際の製造工程においては、加工時間を長くするか、又は保持のために１工程追加することになるため、チタン銅合金材の製造コストを著しく増大させてしまい、現実的ではない。また、加熱温度を高くすると、エネルギーコストの増大を招くだけでなく、α相の結晶粒の巨大化を招き、チタン銅合金材の強度及び曲げ性に悪影響を及ぼすため、これも現実的ではない。
【００３３】
以上の理由から、本発明者等は、均一性が高いチタン銅合金材を作製するためには、第２の溶体化処理においてβ相を析出させないことが必要であり、そのためには、図３の線Ｂに示す昇温速度以上の昇温速度が必要であることを見出した。そして、後述するように、本発明者等は実験の結果、β相を析出させない昇温速度が１０００℃／分以上であることを突き止めた。
【００３４】
なお、第２の溶体化処理における降温中にβ相が析出することもあり得るが、降温中に析出したβ相は結晶粒の成長には影響しないため、結晶粒径のばらつきの原因にはならない。なお、第２の溶体化処理の降温工程において、水冷等により急冷することにより、β相の析出を防止することができる。これにより、後工程である時効処理の効果を十分に引き出すことができる。
【００３５】
上述の如く、本実施形態においては、第２の溶体化処理において、チタン銅合金からなる板材を、１０００℃／分以上の昇温速度で８２０℃以上の温度まで加熱する。これにより、昇温中にβ相が析出することを抑制できる。この結果、Ｔｉがβ相中に偏析することを防止でき、Ｔｉを均一に固溶させることができる。また、β相の析出により、結晶粒の大きさがばらつくことを防止できる。
【００３６】
また、第１の溶体化処理において、前記板材を８２０℃以上の温度に１００秒間以上保持し、マトリックスにＴｉを十分に固溶させると共に再結晶させ、第１の冷間圧延において、５０％以上の加工率で圧延することにより、加工歪みを付与しているため、第２の溶体化処理において、十分に再結晶させることができる。
【００３７】
これらの結果、第２の溶体化処理後の組織を均一化することができ、（結晶粒径の偏差／平均結晶粒径）比の値を０．６０以下とすることができる。これにより、時効処理後のチタン銅合金材の組織を均一化することができる。
【００３８】
β相及び不揃いな結晶粒の粒界に蓄積された加工歪みは、拘束力が弱く、低い熱エネルギーにより開放されてしまうことが多い。一方、均一で且つβ相がない組織に蓄積された加工歪みは、強力且つ均一な拘束力により拘束され、低い熱エネルギーでは開放されにくい。このため、このような組織を有する材料は、応力が緩和されにくく、応力緩和特性が良好となる。
【００３９】
また、チタン銅合金材の組織を均一化することにより、チタン銅合金材の機械的特性を均一化することができる。機械的特性が不均一な材料は、特性が良好な部分と劣った部分とがミクロ的に混在し、外部から応力が印加されると、この応力は特性が劣った部分に集中するため、材料全体のマクロ的な特性は低いものになる。これに対して、本実施形態に係るチタン銅合金材は、組織及び特性が均一であるため、マクロ的な機械的特性、例えば曲げ加工性が優れている。
【００４０】
このように、本実施形態によれば、曲げ加工性及び応力緩和特性が均一且つ良好なチタン銅合金材を作製することができる。この結果、機械的特性のばらつきが少なく、安定性が良好なチタン銅合金材を得ることができる。
【００４１】
【実施例】
以下、本発明の実施例の効果について、その特許請求の範囲から外れる比較例と比較して具体的に説明する。先ず、Ｔｉを３．２質量％含有し、残部がＣｕ及び不可避的不純物からなる組成を有するインゴットを溶解にて作製した。次に、このインゴットに対して、鍛造、熱間圧延及び冷間圧延を順次施し、厚さが１．０ｍｍの板材を作製した。次に、この板材を９００℃の温度まで加熱し、この温度にて１２０秒間保持し、第１の溶体化処理を行った。次に、室温まで冷却し、加工率が６０％の条件で第１の冷間圧延を行った。そして、この圧延後の板材を、昇温速度を相互に異ならせて８４０℃まで加熱し、その温度に１２０秒間保持して、第２の溶体化処理を行った。このときの昇温速度を表１に示す。次に、この板材を水冷して室温まで冷却し、加工率が５０％の条件で第２の冷間圧延を行った。そして、温度が４２０℃、時間が３時間の条件で、時効処理を行い、チタン銅合金材を作製した。時効処理後のチタン銅合金材の板厚は０．２０ｍｍとした。
【００４２】
次に、このようにして作製したチタン銅合金材の結晶粒径及び曲げ加工性を測定した。結晶粒径は、ＪＩＳ Ｈ０５０１−１９８６「伸銅品結晶粒度試験方法」により規定されている「切断法」により測定した。このとき、切断法において既知の長さの線分により切り取られた結晶粒数は約１００個であった。この切断法による測定を数回繰り返して平均値を算出した。この測定結果に基づいて、結晶粒径の偏差及び平均粒径を算出し、（結晶粒径の偏差／平均結晶粒径）比の値を求めた。結晶粒径の測定結果を表１に示す。また、図４（ａ）及び（ｂ）、図５（ａ）及び（ｂ）、図６（ａ）及び（ｂ）並びに図７（ａ）及び（ｂ）は、表１に示すＮｏ．Ａ、Ｂ、Ｃ及びＤの各サンプルの組織を示す光学顕微鏡写真であり、各図の（ａ）は倍率が１３０倍の写真であり、（ｂ）は倍率が６７０倍の写真である。
【００４３】
曲げ加工性は、ＪＩＳ Ｚ２２４８−１９９６「金属材料曲げ試験方法」により規定されている「Ｖブロック法」により９０°曲げ試験を行い、「押曲げ法」により１８０°曲げ試験を行った。曲げ加工性の評価結果を表１に示す。なお、
表１に示す「ＧＷ」及び「ＢＷ」は、伸銅品の分野で通常使用されているサンプルの圧延方向を示す用語であり、「ＧＷ」とはサンプルの長手方向、即ち曲げ方向が圧延平行方向であることを示し、「ＢＷ」とはサンプルの長手方向が圧延直交方向であることを示す。また、表１に示す「Ｒ／ｔ」とは、｛（サンプルが破断しない最小の曲げ加工半径）／（サンプルの板厚）｝の値である。
【００４４】
【表１】
表１に示すＮｏ．Ａ及びＮｏ．Ｂは本発明の実施例である。実施例Ｎｏ．Ａ及びＢは、第２溶体化処理における昇温速度が１０００℃／分以上であり、他の製造条件も全て本発明の規定を満たしているため、（結晶粒径の偏差／平均結晶粒径）比の値が０．６０以下であり、そのため、曲げ加工性のばらつきが小さく、良好であった。これに対して、表１に示すＮｏ．Ｃ及びＤは比較例である。比較例Ｎｏ．Ｃ及びＤは、第２溶体化処理における昇温速度が１０００℃／分未満であるため、（結晶粒径の偏差／平均結晶粒径）比の値が０．６０より大きく、特に、長手方向が圧延直交方向であるサンプルにおいて、曲げ加工性が劣っていた。
【００４６】
【発明の効果】
以上詳述したように、本発明によれば、第２溶体化処理における昇温速度を１０００℃／分以上とすることにより、β相の析出を抑制でき、組織が均一で機械的特性が優れたチタン銅合金材を得ることができる。
【図面の簡単な説明】
【図１】本発明の実施例に係るチタン銅合金材の製造方法を示すフローチャートである。
【図２】横軸にチタン銅合金におけるＴｉ含有量をとり、縦軸に温度をとって、チタン銅合金の相状態を示すＣｕ−Ｔｉ状態図である。
【図３】横軸に昇温開始時点からの時間をとり、縦軸に温度をとって、チタン銅合金の昇温に伴う組織変化を示す恒温変態線図である。
【図４】（ａ）及び（ｂ）は実施例Ｎｏ．Ａのサンプルの組織を示す図面代用写真である（光学顕微鏡写真：（ａ）倍率１３０倍、（ｂ）倍率６７０倍）。
【図５】（ａ）及び（ｂ）は実施例Ｎｏ．Ｂのサンプルの組織を示す図面代用写真である（光学顕微鏡写真：（ａ）倍率１３０倍、（ｂ）倍率６７０倍）。
【図６】（ａ）及び（ｂ）は比較例Ｎｏ．Ｃのサンプルの組織を示す図面代用写真である（光学顕微鏡写真：（ａ）倍率１３０倍、（ｂ）倍率６７０倍）。
【図７】（ａ）及び（ｂ）は比較例Ｎｏ．Ｄのサンプルの組織を示す図面代用写真である（光学顕微鏡写真：（ａ）倍率１３０倍、（ｂ）倍率６７０倍）。
【符号の説明】
Ａ、Ｂ、Ｃ、Ｄ；温度変化を示す線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a titanium-copper alloy material having excellent uniformity in mechanical properties such as bending workability and stress relaxation properties, and a method for producing the same.
[0002]
[Prior art]
Conventionally, titanium-copper alloy materials have been used for members that require mechanical properties such as spring properties, stress relaxation properties, bending workability, and conductivity, such as spring materials for electronic components. Such a titanium copper alloy is defined in, for example, an alloy C1990 of JIS H3130. Recently, the development of titanium copper alloy materials having better and more uniform mechanical properties has been underway.
[0003]
For example, in Japanese Examined Patent Publication No. 62-39215, the content of Ti is 2 to 6% by mass, and the Cu 3 Ti precipitate as the second phase is finely and uniformly formed in the α phase as the matrix (matrix phase). Disclosed is a titanium-copper alloy having an average crystal grain size of 25 μm or less. Japanese Examined Patent Publication No. 62-39215 describes that a titanium-copper alloy with small variations in mechanical properties can be obtained.
[0004]
JP-A-7-258803 discloses a first solution treatment in which a copper alloy containing 0.01 to 4.0% by mass of Ti is subjected to a heat treatment within 800 seconds at a temperature of 800 ° C. or higher. The first cold rolling is performed at a workability of less than 80%, the second solution treatment is performed at a temperature of 800 ° C. or higher for 240 seconds, and the second cold treatment is performed at a workability of less than 50%. A method for producing a titanium-copper alloy by performing hot rolling at a temperature of 300 to 700 ° C. and performing a heat treatment for 1 hour or more and less than 15 hours is disclosed. JP-A-7-258803 describes that a titanium-copper alloy having excellent bendability and stress relaxation characteristics can be obtained thereby.
[0005]
[Problems to be solved by the invention]
However, the conventional techniques described above have the following problems. When a plate material is formed from a titanium-copper alloy described in Japanese Patent Publication No. 62-39215 and Japanese Patent Laid-Open No. 7-258803, depending on the position in the width direction of the plate material, whether the measurement direction is the rolling direction or the orthogonal direction Therefore, mechanical properties such as bending workability and stress relaxation properties vary, and there is a problem that good mechanical properties cannot be obtained stably.
[0006]
This invention is made | formed in view of this problem, Comprising: It aims at providing the titanium copper alloy and its manufacturing method with uniform and favorable mechanical characteristics, such as a bending workability and a stress relaxation characteristic.
[0007]
[Means for Solving the Problems]
The titanium-copper alloy material according to the present invention has a composition containing 1.0 to 5.0% by mass of Ti with the balance being Cu and inevitable impurities, and the ratio of (crystal grain size deviation / average crystal grain size) The value of is not more than 0.60.
[0008]
In the present invention, the titanium-copper alloy material contains 1.0 to 5.0% by mass of Ti, and the value of the (crystal grain size deviation / average crystal grain size) ratio is 0.60 or less. By suppressing the precipitation of the β phase during the crystallization treatment and suppressing the variation in the size of the crystal grains, the mechanical characteristics can be made uniform and good.
[0009]
The method for producing a titanium-copper alloy material according to the present invention is as follows: 820 ° C. with respect to a member made of a titanium-copper alloy having a composition containing 1.0 to 5.0% by mass of Ti and the balance being Cu and inevitable impurities. first a step by facilities to solution treatment and the mean crystal grain size of 15μm or more of the member, the step of applying a first cold rolling at a working ratio of 50% or more to hold more temperature above 100 seconds And a step of performing a second solution treatment for heating to a temperature of 820 ° C. or higher at a rate of temperature increase of 1000 ° C./min or higher, a step of performing a second cold rolling at a processing rate of 5 to 85%, And an aging treatment for holding at a temperature of 350 to 480 ° C. for 2 to 10 hours.
[0010]
In the present invention, in the second solution treatment step, by heating to a temperature of 820 ° C. or higher at a temperature rising rate of 1000 ° C./min or higher, the β phase does not precipitate during the temperature rising, and the temperature is 820 ° C. or higher. When the temperature is reached, the titanium-copper alloy material becomes α single phase. Thereby, the segregation of Ti and the variation in crystal grain size due to the precipitation of β phase do not occur, the structure of the titanium-copper alloy material becomes uniform, and uniform and good mechanical properties can be obtained.
[0011]
In addition, by setting the temperature in the first solution treatment step to 820 ° C. or more and the holding time to 100 seconds or more, Ti is sufficiently dissolved in the matrix and recrystallization is promoted, and the average crystal grain size is increased. The structure can be 15 μm or more. Thereby, in the titanium copper alloy after the first solution treatment, the solid solution state of the structure and Ti can be made uniform. Further, by setting the processing rate in the first cold rolling step to 50% or more, nucleation can be promoted and sufficiently recrystallized in the second solution treatment step. Thereby, a uniform structure can be obtained in the second solution treatment step.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described with reference to the accompanying drawings. The titanium-copper alloy according to the embodiment of the present invention has a composition containing 1.0 to 5.0% by mass of Ti with the balance being Cu and inevitable impurities. The ratio of (crystal grain size deviation / average crystal grain size) ratio is 0.60 or less.
[0013]
The manufacturing method of the titanium copper alloy material which concerns on this embodiment is demonstrated. FIG. 1 is a flowchart showing a method for producing a titanium-copper alloy material according to the present embodiment. First, as shown in step S1 of FIG. 1, by melting, an ingot having a composition containing 1.0 to 5.0% by mass of Ti and the balance of Cu and inevitable impurities is produced. And as shown to step S2 thru | or S4 of FIG. 1, forging, hot rolling, and cold rolling are given to this ingot, for example, it processes into a board | plate material. Next, as shown in step S5, the plate material is held at a temperature of 820 ° C. or higher for 100 seconds or longer to perform a first solution treatment. At this time, the said temperature shall be 30 degreeC or more higher than the solid solution wire of this board | plate material, for example. As a result, Ti is sufficiently dissolved in the matrix and recrystallization occurs, resulting in a structure having an average crystal grain size of 15 μm or more. Then, this board | plate material is cooled to room temperature. Next, as shown in step S6, the first cold rolling is performed on the plate material at a processing rate of 50% or more. Thereby, in the 2nd solution treatment which is the next process, nucleation can be promoted.
[0014]
Next, as shown in step S7, this plate material is heated from room temperature to a temperature of 820 ° C. or higher at a rate of temperature increase of 1000 ° C./min or higher, and held at a temperature of 820 ° C. or higher for 5 seconds or longer, for example, 100 seconds or longer. Then, the second solution treatment is performed. At this time, the said temperature shall be 30 degreeC or more higher than the solid solution wire of this board | plate material, for example. Then, it cools to room temperature. And as shown to step S8, 2nd cold rolling is given with respect to this board | plate material with a processing rate of 5 to 85%. At this time, the processing rate is determined according to the target material and the final plate thickness. Next, as shown in step S9, the plate material is kept at a temperature of 350 to 480 ° C. for 2 to 10 hours and subjected to an aging treatment. Thereby, the said board | plate material carries out precipitation hardening. In this way, the titanium copper alloy material according to the present embodiment is produced.
[0015]
Hereinafter, the reason for the numerical limitation in each constituent requirement of the present invention will be described.
[0016]
Ti content: 1.0 to 5.0 mass%
Ti is added to precipitate and harden the copper alloy. When the Ti content is less than 1.0% by mass, the effect of precipitation hardening is small, and the strength of the titanium-copper alloy material is insufficient. On the other hand, when the Ti content exceeds 5.0 mass%, the workability of the titanium-copper alloy material decreases.
Therefore, the Ti content is 1.0 to 5.0 mass%. More preferably, it is 2.5 to 4.0% by mass.
[0017]
(Crystal grain size deviation / average crystal grain size) ratio value: 0.60 or less (Crystal grain size deviation / average crystal grain size) ratio value greater than 0.60 causes large crystal dispersion, and titanium Variation in bending workability of copper alloy material becomes large. Therefore, the value of (crystal grain size deviation / average crystal grain size) ratio is set to 0.60 or less.
[0018]
Heating temperature in the first solution treatment: 820 ° C. or higher If the heating temperature is lower than 820 ° C., the solid solution of Ti becomes insufficient and recrystallization becomes insufficient, and the average crystal grain size However, recrystallized grains of 15 μm or more are not generated. For this reason, the structure of the titanium copper alloy after the aging treatment becomes non-uniform. Therefore, the heating temperature in the first solution treatment is 820 ° C. or higher. More preferably, the temperature is 30 ° C. or more higher than the solid solution wire of the titanium-copper alloy material.
[0019]
Heating time in the first solution treatment: 100 seconds or more When the heating time is less than 100 seconds, the solid solution of Ti becomes insufficient and recrystallization becomes insufficient, and the average crystal grain size However, recrystallized grains of 15 μm or more are not generated.
For this reason, the structure of the titanium copper alloy after the aging treatment becomes non-uniform. Therefore, the heating time in the first solution treatment is 100 seconds or more.
[0020]
Average crystal grain size after first solution treatment: 15 [mu] m or more If the average crystal grain size is less than 15 [mu] m, the crystal structure becomes a mixed grain in which the crystal size varies. When the structure in this state is observed with a microscope, crystal grains having a grain size of about 1 to 10 μm are mixed. In such a state, solid solution Ti segregates. On the other hand, when the average crystal grain size is 15 μm or more, the crystal grain sizes are almost uniform, and Ti segregation can be suppressed. For this reason, the structure of the titanium-copper alloy material after the first solution treatment can be in a state in which the segregation of Ti suitable for the start condition of the second solution treatment is suppressed.
[0021]
Processing rate in the first cold rolling: 50% or more When the processing rate in the first cold rolling is less than 50%, the processing strain imparted to the titanium-copper alloy material becomes insufficient, and the second In the solution treatment of, sufficient nucleation does not occur. For this reason, recrystallization does not proceed sufficiently. Therefore, the processing rate in the first cold processing is 50% or more.
[0022]
Temperature rise rate in the second solution treatment: 1000 ° C./min or more When the temperature rise rate in the second solution treatment is less than 1000 ° C./min, β phase grain boundary precipitation during the temperature rise The reaction proceeds. For this reason, segregation of titanium and dispersion of crystal grains occur, the structure of the titanium-copper alloy material becomes non-uniform, and the value of (crystal grain size deviation / average crystal grain size) ratio becomes larger than 0.60. As a result, the mechanical properties of the titanium copper alloy material after the aging treatment become non-uniform. Therefore, the temperature increase rate in the second solution treatment is 1000 ° C./min or more.
[0023]
Heating temperature in the second solution treatment: 820 ° C. or higher If the heating temperature is lower than 820 ° C., solid solution of Ti becomes insufficient and recrystallization does not proceed sufficiently. In addition, a β phase is generated during the solution treatment. Thereby, the structure of the titanium copper alloy after the aging treatment becomes non-uniform. Therefore, the heating temperature in the second solution treatment is 820 ° C. or higher. More preferably, the temperature is 30 ° C. or more higher than the solid solution wire of the titanium-copper alloy material.
[0024]
Processing rate in second cold rolling: 5 to 85%
Cold rolling with a processing rate of less than 5% is technically difficult. On the other hand, even if the processing rate is larger than 85%, the effect of increasing the processing rate is saturated, and the characteristics are not improved any more, which is meaningless. Therefore, the processing rate in the second cold rolling is set to 5 to 85%.
[0025]
Heating temperature in aging treatment: 350 to 480 ° C
When the heating temperature in the aging treatment is less than 350 ° C., heating for a long time is required to precipitate Ti, and the production cost increases. On the other hand, when the heating temperature exceeds 480 ° C., precipitation of Ti becomes excessive, leading to a decrease in material strength. That is, the heating temperature in the aging treatment is set to 350 to 480 ° C. in order to efficiently strengthen the solid solution strengthening and precipitation strengthening of the titanium copper alloy material.
[0026]
Heating time in aging treatment: 2 to 10 hours When the heating time in aging treatment is less than 2 hours, precipitation of Ti becomes insufficient and the titanium-copper alloy material does not sufficiently precipitate and harden. On the other hand, when the heating time exceeds 10 hours, the strength of the titanium-copper alloy material decreases due to overaging. Therefore, the heating time in the aging treatment is 2 to 10 hours.
[0027]
Next, the relationship between the temperature increase rate and the structure in the second solution treatment will be described in more detail. FIG. 2 is a Cu—Ti phase diagram showing the phase state of the titanium-copper alloy, with the horizontal axis representing the Ti content in the titanium-copper alloy and the vertical axis representing the temperature. Further, FIG. 3 shows a constant temperature transformation diagram (TTT curve: time-temperature) showing the change in the structure of the titanium-copper alloy with the temperature rise, with the horizontal axis representing the time from the start of temperature rise and the vertical axis representing the temperature. -transformation diagram). In FIG. 3, lines A, B, C, and D indicate temperature changes in the process of heating from room temperature to, for example, 820 ° C. at a constant temperature increase rate, and then maintaining the temperature at 820 ° C., and line A is For example, the rate of temperature increase is 2000 ° C./min, line B indicates the rate of temperature increase of 1000 ° C./min, for example, line C indicates the rate of temperature increase of 670 ° C./min, line D Indicates a case where the temperature rising rate is, for example, less than 670 ° C./min, for example, 330 ° C./min.
[0028]
As shown in FIG. 2, a practical Cu-3 mass% Ti alloy, for example, an alloy having a Ti concentration of 3.2 mass%, is heated to a temperature of 790 ° C. or higher to form a matrix (matrix) made of Cu. Ti dissolves to form an α phase. However, FIG. 2 shows a stable state, and the time element is ignored. Actually, the structure varies depending on the temperature rising process to reach a solid solution state and the holding time after reaching a temperature of 790 ° C. or higher.
[0029]
When the temperature of the titanium-copper alloy material is raised from room temperature so that the temperature of the titanium-copper alloy material enters the two-phase separation region ((α + β) region shown in FIG. 2), Cu and Ti are formed in the matrix α-phase. The β phase is precipitated. However, in order for the β phase to precipitate, it is necessary that the Ti atoms dissolved in the matrix move and aggregate, and therefore, while the Ti atoms move the distance necessary for the β phase precipitation, It is necessary for the temperature of the titanium-copper alloy material to remain in the two-phase separation region. The moving distance of Ti atoms is determined by the moving speed and time, and the moving speed of Ti atoms is determined by the temperature. Therefore, the moving distance of Ti atoms depends on temperature and time.
[0030]
For this reason, as shown by lines A and B in FIG. 3, when the temperature rise rate of the titanium-copper alloy material is sufficiently high, Ti atoms are sufficiently present within the time when the temperature of the titanium-copper alloy material is in the two-phase separation region. Cannot move a long distance, and β phase does not precipitate. As a result, the structure of the titanium-copper alloy material heated to 790 ° C. or higher becomes an α single phase.
[0031]
On the other hand, as shown by lines C and D in FIG. 3, when the rate of temperature increase of the titanium-copper alloy material is slow, Ti atoms are sufficient within the time when the temperature of the titanium-copper alloy material is in the two-phase separation region. It moves a long distance and aggregates, and the β phase is precipitated. In this case, when the temperature of the titanium-copper alloy material passes through the two-phase separation region and reaches the α single phase region, the generated β phase is re-dissolved. However, the re-dissolution of the phase once precipitated requires a heat energy higher than that required for agglomeration, so re-solution does not proceed easily. Actually, even when the temperature of the titanium-copper alloy material reaches 820 ° C., the β phase still remains. If the β phase remains in the second solution treatment, solid solution Ti in the titanium-copper alloy material is precipitated in the β phase, and Ti does not uniformly dissolve. In addition, the precipitation of the β phase increases the variation in the crystal grain size of the titanium-copper alloy material, resulting in a non-uniform structure. As a result, the mechanical properties of the titanium-copper alloy material become non-uniform.
[0032]
The β phase precipitated in the temperature raising process can be extinguished by maintaining the titanium-copper alloy material at a temperature of 820 ° C. for a long time or by increasing the heating temperature of the titanium-copper alloy material. However, if the holding time is lengthened, in the actual manufacturing process, the processing time is lengthened or one step is added for holding, so the manufacturing cost of the titanium-copper alloy material is remarkably increased. Not realistic. In addition, increasing the heating temperature not only increases the energy cost, but also increases the size of the α-phase crystal grains, which adversely affects the strength and bendability of the titanium-copper alloy material. .
[0033]
For the above reasons, in order to produce a highly uniform titanium-copper alloy material, the present inventors need not to precipitate the β phase in the second solution treatment, and for that purpose, FIG. It has been found that a temperature increase rate equal to or higher than the temperature increase rate shown in line B of FIG. As will be described later, the present inventors have as a result of experimentation found that the temperature rising rate at which the β phase is not precipitated is 1000 ° C./min or more.
[0034]
In addition, although the β phase may precipitate during the temperature decrease in the second solution treatment, the β phase precipitated during the temperature decrease does not affect the growth of crystal grains. Don't be. In addition, in the temperature decreasing step of the second solution treatment, precipitation of β phase can be prevented by quenching with water cooling or the like. Thereby, the effect of the aging process which is a post process can fully be drawn out.
[0035]
As described above, in the present embodiment, in the second solution treatment, the plate material made of titanium copper alloy is heated to a temperature of 820 ° C. or higher at a temperature increase rate of 1000 ° C./min or higher. Thereby, it can suppress that beta phase precipitates during temperature rising. As a result, Ti can be prevented from segregating in the β phase, and Ti can be uniformly dissolved. Further, it is possible to prevent the crystal grains from being dispersed due to the precipitation of the β phase.
[0036]
Further, in the first solution treatment, the plate material is held at a temperature of 820 ° C. or more for 100 seconds or more, Ti is sufficiently dissolved in the matrix and recrystallized, and in the first cold rolling, 50% or more. Since the processing strain is imparted by rolling at the processing rate of 2, it can be sufficiently recrystallized in the second solution treatment.
[0037]
As a result, the structure after the second solution treatment can be made uniform, and the value of (crystal grain size deviation / average crystal grain size) ratio can be made 0.60 or less. Thereby, the structure | tissue of the titanium copper alloy material after an aging treatment can be equalize | homogenized.
[0038]
The processing strain accumulated in the grain boundaries of the β phase and the irregular crystal grains has a low binding force and is often released by low thermal energy. On the other hand, the processing strain accumulated in a uniform and non-β phase structure is restrained by a strong and uniform restraining force, and is difficult to be released with low thermal energy. For this reason, the material having such a structure is less likely to relieve stress and has good stress relieving properties.
[0039]
Further, by making the structure of the titanium-copper alloy material uniform, the mechanical properties of the titanium-copper alloy material can be made uniform. For materials with non-uniform mechanical properties, parts with good characteristics and inferior parts are mixed microscopically, and when stress is applied from the outside, this stress concentrates on parts with inferior characteristics. The overall macro characteristics are low. On the other hand, the titanium-copper alloy material according to the present embodiment has a uniform structure and characteristics, and thus has excellent macro mechanical characteristics such as bending workability.
[0040]
Thus, according to this embodiment, a titanium copper alloy material with uniform and good bending workability and stress relaxation characteristics can be produced. As a result, it is possible to obtain a titanium-copper alloy material with little variation in mechanical properties and good stability.
[0041]
【Example】
Hereinafter, the effect of the embodiment of the present invention will be specifically described in comparison with a comparative example that deviates from the scope of the claims. First, an ingot having a composition containing 3.2% by mass of Ti and the balance of Cu and inevitable impurities was prepared by melting. Next, forging, hot rolling, and cold rolling were sequentially performed on the ingot to produce a plate material having a thickness of 1.0 mm. Next, this board | plate material was heated to the temperature of 900 degreeC, and it hold | maintained at this temperature for 120 second, and performed the 1st solution treatment. Next, it cooled to room temperature and performed the 1st cold rolling on the conditions whose processing rate is 60%. And the board | plate material after this rolling was heated to 840 degreeC, making temperature rising speed mutually different, and it hold | maintained at the temperature for 120 second, and performed the 2nd solution treatment. Table 1 shows the heating rate at this time. Next, the plate material was cooled with water and cooled to room temperature, and second cold rolling was performed under the condition of a processing rate of 50%. Then, an aging treatment was performed under the conditions of a temperature of 420 ° C. and a time of 3 hours to produce a titanium copper alloy material. The thickness of the titanium copper alloy material after the aging treatment was 0.20 mm.
[0042]
Next, the crystal grain size and bending workability of the titanium-copper alloy material thus produced were measured. The crystal grain size was measured by the “cutting method” defined by JIS H0501-1986 “Copper grain size test method”. At this time, the number of crystal grains cut by a line segment of a known length in the cutting method was about 100. The average value was calculated by repeating this cutting method several times. Based on the measurement result, the deviation of the crystal grain size and the average grain size were calculated, and the value of (crystal grain deviation / average crystal grain size) ratio was determined. Table 1 shows the measurement results of the crystal grain size. 4 (a) and 4 (b), FIGS. 5 (a) and 5 (b), FIGS. 6 (a) and 6 (b), and FIGS. It is an optical microscope photograph which shows the structure | tissue of each sample of A, B, C, and D, (a) of each figure is a photograph with a magnification of 130 times, (b) is a photograph with a magnification of 670 times.
[0043]
Regarding the bending workability, a 90 ° bending test was performed by the “V block method” defined by JIS Z2248-1996 “Metal material bending test method”, and a 180 ° bending test was performed by the “push bending method”. The evaluation results of bending workability are shown in Table 1. In addition,
“GW” and “BW” shown in Table 1 are terms indicating the rolling direction of a sample that is usually used in the field of copper products, and “GW” is the longitudinal direction of the sample, that is, the bending direction is parallel to the rolling. “BW” indicates that the longitudinal direction of the sample is the rolling orthogonal direction. “R / t” shown in Table 1 is a value of {(minimum bending radius at which the sample does not break) / (sample thickness)}.
[0044]
[Table 1]
No. shown in Table 1. A and No. B is an example of the present invention. Example No. A and B have a temperature increase rate of 1000 ° C./min or more in the second solution treatment, and all other production conditions also satisfy the provisions of the present invention. Therefore, (crystal grain size deviation / average crystal grain size) ) The ratio value was 0.60 or less, so that the variation in bending workability was small and good. In contrast, No. 1 shown in Table 1. C and D are comparative examples. Comparative Example No. C and D have a ratio of (crystal grain size deviation / average crystal grain size) ratio larger than 0.60 because the rate of temperature rise in the second solution treatment is less than 1000 ° C./min. In the sample in which is in the direction perpendicular to the rolling, the bending workability was inferior.
[0046]
【The invention's effect】
As described above in detail, according to the present invention, by setting the rate of temperature rise in the second solution treatment to 1000 ° C./min or more, precipitation of β phase can be suppressed, the structure is uniform, and the mechanical properties are excellent. Titanium copper alloy material can be obtained.
[Brief description of the drawings]
FIG. 1 is a flowchart showing a method for manufacturing a titanium-copper alloy material according to an embodiment of the present invention.
FIG. 2 is a Cu—Ti phase diagram showing the phase state of the titanium-copper alloy with the horizontal axis representing the Ti content in the titanium-copper alloy and the vertical axis representing the temperature.
FIG. 3 is a constant temperature transformation diagram showing a change in structure accompanying a temperature increase of a titanium-copper alloy, with the horizontal axis representing the time from the start of temperature increase and the vertical axis representing the temperature.
4 (a) and (b) show Example Nos. It is a drawing substitute photograph which shows the structure | tissue of the sample of A (an optical micrograph: (a) 130-times magnification, (b) 670-times magnification).
5 (a) and 5 (b) show Example Nos. It is a drawing substitute photograph showing the structure of the sample of B (optical micrograph: (a) magnification 130 times, (b) magnification 670 times).
6 (a) and (b) are comparative example Nos. It is a drawing-substituting photograph showing the structure of the sample of C (optical micrograph: (a) magnification 130 times, (b) magnification 670 times).
7 (a) and (b) are comparative example Nos. It is a drawing-substituting photograph showing the structure of the sample of D (optical micrograph: (a) magnification 130 times, (b) magnification 670 times).
[Explanation of symbols]
A, B, C, D: lines indicating temperature changes
Claims (6)
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| JP5170881B2 (en) * | 2007-03-26 | 2013-03-27 | 古河電気工業株式会社 | Copper alloy material for electrical and electronic equipment and method for producing the same |
| JP4563480B2 (en) * | 2008-11-28 | 2010-10-13 | Ｄｏｗａメタルテック株式会社 | Copper alloy sheet and manufacturing method thereof |
| JP5226057B2 (en) * | 2010-10-29 | 2013-07-03 | Ｊｘ日鉱日石金属株式会社 | Copper alloys, copper products, electronic components and connectors |
| JP6368518B2 (en) * | 2014-03-28 | 2018-08-01 | Ｄｏｗａメタルテック株式会社 | Cu-Ti copper alloy sheet, method for producing the same, and energized component |
| JP6310130B1 (en) | 2017-09-22 | 2018-04-11 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| JP6310131B1 (en) | 2017-09-22 | 2018-04-11 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| CN115011823B (en) * | 2022-06-28 | 2023-04-18 | 沈阳有色金属研究所有限公司 | Processing method of Cu-Ni-Sn alloy product |
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