JP3634257B2 - Ni diffusion-plated steel sheet manufacturing method and steel sheet - Google Patents
Ni diffusion-plated steel sheet manufacturing method and steel sheet Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、Ｎｉ拡散メッキ層が軟質でプレス加工時の塑性加工性、加工後の耐食性に優れ、更に、優れた光沢度のミラーブライト表面を有するＮｉ拡散メッキ鋼板の製造方法および鋼板に関するものである。
【０００２】
【従来の技術】
Ｎｉメッキ後、 熱処理を施すＮｉ拡散メッキ鋼板の製造方法としては、 文献−１（大村等、大村英雄： 東洋鋼鈑，２９（１９９１），ｐ４３）、特開昭６１−２３５５９４号公報、特開平６−２１０４号公報の方法がある。これらのいずれの方法においても、 Ｎｉメッキ後熱処理を施すことによって、 Ｎｉメッキ層が再結晶すると共に軟質化し、プレス加工後においてもＮｉメッキ層の良好な塑性加工性が確保され、 優れた耐食性が得られるのであるが、 本発明が目標とする光沢度の良好なＮｉ拡散メッキ鋼板は得られない。
【０００３】
文献−１は、 該社のＮｉメッキ鋼板の製造品種の製造法とその特性を紹介したものである。 同文献は、 「Ｎｉ拡散メッキ法はブライトとダル仕上げ表面（文献ではｂｒｉｇｈｔ ａｎｄ ｄｕｌｌ ｆｉｎｉｓｈと記載） の製品が製造でき、 本発明が目標とするミラーブライト表面を有する光沢度の優れたＮｉメッキ鋼板は、 半光沢Ｎｉメッキ層の上に光沢Ｎｉメッキを施してミラーブライト（文献ではｍｉｒｒｏｒ−ｌｉｋｅ Ｉｕｓｔｒｏｕｓ ｓｕｒｆａｃｅと記載）表面の製品が造れること（ 熱拡散処理無しの２重めっき処理） が、 また、 硫黄が添加される光沢メッキは、 硫黄がＮｉメッキ層中に吸着され、 その後の拡散熱処理時に硫黄の影響でＮｉ拡散メッキ層が脆化する。 従って、 光沢メッキには熱拡散処理の適用は困難である。」を明らかにしている。
【０００４】
また、 特開平６−２１０４号公報は、 文献−１とほぼ同じ技術に基づいたものでブライト或はダルの表面仕上げのものはできる技術を開示しているが、ミラーブライト表面のＮｉ拡散メッキ鋼板の開示はない。 更に、 特開昭６１−２３５５９４号公報も同様にミラーブライト表面のＮｉ拡散メッキ鋼板の開示はない。
尚、特開平１０−２８０１８４号公報には、本発明と目的を同じくする発明が開示され、最も高い光沢度のものは、調質圧延ロールを硬質Ｃｒロールにすることによって、最高で、光沢度が１０２０が得られている実施例が示されているが、硬質Ｃｒメッキロールを使わねばならず製造コストが高くなる。
【０００５】
以上、 上述のように、 本発明が狙いとするＮｉメッキ層が軟質でプレス加工時の塑性加工性に優れ加工後の耐食性にも優れた光沢度が１０２０超のミラーブライト表面を有するＮｉ拡散メッキ鋼板はなく、又、製造コストの高い硬質Ｃｒメッキロールを使用しないで通常の調質圧延ロールで９５０以上の良好な光沢度を有する鋼板の製造方法もない。
【０００６】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、 Ｎｉ拡散メッキ層が軟質でプレス加工時の塑性加工性、加工後の耐食性に優れ、更に、優れた光沢度のミラーブライト表面を有するＮｉ拡散メッキ鋼板の製造方法および鋼板を提供することである。
【０００７】
【課題を解決するための手段】
本発明者らは、 Ｎｉ拡散メッキ層が軟質でプレス加工時の塑性加工性に優れ加工後の耐食性にも優れたミラーブライト表面を有する光沢度の優れたＮｉ拡散メッキ鋼板の製造方法および鋼板を提供することについて、 鋭意検討を行い本発明を完成したものであり、 その要旨とするところは下記の通りである。
（１）通常の製法で造られた熱延鋼板を酸洗後、冷間圧延を行うに当り、少なくとも最終スタンドの圧延ロールをＲａ：０．３〜２．０μｍのダルロールを用い冷間圧延鋼板を製造し、脱脂、 酸洗を経て、 Ｎｉメッキを行うに当り、 無光沢或は半光沢Ｎｉメッキ浴で浴中のＳ濃度を規制し、 Ｎｉメッキ層中のＳ含有量を０．０５％以下に制御した５〜５０ｇ／ｍ２ のＮｉメッキ鋼板を製造した後、 ６５０℃以上で再結晶焼鈍とＮｉメッキ層の合金化拡散熱処理を行い、 その後、 表面粗さＲａが０．０７μｍ以下のロールでの伸び率が１．３％以上でドライ調質圧延を施すことを特徴とする光沢度が９５０超のミラーブライト表面を有し、 最表層のＦｅ濃度が５０％以下であることを特徴とする塑性加工性と耐食性に優れたＮｉ拡散メッキ層を有するＮｉ拡散メッキ鋼板の製造方法。
【０００８】
（２）通常の製法で造られた熱延鋼板を酸洗後、冷間圧延を行うに当り、少なくとも最終スタンドの圧延ロールをＲａ：０．３〜２．０μｍのダルロールを用い冷間圧延鋼板を製造し、再結晶焼鈍後、必要に応じ調質圧延を施し、その後、Ｎｉメッキを行うに当り、 無光沢或は半光沢Ｎｉメッキ浴で浴中のＳ濃度を規制し、 Ｎｉメッキ層中のＳ含有量を０．０５％以下に制御した５〜５０ｇ／ｍ２ のＮｉメッキ鋼板を製造した後、 ５５０℃以上でＮｉメッキ層の合金化拡散熱処理を行い、 その後、 表面粗さＲａが０．０７μｍ以下のロールでの伸び率が１．３％以上でドライ調質圧延を施すことを特徴とする光沢度が９５０超のミラーブライト表面を有し、 最表層のＦｅ濃度が５０％以下であることを特徴とする塑性加工性と耐食性に優れたＮｉ拡散メッキ層を有するＮｉ拡散メッキ鋼板の製造方法。
【０００９】
（３）前記（１）または（２）記載のＮｉ拡散メッキ鋼板の製造法において、 Ｎｉメッキ後の調質圧延工程での、Ｒａが０．０７以下のロールでの伸び率が１．８％以上で、 ドライ調質圧延を施すことを特徴とする光沢度が１０２０超であるＮｉ拡散メッキ鋼板の製造方法。
（４）前記（１）〜（３）のＮｉ拡散メッキ鋼板の製造法において、Ｎｉメッキ後の調質圧延を施すに当り、 少なくともＲａ：０．０７μｍ以下のロールが硬質Ｃｒメッキロールであることを特徴とする光沢度が１０２０超のＮｉ拡散メッキ鋼板の製造方法。
【００１０】
（５）Ｎｉのめっき量が５〜５０ｇ／ｍ２ で、 熱処理によりそのＮｉメッキ層の少なくとも一部がＦｅ−Ｎｉ合金層を形成しているＮｉ拡散メッキ鋼板において、 Ｎｉ拡散メッキ層のＳ含有量が０．０５％以下で、 且つ、 Ｎｉ拡散メッキ層が圧延ロールで平滑化された光沢度が１０２０超のミラーブライト表面を有し、 最表層のＦｅ濃度が５０％以下であることを特徴とする塑性加工性と耐食性に優れたＮｉ拡散メッキ鋼板である。
尚、本発明では、Ｎｉ拡散メッキ層とは、焼鈍によって延性が向上した「純Ｎｉメッキ層＋Ｆｅ−Ｎｉ拡散メッキ層」或いは、「Ｆｅ−Ｎｉ拡散メッキ層」をさす。又、Ｎｉ拡散メッキ鋼板とは、上記のＮｉ拡散メッキ層を有する鋼板をさす。
【００１１】
以下に本発明について詳細に述べる。
本発明者らは、 まず、 Ｎｉメッキ後、 熱処理を施すＮｉ拡散メッキ層が優れた塑性加工性を有し、且つ耐食性にも優れたＮｉ拡散メッキ鋼板について、 種々の検討を行った。Ｎｉ拡散メッキ層の塑性加工性について、 再結晶焼鈍を施していない冷間圧延後のＩＦ鋼に、 無光沢、 半光沢、 光沢Ｎｉメッキを施し、 ２６．４ｇ／ｍ２ のＮｉメッキ鋼板を施し、 連続焼鈍で焼鈍温度時間を変え拡散状態を変えた種々のＮｉ拡散メッキ鋼板に１．０％の調質圧延を施した試験片を造り、 Ｎｉメッキ層中のＳ含有量とＮｉ拡散メッキ最表層のＦｅ濃度とを測定すると共に、 試験片を円筒深絞り加工を行い側壁部のＮｉ拡散メッキ層表面を倍率２００倍で走査型顕微鏡でＮｉ拡散メッキ層にクラックが入っているか否かの観察（以下、Ｎｉ拡散メッキ層の割れ評価試験と記す） と、 絞り缶を塩水噴霧試験（５％塩水、３５℃、６Ｈｒ．：以下、単にＳＳＴ試験という） を行い赤錆発生率（面積％）の調査を行った。
【００１２】
絞り加工後の側壁のＮｉ拡散メッキ層の割れ性は、１）Ｎｉ拡散メッキ層中のＳ含有率が０．０５％超になると割れが発生し始めることが明らかとなりＮｉ拡散メッキ層中のＳ含有率は少なくとも０．０５％以下でなければ良好な塑性加工性を有するＮｉ拡散メッキ層が得られないことが判明した。 ２）Ｎｉ拡散メッキ層の最表層まで拡散してきたＦｅの含有率は、 少なくとも５０％以下でなければならないことが判明した。 尚、 本発明の場合は、Ｎｉ拡散メッキ層の最表層のＦｅ含有率が５０％まで良好な塑性加工性が得られる理由はＮｉ拡散メッキの拡散条件が連続焼鈍で均熱時間が１０〜１２０ｓｅｃと短いことに起因しているものと思われる。
【００１３】
絞り缶のＳＳＴ試験での赤錆発生率は、 Ｎｉ拡散メッキ層の健全性で整理できＮｉ拡散メッキ層が割れていなければ良好な加工後の耐食性が得られず、 優れた加工後の耐食性を得るには、 Ｎｉ拡散メッキ最表層の拡散してきたＦｅの含有率は、 少なくとも５０％以下にする必要がある。
Ｎｉメッキは、 良好な耐食性とメッキ層の加工性を得るには、 少なくとも、 無光沢或は半光沢ＮｉメッキでＳ含有量が０．０５％以下で、 Ｎｉメッキ目付量が５ｇ／ｍ２ 以上に規制しなければならない。 Ｎｉ目付量が５ｇ／ｍ２ 未満では、 Ｎｉメッキ後拡散処理を行った場合でも目付量が少なすぎピンホール欠陥を防止できなくなり耐食性が確保できなくなる。
【００１４】
次に、 本発明者らは、 Ｎｉ拡散メッキ層が軟質でプレス加工時の塑性加工性に優れ加工後の耐食性にも優れ、 且つ、ミラーブライト表面を有する光沢度の優れたＮｉ拡散メッキ鋼板の製造方法および鋼板を提供することについて検討を行った。本発明者らは、 特開平１０−２８０１８４号公報と同様に、上述の検討において、 一般的に行われている光沢Ｎｉメッキはメッキ層中にＳが含有されるため、 Ｎｉ拡散メッキ層が脆くなりプレス加工時に剥離すること、またプレス加工後の耐食性も劣化すると言う問題を有していることが明らかとなったので、 無光沢メッキ後拡散処理を行いその上に光沢Ｎｉメッキを行うことを検討した。 その結果、 優れた光沢度が得られプレス加工後の耐食性も確保できるが、 表層の光沢メッキは熱処理が成されていないため硬く脆いのでプレス加工時に光沢メッキ部が割れ剥離脱落しやすいことが判明した。 また、 この方法は２重メッキを施す必要があり製造コストも高くなる。
【００１５】
そこで、 本発明者らは、 特開平１０−２８０１８４号公報の請求項６の硬質Ｃｒメッキロールで調質圧延で得られる良好な光沢度のＮｉ拡散メッキ鋼板を、製造コストの安い通常のミラーブライトロールで製造する方法、および、光沢度が１０２０超の更に優れたＮｉ拡散メッキ鋼板並びに製造方法を種々検討し、本発明の鋼板および製造方法を見出した。
通常のミラーブライトロールを用いた調質圧延方法で更に優れたミラーブライト表面光沢を得る方法について、種々検討した結果、特開平１０−２８０１８４号公報のような調質圧延方法のみでは達成が困難で、冷間圧延時のタンデム圧延の少なくとも最終スタンドのロールを、通常使用されているスムースロールから、Ｒａが０．３〜２．０μｍのダルロールにすることが必要であることを見いだした。
【００１６】
即ち、より光沢度の優れたＮｉ拡散メッキ鋼板を得るには、冷間圧延ロールよりも平滑なロールにするのが好ましいと考えられるが、結果は逆で、より粗いダルロールとすることで、特開平１０−２８０１８４号公報の発明の効果を更に向上させることが可能であることを見いだしたのである。
本発明者等は、その原因を究明した結果、スムースロールで冷間圧延を施すと、冷間圧延の後段でロールがスリップしたり焼き付いてできるスリップ痕が全面に多数発生し、ミラーブライトロールを用いた調質圧延でもそのスリップ痕が除去できず残るため到達する光沢度に限界があるが、ダルロールではスリップ痕が入らず、金属光沢をした冷間圧延鋼帯ができ、その後のミラーブライトロールを用いた調質圧延でより高いレベルの光沢度が得られることを見いだした。又、更に、製造コストは高くなるが、硬質Ｃｒメッキのミラーブライトロールで調質圧延を施すと、更に光沢度が向上し１０５０以上の極めて優れた光沢度が得られることも見いだした。
【００１７】
【発明の実施の形態】
以下に、本発明の構成条件の詳細な説明を行う。
対象となるＮｉ拡散メッキ鋼板は、 ５ 〜５０ｇ／ｍ２ 厚みのＮｉ拡散メッキ鋼板で、 メッキ厚みが５ｇ／ｍ２ 未満では処理中に地鉄からのＦｅの拡散が速くＮｉ最表層にＦｅ濃度が５０％を越えやすくなるとともに、５ｇ／ｍ２ 未満ではＮｉメッキ時のピンホールが多くなり耐食性が劣化するので５ｇ／ｍ２ 以上に規制する必要がある。 又、 上限を５０ｇ／ｍ２ としたのは、 耐食性の向上効果が飽和しかつ電気メッキで５０ｇ／ｍ２ 超のメッキを施すには製造コストが高くなりするので、 上限値を５０ｇ／ｍ２ とした。
【００１８】
下地の鋼板は、 Ｎｉメッキを施せるものであれば特に限定する必要がないが、 冷間圧延時に、少なくとも最終スタンドの圧延ロールをＲａ：０．３〜２．０μｍのダルロールを用いて冷間圧延された未再結晶の鋼板を用いる必要がある。
尚、 再結晶焼鈍後の鋼板でも更に調質圧延後の鋼板でも同等の品質が得られるが焼鈍を２ 回行うことになるので経済的には未再結晶板にＮｉメッキを行う１回焼鈍法が好ましい。
【００１９】
Ｎｉメッキ条件は、 例えばワット浴のような通常行われているメッキ方法で、 無光沢或は半光沢ＮｉメッキでＮｉメッキ層中のＳ含有量が０．０５％以下に規制し、 Ｎｉメッキ目付量を５ｇ／ｍ２ 以上にしなければならない。 絞り加工後の側壁のＮｉメッキ層の割れ性は、メッキ層中のＳ含有率が０．０５％超になると割れが発生し始めるようになるのでＮｉメッキ層中のＳ含有率は少なくとも０．０５％以下でなければならない。 尚、 Ｎｉ目付量が５〜５０ｇ／ｍ２ でなければならない理由は上述の通りである。
【００２０】
鋼板自体の再結晶焼鈍を兼ねたＮｉ拡散熱処理は、 連続焼鈍炉で６５０℃以上で、鋼板の再結晶焼鈍とＮｉメッキ層の合金化拡散熱処理とを行う必要がある。又、２回焼鈍法の場合は、鋼板の再結晶焼鈍を行い、Ｎｉメッキを施し、その後、Ｎｉ拡散熱処理を５５０℃以上で連続焼鈍或いは箱焼鈍で行えばよい。但し、箱焼鈍法の場合には焼鈍時間が非常に長いのでＮｉ−Ｆｅの相互拡散の距離が長すぎＮｉメッキ層の最表層のＦｅ濃度が５０％超にならないようにする必要がある。この拡散処理により、Ｎｉ拡散メッキ層の塑性加工時並びに耐食性がすぐれたものになる。
【００２１】
調質圧延条件は， 表面粗さＲａが０．０７μｍ以下のロールで、 伸び率が１．３％以上になるように行わなければならない。又、１０２０超の優れた光沢度を得るには、表面粗さＲａが０．０７μｍ以下のロールで、 全伸び率を１．８％以上でなければならない。又、調質圧延ロールを硬質Ｃｒメッキロールとするときは、硬質Ｃｒメッキロールでの伸び率を１．３％以上にすると１０２０超の光沢度が得られ、更に、硬質Ｃｒメッキロールでの伸び率を１．８％以上にすると１０５０超の極めて優れた光沢度が得られる。
以上の製造方法で得られためっき量が５〜５０ｇ／ｍ２ 、Ｎｉ拡散メッキ層中のＳ含有量が０．０５％以下で、 且つ、 Ｎｉ拡散メッキ層が圧延ロールで平滑化され光沢度の優れたミラーブライト表面を有し、 最表層のＦｅ濃度が５０％以下であるＮｉ拡散メッキ鋼板は、優れた光沢とＮｉ拡散メッキ層の優れた塑性加工性と耐食性とを両立させることができる。
【００２２】
【実施例】
以下に本発明の効果を実施例により説明する。
表１および表２に示す組成、 熱延、冷延条件で０．２６ｍｍ厚みの冷間圧延コイルを製造し、表２に示す条件で、アルカリ脱脂、 酸洗後ワット浴でのＮｉメッキ、鋼板の再結晶焼鈍を兼ねたＮｉ拡散熱処理或いは、鋼板の再結晶焼鈍後ＮｉメッキおよびＮｉ拡散熱処理を行い、表３に示す調質圧延を施しＮｉ拡散メッキ鋼板を試作した。試作したＮｉ拡散メッキ鋼板の品質を調査するため、 前述と同様の条件で、 光沢度、 Ｆｅ濃度（Ｆｅ／Ｆｅ＋Ｎｉ比％）、円筒絞り加工後の側壁外面をＳＥＭ観察し評価したＮｉ拡散メッキ層の割れ（０：割れ無し、 ×： 割れ発生）、胴缶外側面のＳＳＴ耐食試験後の赤錆発生面積率％を調査し、 その結果を表３に示す。
【００２３】
【表１】
【表２】
【表３】
供試鋼Ａは、 Ｃ含有量が０．００１９％で、Ｔｉを０．０３５％、Ｎｂを０．００８％、Ｂを０．０００３％添加したＮｂ−Ｔｉ添加極低炭素鋼で、軟質で深絞り性に優れた特性が得られる鋼である。
供試鋼Ｂは、 Ｃ含有量が０．０４０％のブリキ原板として一般に用いられるＡｌ−Ｋ鋼である。
試料Ｎｏ．１，２は、特開平１０−２８０１８４号公報の従来例で、絞り缶のＮｉメッキ層の割れ、赤錆の発生はなく、光沢度も８５０，８００とまずまずではあるが、本発明の目標とするレベルには未達である。
【００２７】
試料Ｎｏ．３，４−１は本発明の請求項２の実施例で、 光沢度も１０２５，１０４０と優れた値が得られている。
試料Ｎｏ．４−２は、調質圧延ロールを硬質ＣｒメッキしたＭＢ（ミラーブライト）仕様のＲａが０．０４μｍの調質圧延ロールで２．０％の調質圧延を行った本請求項４、５の実施例で、１１００の極めて優れた光沢度が得られている。
試料Ｎｏ．４−３は、タンデムロールをダルロールとした本発明の冷間圧延条件であるが、調質圧延ロールをＲａ：０．１０μｍのブライトロールとした比較例で、光沢度は８００にとどまっている。
【００２８】
試料Ｎｏ．５は、冷間圧延時のロールがダルロールであるがＲａが３．５０μｍと粗すぎた比較例で、目標の９５０以上の光沢度が得られていない。
試料Ｎｏ．６は、低炭Ａｌ−Ｋ鋼を用いた本発明の実施例で、良好な光沢度が得られている。
試料Ｎｏ．７は、冷間圧延時のロールを硬質Ｃｒメッキのダルロールを使用した本発明の実施例で、光沢度が１０９０と極めて優れた値が得られている。
【００２９】
試料Ｎｏ．８，９は、何れも２回焼鈍方式の本発明の実施例で、良好な光沢度並びに絞り缶のＮｉメッキ層の割れおよび赤錆発生のないＮｉメッキ鋼板が得られた。
試料Ｎｏ．１０は、冷間圧延ロールがスムースロールで、且つメッキ層中のＳ濃度が本発明の限度を超えた比較例で、光沢度が未達で、絞り加工後のＮｉ拡散メッキ層が割れ、そして耐食性が劣悪となっている。
以上の実施例の結果から明らかなように、 本発明の方法によって、 「Ｎｉ拡散メッキ層が軟質でプレス加工時の塑性加工性，加工後の耐食性に優れ、更に、優れた光沢度のミラーブライト表面を有するＮｉ拡散メッキ鋼板の製造方法および鋼板を提供すること」が十分に達成できる。
【００３０】
【発明の効果】
以上の実施例の結果から明らかなように、 本発明の方法によって、 本発明が解決しようとする課題の、 「Ｎｉ拡散メッキ層が軟質でプレス加工時の塑性加工性、加工後の耐食性に優れ、更に、優れた光沢度のミラーブライト表面を有するＮｉ拡散メッキ鋼板の製造方法および鋼板を提供すること」が十分に達成でき、 工業的価値が極めて大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a Ni diffusion-plated steel sheet having a mirror bright surface with excellent gloss, a Ni diffusion-plated layer that is soft and excellent in plastic workability during post-processing and corrosion resistance after processing, and a steel sheet. is there.
[0002]
[Prior art]
As a method for producing a Ni diffusion-plated steel sheet that is subjected to heat treatment after Ni plating, literature-1 (Omura et al., Hideo Omura: Toyo Kohan, 29 (1991), p43), JP-A-61-235594, 6-2104. In any of these methods, the Ni plating layer is recrystallized and softened by performing heat treatment after Ni plating, and good plastic workability of the Ni plating layer is ensured even after pressing, and excellent corrosion resistance is achieved. Although it is obtained, the Ni diffusion plated steel sheet having a good gloss level targeted by the present invention cannot be obtained.
[0003]
Reference-1 introduces the manufacturing method and characteristics of the Ni-plated steel sheet manufactured by the company. The Ni-plated steel plate with excellent glossiness that has the mirror bright surface targeted by the present invention can manufacture products with bright and dull finish surfaces (described in the literature as bright and double finish). It is possible to produce a product with a mirror bright (described as “mirror-like Iustrous surface” in the literature) with a bright Ni plating on a semi-gloss Ni plating layer (double plating without thermal diffusion treatment). In bright plating to which sulfur is added, sulfur is adsorbed in the Ni plating layer, and the Ni diffusion plating layer becomes brittle due to the influence of sulfur during the subsequent diffusion heat treatment. It is clarified.
[0004]
Japanese Laid-Open Patent Publication No. 6-2104 discloses a technology that is based on almost the same technology as that of Literature-1 and can be bright or dull surface-finished. There is no disclosure. Further, Japanese Patent Application Laid-Open No. 61-235594 does not disclose a Ni diffusion plated steel sheet on the mirror bright surface.
Japanese Patent Application Laid-Open No. 10-280184 discloses an invention having the same object as the present invention. The highest glossiness is obtained by changing the temper rolling roll to a hard Cr roll. Although an example in which 1020 is obtained is shown, a hard Cr plating roll must be used, which increases the manufacturing cost.
[0005]
As described above, the Ni diffusion plating having a mirror bright surface having a glossiness of more than 1020 and excellent in soft workability during press working and excellent in corrosion resistance after working as described above. There is no steel plate, and there is no method for producing a steel plate having a good glossiness of 950 or more with a normal temper rolling roll without using a hard Cr plating roll having a high production cost.
[0006]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that the Ni diffusion plating layer is soft and excellent in plastic workability at the time of press processing, excellent corrosion resistance after processing, and manufacturing a Ni diffusion plated steel plate having a mirror bright surface with excellent glossiness. It is to provide a method and a steel sheet.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have disclosed a method for producing a Ni diffusion-plated steel sheet having excellent glossiness and a steel sheet having a mirror bright surface having a Ni diffusion plating layer that is soft and excellent in plastic workability during press processing and excellent in corrosion resistance after processing. The present invention has been completed by earnestly examining the provision, and the gist of the present invention is as follows.
(1) After pickling a hot-rolled steel sheet produced by a normal manufacturing method and performing cold rolling, at least the rolling roll of the final stand is a cold-rolled steel sheet using a dull roll of Ra: 0.3 to 2.0 μm. In the Ni plating after degreasing and pickling, the S concentration in the bath is regulated with a matte or semi-gloss Ni plating bath, and the S content in the Ni plating layer is 0.05% After manufacturing a Ni-plated steel sheet of 5 to 50 g / m 2 controlled as described below, recrystallization annealing and alloying diffusion heat treatment of the Ni plating layer are performed at 650 ° C. or higher, and then the surface roughness Ra is 0.07 μm or less. It has a mirror bright surface with glossiness of over 950, characterized by performing dry temper rolling with a roll elongation of 1.3% or more, and Fe concentration of the outermost layer is 50% or less Ni diffusion plating with excellent plastic workability and corrosion resistance The manufacturing method of the Ni diffusion plating steel plate which has a layer.
[0008]
(2) After pickling a hot-rolled steel sheet produced by a normal manufacturing method and performing cold rolling, at least the rolling roll of the final stand is a cold-rolled steel sheet using a Ra: 0.3-2.0 μm dull roll. After recrystallization annealing, temper rolling is performed as necessary, and then Ni plating is performed by regulating the S concentration in the bath with a matte or semi-gloss Ni plating bath. After manufacturing a Ni-plated steel sheet of 5 to 50 g / m 2 in which the S content is controlled to 0.05% or less, an alloying diffusion heat treatment of the Ni-plated layer is performed at 550 ° C. or higher, and then the surface roughness Ra is It has a mirror bright surface with a glossiness exceeding 950, characterized by performing dry temper rolling with an elongation of 1.3% or more with a roll of 0.07 μm or less, and Fe concentration of the outermost layer being 50% or less Excellent plastic workability and corrosion resistance Manufacturing method of Ni diffusion-plated steel sheet having an Ni diffusion plating layer.
[0009]
(3) In the method for producing a Ni diffusion plated steel sheet according to the above (1) or (2), in the temper rolling step after Ni plating, the elongation at a roll having a Ra of 0.07 or less is 1.8%. Above, the manufacturing method of the Ni diffusion plating steel plate whose glossiness exceeds 1020 characterized by performing dry temper rolling.
(4) In the method for producing a Ni diffusion plated steel sheet according to the above (1) to (3), at the time of temper rolling after Ni plating, at least a roll of Ra: 0.07 μm or less is a hard Cr plated roll A method for producing a Ni diffusion-plated steel sheet having a glossiness exceeding 1020, characterized by
[0010]
(5) In a Ni diffusion plating steel sheet in which the Ni plating amount is 5 to 50 g / m 2 and at least a part of the Ni plating layer forms a Fe—Ni alloy layer by heat treatment, the Ni diffusion plating layer contains S The amount is 0.05% or less, the Ni diffusion plating layer has a mirror bright surface with a glossiness of more than 1020 smoothed by a rolling roll, and the Fe concentration of the outermost layer is 50% or less This is a Ni diffusion plated steel sheet excellent in plastic workability and corrosion resistance.
In the present invention, the Ni diffusion plating layer refers to a “pure Ni plating layer + Fe—Ni diffusion plating layer” or “Fe—Ni diffusion plating layer” whose ductility is improved by annealing. The Ni diffusion plated steel sheet refers to a steel sheet having the Ni diffusion plating layer.
[0011]
The present invention is described in detail below.
The inventors of the present invention first made various studies on a Ni diffusion plated steel sheet in which a Ni diffusion plating layer subjected to heat treatment after Ni plating has excellent plastic workability and excellent corrosion resistance. The plastic workability of the Ni diffusion plating layer, the IF steel after cold rolling is not subjected to recrystallization annealing, matte, subjected semi-gloss, gloss Ni plating, plated with Ni steel 26.4 g / m 2 Various specimens of Ni diffusion-plated steel sheets with 1.0% temper rolling applied to various Ni diffusion-plated steel sheets with varying annealing temperature time by continuous annealing were prepared. In addition to measuring the Fe concentration of the surface layer, the specimen was subjected to cylindrical deep drawing and the surface of the Ni diffusion plating layer on the side wall was observed with a scanning microscope at a magnification of 200 times to see if the Ni diffusion plating layer was cracked. (Hereinafter referred to as a Ni diffusion plating layer cracking evaluation test) and the cans were subjected to a salt spray test (5% salt water, 35 ° C., 6 hours: simply referred to as an SST test hereinafter), and the red rust occurrence rate (area%) We conducted a survey.
[0012]
The cracking properties of the Ni diffusion plating layer on the side wall after drawing are as follows: 1) It becomes clear that cracks start to occur when the S content in the Ni diffusion plating layer exceeds 0.05%, and S in the Ni diffusion plating layer becomes clear. It has been found that a Ni diffusion plating layer having good plastic workability cannot be obtained unless the content is at least 0.05%. 2) It has been found that the content of Fe diffused to the outermost layer of the Ni diffusion plating layer must be at least 50% or less. In the case of the present invention, the reason why good plastic workability can be obtained up to 50% of the Fe content of the outermost layer of the Ni diffusion plating layer is that the diffusion conditions of Ni diffusion plating are continuous annealing and the soaking time is 10 to 120 sec. This seems to be due to the shortness.
[0013]
The red rust occurrence rate in the SST test of drawn cans can be arranged by the soundness of the Ni diffusion plating layer, and if the Ni diffusion plating layer is not cracked, good post-processing corrosion resistance cannot be obtained, and excellent post-processing corrosion resistance is obtained. In this case, the content of Fe diffused in the outermost layer of Ni diffusion plating needs to be at least 50% or less.
In order to obtain good corrosion resistance and workability of the plating layer, Ni plating should be at least matte or semi-gloss Ni plating with an S content of 0.05% or less and a Ni plating basis weight of 5 g / m 2 or more. Must be regulated. When the Ni areal weight is less than 5 g / m 2 , even when the diffusion treatment is performed after Ni plating, the weight is too small to prevent the pinhole defect and the corrosion resistance cannot be ensured.
[0014]
Next, the inventors of the present invention have proposed a Ni diffusion plated steel sheet having an excellent glossiness having a mirror bright surface and a Ni diffusion plating layer that is soft and has excellent plastic workability during press processing and excellent corrosion resistance after processing. The production method and the provision of steel sheets were studied. As in JP-A-10-280184, the present inventors, in the above-described study, have a Ni diffusion plating layer that is brittle because the bright Ni plating that is generally performed contains S in the plating layer. It has become clear that there is a problem of peeling during press working, and that corrosion resistance after press working is also deteriorated, so it is necessary to carry out diffusion treatment after matte plating and to perform bright Ni plating on it investigated. As a result, excellent glossiness can be obtained and corrosion resistance after press working can be secured, but it is clear that the bright plating on the surface layer is hard and brittle because it is not heat-treated, so that the bright plating part is easily cracked and peeled off during pressing. did. In addition, this method requires double plating, which increases the manufacturing cost.
[0015]
Therefore, the present inventors used a Ni diffused plated steel sheet having good gloss obtained by temper rolling with the hard Cr plating roll according to claim 6 of Japanese Patent Laid-Open No. 10-280184. Various studies were made on a roll production method, a more excellent Ni diffusion plated steel plate having a glossiness of more than 1020, and a production method, and the steel plate and production method of the present invention were found.
As a result of various studies on a method for obtaining a more excellent mirror bright surface gloss by a temper rolling method using a normal mirror bright roll, it is difficult to achieve only by a temper rolling method such as JP-A-10-280184. It has been found that at least the final stand roll of tandem rolling during cold rolling needs to be a dull roll having a Ra of 0.3 to 2.0 μm from a commonly used smooth roll.
[0016]
That is, in order to obtain a Ni diffusion plated steel sheet with better glossiness, it is considered preferable to use a roll that is smoother than a cold rolling roll. It has been found that the effects of the invention of Kaihei 10-280184 can be further improved.
As a result of investigating the cause, the inventors of the present invention, when performing cold rolling with a smooth roll, a lot of slip marks formed on the entire surface by slipping or seizing the roll after the cold rolling, Even if the temper rolling is used, the slip marks remain unremovable, so there is a limit to the glossiness that can be reached, but the dull roll does not contain slip marks and a cold-rolled steel strip with a metallic luster is formed, and then the mirror bright roll It has been found that a higher level of glossiness can be obtained by temper rolling using. Further, although the manufacturing cost is increased, it has also been found that when temper rolling is performed with a mirror bright roll of hard Cr plating, the gloss is further improved and an extremely high gloss of 1050 or more can be obtained.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Below, the detailed description of the structural conditions of the present invention will be given.
Ni diffusion plated steel sheet of interest is a Ni diffusion plated steel sheet of 5 to 50 g / m 2 thickness, Fe concentration is high Ni outermost layer diffusion of Fe from the base steel during processing plating thickness is less than 5 g / m 2 However, if it is less than 5 g / m 2 , pinholes during Ni plating increase and the corrosion resistance deteriorates, so it is necessary to regulate to 5 g / m 2 or more. Further, the upper limit is set to 50 g / m 2 because the effect of improving the corrosion resistance is saturated and the production cost becomes higher when plating over 50 g / m 2 by electroplating, so the upper limit is set to 50 g / m 2. It was.
[0018]
The base steel plate is not particularly limited as long as it can be plated with Ni, but at the time of cold rolling, at least the rolling roll of the final stand is cold-rolled using a dull roll of Ra: 0.3 to 2.0 μm. It is necessary to use a non-recrystallized steel sheet.
In addition, although the same quality can be obtained with both the steel sheet after recrystallization annealing and the steel sheet after temper rolling, since annealing is performed twice, economically, a single annealing method in which Ni plating is applied to a non-recrystallized sheet. Is preferred.
[0019]
The Ni plating condition is a plating method that is usually performed, such as a Watt bath, and the S content in the Ni plating layer is regulated to 0.05% or less by matte or semi-gloss Ni plating. The amount must be 5 g / m 2 or more. As for the cracking property of the Ni plating layer on the side wall after drawing, cracking starts to occur when the S content in the plating layer exceeds 0.05%, so the S content in the Ni plating layer is at least 0. Must be less than 05%. The reason why the Ni basis weight must be 5 to 50 g / m 2 is as described above.
[0020]
The Ni diffusion heat treatment that also serves as recrystallization annealing of the steel sheet itself needs to be performed at 650 ° C. or higher in a continuous annealing furnace, and recrystallization annealing of the steel sheet and alloying diffusion heat treatment of the Ni plating layer. In the case of the two-time annealing method, the steel sheet may be recrystallized and annealed, Ni-plated, and then Ni diffusion heat treatment may be performed at 550 ° C. or higher by continuous annealing or box annealing. However, in the case of the box annealing method, since the annealing time is very long, it is necessary that the Ni-Fe interdiffusion distance is too long so that the Fe concentration of the outermost layer of the Ni plating layer does not exceed 50%. By this diffusion treatment, the Ni diffusion plating layer is excellent in plastic processing and corrosion resistance.
[0021]
The temper rolling conditions must be such that the surface roughness Ra is 0.07 μm or less and the elongation is 1.3% or more. Further, in order to obtain an excellent glossiness of more than 1020, the roll must have a surface roughness Ra of 0.07 μm or less and the total elongation must be 1.8% or more. When the temper rolling roll is a hard Cr plating roll, if the elongation percentage of the hard Cr plating roll is 1.3% or more, a glossiness of more than 1020 can be obtained, and further the elongation of the hard Cr plating roll. When the ratio is 1.8% or more, extremely excellent glossiness exceeding 1050 is obtained.
The plating amount obtained by the above production method is 5 to 50 g / m 2 , the S content in the Ni diffusion plating layer is 0.05% or less, and the Ni diffusion plating layer is smoothed by a rolling roll and glossiness The Ni diffusion plated steel sheet having an excellent mirror bright surface and an outermost layer Fe concentration of 50% or less can achieve both excellent luster and excellent plastic workability and corrosion resistance of the Ni diffusion plated layer. .
[0022]
【Example】
The effects of the present invention will be described below with reference to examples.
A cold rolled coil having a thickness of 0.26 mm was manufactured under the composition, hot rolling and cold rolling conditions shown in Table 1 and Table 2. Under the conditions shown in Table 2, Ni plating in a watt bath after alkaline degreasing and pickling, steel plate Ni diffusion heat treatment also serving as recrystallization annealing, or after recrystallization annealing of the steel sheet, Ni plating and Ni diffusion heat treatment were performed, and the temper rolling shown in Table 3 was performed to produce a Ni diffusion plated steel sheet. In order to investigate the quality of the prototype Ni diffusion plated steel sheet, the Ni diffusion plating layer was evaluated by SEM observation of the glossiness, Fe concentration (Fe / Fe + Ni ratio%), and the side wall outer surface after cylindrical drawing under the same conditions as described above. (0: no crack, x: occurrence of cracking), the area ratio of red rust after the SST corrosion test on the outer surface of the barrel can was investigated, and the results are shown in Table 3.
[0023]
[Table 1]
[Table 2]
[Table 3]
Test steel A is an Nb-Ti-added ultra-low carbon steel with a C content of 0.0019%, Ti added to 0.035%, Nb added to 0.008%, and B added to 0.0003%. Steel with excellent deep drawability.
Test steel B is an Al—K steel generally used as a tin plate having a C content of 0.040%.
Sample No. Nos. 1 and 2 are conventional examples of Japanese Patent Application Laid-Open No. 10-280184. The Ni plating layer of the drawing can is not cracked, red rust is not generated, and the glossiness is 850,800, which is a target of the present invention. The level is not reached.
[0027]
Sample No. 3,4-1 is an embodiment of claim 2 of the present invention, and the glossiness of 1025 and 1040 is excellent.
Sample No. 4-2 is a temper rolling roll having a Ra of 0.04 μm for MB (mirror bright) specification in which a temper rolling roll is hard Cr plated, and 2.0% temper rolling was performed. In the examples, a very good gloss of 1100 is obtained.
Sample No. 4-3 is the cold rolling conditions of the present invention in which the tandem roll is a dull roll, but the comparative example is a bright roll with Ra: 0.10 μm as the temper roll, and the glossiness is only 800.
[0028]
Sample No. No. 5 is a comparative example in which the roll at the time of cold rolling is a dull roll, but Ra is too coarse at 3.50 μm, and the target glossiness of 950 or more is not obtained.
Sample No. No. 6 is an example of the present invention using low-carbon Al-K steel, and good glossiness is obtained.
Sample No. No. 7 is an example of the present invention using a hard Cr-plated dull roll as a roll during cold rolling, and an extremely excellent gloss value of 1090 is obtained.
[0029]
Sample No. Nos. 8 and 9 are examples of the present invention using the two-time annealing method, and a Ni-plated steel sheet having good glossiness, cracking of the Ni-plated layer of the drawn can and no occurrence of red rust was obtained.
Sample No. 10 is a comparative example in which the cold rolling roll is a smooth roll and the S concentration in the plating layer exceeds the limit of the present invention, the glossiness has not reached, the Ni diffusion plating layer after drawing is cracked, and Corrosion resistance is poor.
As is clear from the results of the above examples, according to the method of the present invention, “the Ni diffusion plating layer is soft and excellent in plastic workability during press working, corrosion resistance after processing, and mirror brightness with excellent glossiness. It is possible to sufficiently achieve “a method for producing a Ni diffusion-plated steel sheet having a surface and a steel sheet”.
[0030]
【The invention's effect】
As is clear from the results of the above examples, the method of the present invention is to solve the problem to be solved by the present invention: “The Ni diffusion plating layer is soft and has excellent plastic workability during press working and excellent corrosion resistance after working. Furthermore, it is possible to satisfactorily achieve “to provide a Ni diffusion-plated steel sheet production method and a steel sheet having a mirror bright surface with excellent glossiness”, and the industrial value is extremely large.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000344558A JP3634257B2 (en) | 2000-11-13 | 2000-11-13 | Ni diffusion-plated steel sheet manufacturing method and steel sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000344558A JP3634257B2 (en) | 2000-11-13 | 2000-11-13 | Ni diffusion-plated steel sheet manufacturing method and steel sheet |
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| Publication Number | Publication Date |
|---|---|
| JP2002143903A JP2002143903A (en) | 2002-05-21 |
| JP3634257B2 true JP3634257B2 (en) | 2005-03-30 |
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| CN100462194C (en) * | 2005-07-20 | 2009-02-18 | 林榆滨 | Method for producing nickel belt |
| JP4893540B2 (en) * | 2007-09-03 | 2012-03-07 | 住友金属工業株式会社 | Dull steel plate and manufacturing method thereof |
| SG178584A1 (en) * | 2009-08-26 | 2012-04-27 | Toyo Kohan Co Ltd | Ni-plated steel sheet for battery can having excellent pressability |
| KR101266451B1 (en) * | 2010-10-13 | 2013-05-24 | 주식회사 포스코 | Method for preparing galvanazed steel sheet |
| CN102581002B (en) * | 2012-02-23 | 2014-02-26 | 西部钛业有限责任公司 | Method for preparing pure nickel sheet |
| CN106269861B (en) * | 2016-08-26 | 2019-02-01 | 首钢京唐钢铁联合有限责任公司 | Process method for flattening cold-rolled galvanized strip steel by utilizing flattening machine |
| CN109772886A (en) * | 2018-12-31 | 2019-05-21 | 陕西航宇有色金属加工有限公司 | Pure nickel plate processing method |
| CN118099554A (en) * | 2022-11-25 | 2024-05-28 | 宝山钢铁股份有限公司 | Nickel-plated steel, manufacturing method thereof and battery shell |
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