JP3643333B2 - Steel sheet for galvannealed alloy and galvannealed steel sheet - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は合金化溶融亜鉛めっき用鋼板にかかり、さらに詳しくは深絞り性をはじめとする成形性、加工性に格段に優れると同時に優れためっき密着性を得ることができる鋼板に関する。
【０００２】
【従来の技術】
合金化溶融亜鉛めっき鋼板は、塗装密着性、塗装耐食性、溶接性などの点に優れることから、自動車用をはじめとして、家電、建材等に非常に多用されている。合金化溶融亜鉛めっき鋼板は鋼板表面に溶融亜鉛をめっきした後、直ちに亜鉛の融点以上の温度に加熱保持して、鋼板中からＦｅを亜鉛中に拡散させることで、Ｚｎ−Ｆｅ合金を形成させるものであるが、鋼板の組成や組織によって合金化速度が大きく異なるため、その制御はかなり高度な技術を要する。一方、自動車の外板や難成形部材に適用される鋼板には、非常に高い成形性が要求されるとともに、近年では自動車の防錆性能への要求が高まったことによって、合金化溶融亜鉛めっきが適用されるケースが増加している。この場合、鋼板は非常に高い加工度の成形が施されるので、鋼板には優れた加工性と高いめっき密着性とが同時に要求される。
【０００３】
合金化溶融亜鉛めっき鋼板では、鋼板と亜鉛層とを合金化反応させた結果、めっき層はζ相、δ1相、Γ相とよばれるＺｎ−Ｆｅ系金属間化合物に変化する。これらの合金相は塗装性、塗料密着性、溶接性を改善する一方で、合金層自身の硬度が高く、特にΓ相は脆弱であることから、プレス成形等の加工を受けるとめっきが粉状になって剥離する、いわゆるパウダリング現象を生じやすくなる。パウダリングはめっきの健全性を損なうことに加えて、剥離した粉状のめっきがプレス型に堆積してプレス品の外観を著しく劣化させる。近年は自動車車体の防錆性能強化を目的として、厚目付合金化溶融亜鉛めっき鋼板が一般的になりつつあるが、上述のパウダリング現象はめっき付着量が多いほど発生しやすいため、耐パウダリング性の向上に対する要求は強い。
【０００４】
一方、自動車車体形状が一段と複雑になるのに従って、鋼板の成形性に対する要求も一段と厳しくなっており、従来にもまして深絞り性等の成形性の優れた鋼板が、合金化溶融亜鉛めっき鋼板にも要求されている。かかる加工性を得るためには、鋼板の成分として、Ｃを極めて低いレベルにまで低減した上でＴｉを添加した鋼、あるいはＴｉとＮｂを複合添加した鋼が代表的である。しかし、これらの鋼は溶融亜鉛めっきの合金化における合金化速度が非常に速いために、合金化が進みすぎてΓ相が厚く成長し、パウダリング性能が低下しやすい、という問題がある。かかる鋼に対しては、めっき浴温を低下させる、めっき浴中のＡｌ濃度を増加させる、合金化温度を低くして加熱時間を増加させる、などの操業面からの対応が図られているが、合金化不足はフレーキングと称する片状のめっき剥離を生じやすいことから、必ずしも安定しためっき密着性が得られていない。また、これらの操業条件の変更は生産ラインの停止を伴うために生産性を低下させ、コストを上昇させる。
【０００５】
耐パウダリング性の優れた合金化溶融亜鉛めっき鋼板の製造方法としては、特開平２−３１０３５２号公報、特開平２−３１０３５３号公報において、合金化熱処理条件、冷却条件とともに合金化後の均熱処理条件を規定する技術が提案されているが、長時間の均熱処理を要するため、めっきラインの生産性が低下し、経済的ではない。また、深絞り性とめっき密着性の優れた合金化溶融亜鉛めっき鋼板の製造方法としては、特開平５−３３１６１２号公報において、鋼板の組成、熱延条件および冷却条件、冷延後の焼鈍条件に加えて、鋼板のＰおよびＴｉ含有量とめっき浴中の有効Ａｌ濃度との関係式を限定する技術が提案されており、特開平６−１７１４２号公報においては、鋼板の組成、熱延条件、冷延後の焼鈍条件に加えて、鋼板のＰおよびＴｉ含有量とめっき浴中の有効Ａｌ濃度との関係式を限定する技術が提案されている。しかし、これらの方法においては、Ａｌ濃度を制御することによるめっきラインの操業条件の変更や調整のために、めっきラインの生産性が低下し、コストが上昇する。
【０００６】
【発明が解決しようとする課題】
本発明は上記の現状に鑑みて、優れた加工性・成形性と高いめっき密着性を同時に達成できる、合金化溶融亜鉛めっき用鋼板を提供することを目的としている。
【０００７】
【課題を解決するための手段】
本発明者は鋼板の加工性および溶融亜鉛めっきラインの生産性を低下させずにめっき密着性を向上させる手段を種々検討した結果、Ｃ、Ｐ、Ｎ等を低減した被めっき鋼板に添加するＡｌ質量を制御することによって、鋼板の加工性とめっき密着性を両立できることを見出して本発明に至った。
【０００８】
すなわち、本発明の趣旨とするところは、以下のとおりである。
【０００９】
（１） 質量％で，
Ｃ： ０．０００１〜０．００４％，
Ｓｉ：０．００１〜０．１０％，
Ｍｎ：０．０１〜０．５０％，
Ｐ： ０．００１〜０．０１５％，
Ｓ： ０．０１５％以下，
Ａｌ：０．１２〜０．５０％，
Ｔｉ：０．００２〜０．１０％，
Ｎ： ０．０００５〜０．００４％，
を含有し，残部Ｆｅおよび不可避不純物からなることを特徴とする合金化溶融亜鉛めっき用鋼板．
【００１０】
（２） 鋼板が付加成分としてさらに、質量％で、Ｎｂ：０．００２〜０．１％を含有することを特徴とする前記（１）項に記載の合金化溶融亜鉛めっき用鋼板。
【００１１】
（３） 鋼中Ｔｉ含有量が、下記（１）〜（２）式（［％Ｘ］は、質量％で表わした合金元素Ｘの含有量）で与えられる条件を満足することを特徴とする前記（１）または（２）項に記載の合金化溶融亜鉛めっき用鋼板。
（４） 鋼板が付加成分としてさらに、質量％で、Ｂ：０．０００２〜０．００３％を含有することを特徴とする前記（１）乃至（３）項のいずれかに記載の合金化溶融亜鉛めっき用鋼板。
【００１３】
（５） 前記（１）乃至（４）項のいずれかに記載の合金化溶融亜鉛めっき用鋼板にＡｌ：０．０５〜０．５質量％、Ｆｅ：７〜１５質量％、残部がＺｎおよび不可避的不純物からなる合金化溶融亜鉛めっき層を形成させた合金化溶融亜鉛めっき鋼板。
【００１４】
【発明の実施の形態】
以下、本発明を詳細に説明する。まず、本発明において各成分の範囲を限定した理由を述べる。なお、本発明において％は、特に明記しない限り、質量％を意味する。
【００１５】
Ｃ：Ｃは鋼の強度を高める元素であって０．０００１％以上を含有させることが有効であるが、過剰に含有すると強度が上昇しすぎて加工性が低下するので上限含有量は０．００４％とする。特に高い加工性を必要とする場合には、Ｃ含有量は０．００３％以下とすることが好ましく、０．００２％以下とするとさらに好ましい。
【００１６】
Ｓｉ：Ｓｉも鋼の強度を向上させる元素であって０．００１％以上を含有させるが、過剰に含有すると加工性および溶融亜鉛めっき性を損なうので、上限は０．１％とする。特に高い加工性を必要とする場合には、Ｓｉ含有量は０．０５％以下とする。
【００１７】
Ｍｎ：Ｍｎも鋼の強度を高める一方で加工性を低下させる元素であるので、上限含有量は０．５％とする。Ｍｎが少ないほど加工性は良好であるが、０．０１％以下とするためには精練コストが多大となるので下限含有量は０．０１％とする。
【００１８】
Ｐ：Ｐも鋼の強度を高める一方で加工性を低下させる元素であるので、上限含有量は０．０１５％とする。Ｐが少ないほど加工性は良好であり、０．０１％以下とするとより好ましい。一方、Ｐ含有量を０．００１％未満に低減するためには精練コストが多大となるので、下限含有量は０．００１％とする。強度、加工性とコストのバランスからはＰ含有量は０．００３〜０．０１％とすることがより好ましい。
【００１９】
Ｓ：Ｓは鋼の熱間加工性、耐食性を低下させる元素であるから少ないほど好ましく、上限含有量は０．０１５％とし、より好ましくは０．０１％以下とする。但し、本発明のような極低炭素鋼のＳ量を低減するためにはコストがかかるので、加工性およびめっき密着性の観点からはＳを過度に低減する必要はなく、熱間加工性、耐食性等から必要なレベルにまでＳを低減すれば良い。
【００２０】
Ａｌ：Ａｌは鋼の脱酸元素として，またＡｌＮによる熱延素材の細粒化，および一連の熱処理工程における結晶粒の粗大化を抑制し材質を改善するために０．００５〜０．１０％添加する必要があるが，さらに添加することにより，溶融亜鉛めっき層と鋼板の合金化反応を制御し，良好な特性を有する合金化溶融亜鉛めっき鋼板を得ることが可能となる．Ａｌ含有量を高めた場合，鋼板の強度をほとんど上昇させずに合金化速度を遅くすることが可能となるため，鋼板の加工性とめっき密着性を満足することができる．ここで，鉄／めっき界面においてΓ相に代表される脆い金属間化合物の生成を抑制し，めっき密着性を改善する目的からＡｌの添加量は０．１２％以上必要である．ただし，０．５％を超えるとコスト高となるばかりか，表面性状を劣化させるためＡｌの添加量は０．５％以下とする．
めっき密着性とコストのバランスからはＡｌ含有量は０．１５〜０．４％とすることがより好ましい．
【００２１】
めっき密着性とコストのバランスからはＡｌ含有量は０．１５〜０．４％とすることがより好ましい。
【００２２】
Ｔｉ：鋼中のＣおよびＮを炭化物、窒化物として固定するために、０．００２％以上の添加が必要であり、０．０１％以上含有させるとより好ましい。一方、０．１％を超えて添加してももはやその効果は飽和しているのに対して、いたずらに合金添加コストが上昇するだけであるので、上限含有量は０．１％とする。過剰な固溶Ｔｉは鋼板の加工性および表面品質を損なう場合があるので、０．０５％以下とするとより好ましい。
【００２３】
Ｎ：Ｎは鋼の強度を上昇させる一方で加工性を低下させるので上限は０．００４％とし、特に高い加工性を必要とする場合には０．００３％以下とすることがより好ましく、０．００２％以下とするとさらに好ましい。Ｎはより少ないほど好ましいが、０．０００５％未満に低減することは過剰なコストを要するので、下限含有量は０．０００５％とする。
【００２４】
本発明では上記に加えて、さらに付加成分として、鋼中のＣおよびＮを炭化物、窒化物として固定するために、前記のＴｉ添加のもとでＮｂを添加することができるが、Ｎｂ添加によるＣ、Ｎ固定効果を充分発揮させるためには０．００２％以上の添加が必要であり、０．００５％以上とするとより好ましい。Ｎｂを０．１％を超えて添加しても、もはやその効果は飽和している一方、いたずらにコストが上昇するだけであるので、上限含有量は０．１％とする。過剰なＮｂ添加は鋼板の再結晶温度を上昇させ、溶融亜鉛めっきラインの生産性を低下させるので、０．０５％以下とするとより好ましい。
【００２５】
本発明においては、さらに鋼板の成形性、加工性を一段と高くする場合には、ＴｉおよびＮｂ含有量を下記（１）および（２）式を満足する範囲とする。
これは、ＴｉおよびＮｂの含有量を上記の範囲とすると、加工性を阻害する元素であるＣおよびＮをＴｉ、またはＴｉとＮｂの複合効果で有効に固定し、鋼板の加工性を高めることができるからであるが、Ｎｂ単独の添加ではかかる加工性向上効果は充分ではなく、Ｔｉ含有量が０．００９％以上である場合にＴｉとＮｂの複合添加効果が顕著となり、この場合においてＴｉおよびＮｂの含有量が（１）式を満足すると、ＣおよびＮをＴｉとＮｂとで有効に固定することができる。
【００２７】
本発明においてはさらに、鋼板に付加成分として、Ｂを０．０００２〜０．００３％含有させることができるが、これは２次加工性の改善を目的としている。Ｂの含有量が０．０００２％未満では２次加工性改善効果が充分ではなく、０．００３％を超えて添加してももはやその効果は飽和しているのに加えて、成形性が低下するので、Ｂを添加する場合にはその範囲は０．０００２〜０．００３％とする。特に高い深絞り性を必要とする場合には、Ｂの添加量は０．００１５％以下とするとより好ましい。
【００２８】
本発明において合金化溶融亜鉛めっき層のＡｌ組成を０．０５〜０．５質量％に限定した理由は、０．０５質量％未満では合金化処理時においてＺｎ−Ｆｅ合金化が進みすぎ、地鉄界面に脆い合金層が発達しすぎてめっき密着性が劣化するためであり、０．５質量％を超えるとＦｅ−Ａｌ−Ｚｎ系バリア層が厚く形成されすぎ合金化処理時において合金化が進まないため目的とする鉄含有量のめっきが得られないためである。
【００２９】
また、Ｆｅ組成を７〜１５質量％に限定した理由は、７質量％未満だとめっき表面に柔らかいＺｎ−Ｆｅ合金が形成されプレス成形性を劣化させるためであり、１５質量％を超えると地鉄界面に脆い合金層が発達しすぎてめっき密着性が劣化するためである。
【００３０】
本発明鋼板の製造工程としては、通常の熱延鋼板（ホットストリップ）、あるいは冷延鋼板（コールドストリップ）の製造工程を適用して製造すれば良い。
【００３１】
本発明では鋼板中のＯは特に限定しないが、Ｏは酸化物系介在物を生成して鋼の加工性や耐食性を損なうので、０．００４％以下とすることが望ましく、少ないほど好ましい。
【００３２】
本発明の鋼板には上記の成分の他に、鋼板自体の耐食性や熱間加工性を一段と改善する目的で、あるいはスクラップ等副原料からの不可避不純物として、他の合金元素を含有することも可能であり、他の合金元素を含有したとしても本発明の範囲を逸脱するものではない。かかる合金元素として、Ｃｕ、Ｎｉ、Ｃｒ、Ｍｏ、Ｗ、Ｃｏ、Ｃａ、希土類元素（Ｙを含む）、Ｖ、Ｚｒ、Ｔａ、Ｈｆ、Ｐｂ、Ｓｎ、Ｚｎ、Ｍｇ、Ｔａ、Ａｓ、Ｓｂ、Ｂｉが挙げられる。
【００３３】
本発明鋼板は、通常の溶融亜鉛めっき鋼板製造ラインに適用して、加工性・成形性とめっき密着性の優れた合金化溶融亜鉛めっき鋼板を得ることができるので、製造プロセスに対する制約は特にない。コスト、生産性を考慮して、適宜プロセスを選択すれば良い。
【００３４】
本発明鋼板は、溶融亜鉛めっき浴中あるいは亜鉛めっき中にＰｂ、Ｓｂ、Ｓｉ、Ｆｅ、Ｓｎ、Ｍｇ、Ｍｎ、Ｎｉ、Ｃｒ、Ｃｏ、Ｃａ、Ｃｕ、Ｌｉ、Ｔｉ、Ｂｅ、Ｂｉ、希土類元素の１種または２種以上を含有、あるいは混入してあっても本発明の効果を損なわず、その量によっては耐食性が改善される等好ましい場合もある。合金化溶融亜鉛めっきの付着量については特に制約は設けないが、耐食性の観点から２０ｇ／ｍ2以上、経済性の観点から１５０ｇ／ｍ2以下であることが望ましい。
【００３５】
本発明において、めっき鋼板の製造方法については特に限定するところはなく、通常の無酸化炉方式の溶融めっき法が適用できる。合金化処理条件については特に定めないが、処理温度４６０〜５５０℃、処理時間１０〜４０秒の範囲が実際の操業上適切である。
【００３６】
また、本発明において鋼板の板厚は本発明に何ら制約をもたらすものではなく、通常用いられている板厚であれば本発明を適用することが可能である。さらに、本発明鋼板は通常のプロセスで製造される冷延鋼板、熱延鋼板のいずれであってもその効果は充分に発揮されるものであり、鋼板の履歴によって効果が大きく変化するものではない。また、熱間圧延条件、冷間圧延条件、焼鈍条件等は鋼板の寸法、必要とする強度に応じて所定の条件を選択すれば良く、熱間圧延条件、冷間圧延条件、焼鈍条件等によって本発明鋼板の効果が損なわれるものではない。
【００３７】
当然のことながら、本発明鋼板を使用して得られた合金化溶融亜鉛めっき鋼板上に、塗装性、溶接性を改善する目的で、各種の上層めっき、特に電気めっき、を施すことも勿論可能であり、本発明を逸脱するものではない。また、本発明の方法で得られた合金化溶融亜鉛めっき鋼板上に、各種の処理を付加して施すことも勿論可能であり、例えば、クロメート処理、りん酸塩処理、りん酸塩処理性を向上させるための処理、潤滑性向上処理、溶接性向上処理、樹脂塗布処理、等を施したとしても、本発明の範囲を逸脱するものではなく、付加して必要とする特性に応じて、各種の処理を施すことができる。
【００３８】
本発明鋼板の強度としては、引張強度が３００Ｎ／ｍｍ2未満の普通鋼あるいは超深絞り用鋼板から、３００Ｎ／ｍｍ2以上の高強度鋼（３００、３４０、４００、４４０Ｎ／ｍｍ2級）などの広範囲にわたるものである。
【００３９】
【実施例】
以下、実施例により本発明を具体的に説明する。
【００４０】
（実施例１）
まず、表１に示す供試材を用意し、ライン内焼鈍方式の連続溶融亜鉛めっき設備を用いて、合金化溶融亜鉛めっき鋼板を製造した。めっきに際しては、焼鈍雰囲気は５％水素＋９５％窒素混合ガスとし、焼鈍温度は８００〜８４０℃、焼鈍時間は９０秒とした。溶融亜鉛浴はＡｌを０．１２％含有する溶融亜鉛とし、ガスワイパーで亜鉛の目付量を６０ｇ／ｍ2に調整した。合金化の加熱は誘導加熱方式の加熱設備を使用し、合金化溶融亜鉛めっき中のＦｅ含有量が１０〜１１％となるようにした。但し、熱延鋼板では焼鈍、冷却に代えて５００℃に予熱（９０秒）した。このようにして得られた合金化溶融亜鉛めっき鋼板のめっき中のＡｌ含有量は０．１５〜０．２５％であった。
【００４１】
各鋼板からサンプルを採取し、Ｖ曲げ方式でめっき密着性を評価した。即ち、あらかじめ圧縮側に密着テープ（セロハンテープ）を貼った試験片を曲げ角度が６０゜となるようにＶ字状に試験片を曲げ、曲げ戻し後に密着テープをはがして、めっきの剥離の程度を目視で観察して、以下の分類でめっき密着性を評価した。
◎：めっき層がまったく剥離しないもの
○：めっきの剥離が軽微であるもの
△：めっきが相当程度剥離したもの
×：めっきがほとんど剥離したもの
【００４２】
また、加工性の指標としては、各合金化溶融亜鉛めっき用鋼板の引張試験を行なって、伸びおよびランクフォード値（ｒ値：０゜、４５゜、９０゜の平均ｒ値、但し冷延鋼板のみ）を測定し、冷延板は伸び４８％以上、ｒ値１．５以上を合格、熱延鋼板は伸び４５％以上を合格とした。
【００４３】
結果を表１にあわせて示す。表１から明らかなように、本発明例である記号Ａ〜Ｒはめっき密着性が優れており、かつ鋼板の加工性にも優れているのに対して、比較例である記号Ｓ〜ＶとＸはめっき密着性が劣っており、記号Ｗは鋼板の加工性が不充分であった。
【００４４】
【表１】
（実施例２）
まず、表１に示す供試材を用意し、ライン内焼鈍方式の連続溶融亜鉛めっき設備を用いて、合金化溶融亜鉛めっき鋼板を製造した。めっきに際しては、焼鈍雰囲気は５％水素＋９５％窒素混合ガスとし、焼鈍温度は８００〜８４０℃、焼鈍時間は９０秒とした。溶融亜鉛浴はＡｌを含有する溶融亜鉛とし、ガスワイパーで亜鉛の目付量を６０ｇ／ｍ2に調整した。合金化の加熱は誘導加熱方式の加熱設備を使用し、合金化溶融亜鉛めっき中のＦｅ含有量が表２に示す値となるようにした。めっき浴中のＡｌ濃度は種々変化させ、合金化溶融亜鉛めっき中のＡｌ含有量が表２に示す値となるようにした。
【００４６】
得られためっき鋼板はプレス成形性とめっき密着性を調査した。
【００４７】
プレス成形性は、プレス加工におけるめっきのかじりを調べるため、ビード引き抜き試験を行った。試験条件を以下に示す。
・サンプル引き抜き巾：３０ｍｍ
・金型：片側がφ４ｍｍ凸型、反対側が肩Ｒ２ｍｍＲの凹型
・押しつけ荷重：９００ｋｇ
・引き抜き速度：２００ｍｍ／ｍｉｎ
・塗油：防錆油塗布
プレス成形性の評価は、かじりが発生し試験片が破断したものを不合格、引き抜けたものを合格とした。
【００４８】
めっき密着性は、あらかじめ圧縮側に密着テープ（セロハンテープ）を貼った試験片を曲げ角度が６０゜となるようにＶ字状に試験片を曲げ、曲げ戻し後に密着テープをはがして、めっきの剥離の程度を目視で観察して、以下の分類で評価した。
◎：めっき層がまったく剥離しないもの
○：めっきの剥離が軽微であるもの
△：めっきが相当程度剥離したもの
×：めっきがほとんど剥離したもの
【００４９】
評価結果は表２に示すとおりである。番号１はめっき中のＦｅ含有量が本発明の範囲外であるためプレス成形性が不合格となった。番号６はめっき中のＦｅ含有量が本発明の範囲外であるためめっき密着性が不合格となった。番号７はめっき中のＡｌ含有量が本発明の範囲外であるためめっき密着性が不合格となった。番号９はめっき中のＡｌ含有量が本発明の範囲外であるため十分なＦｅ含有量が確保できずプレス成形性が不合格となった。これら以外の本発明品は、プレス成形性とめっき密着性が良好な合金化溶融亜鉛めっき鋼板であった。
【００５０】
【表２】
【発明の効果】
以上述べたように、本発明は加工性、成形性とめっき密着性のいずれにも優れる合金化溶融亜鉛めっき鋼板を製造できる被めっき鋼板を提供することを可能としたものであり、産業の発展に貢献するところが極めて大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a steel sheet for alloying hot dip galvanizing, and more particularly relates to a steel sheet that is remarkably excellent in formability including deep drawability and workability and at the same time has excellent plating adhesion.
[0002]
[Prior art]
Alloyed hot-dip galvanized steel sheets are extremely used in automobiles, home appliances, building materials and the like because they are excellent in coating adhesion, coating corrosion resistance, weldability, and the like. An alloyed hot-dip galvanized steel sheet forms a Zn-Fe alloy by coating hot-dip zinc on the surface of the steel sheet and immediately holding it at a temperature equal to or higher than the melting point of zinc and diffusing Fe from the steel sheet into the zinc. However, since the alloying speed varies greatly depending on the composition and structure of the steel sheet, the control thereof requires a considerably advanced technique. On the other hand, steel sheets applied to automotive outer plates and difficult-to-form members are required to have extremely high formability, and in recent years, the demand for rust prevention performance of automobiles has increased. The number of cases where is applied is increasing. In this case, since the steel sheet is formed with a very high degree of processing, the steel sheet is required to have both excellent workability and high plating adhesion.
[0003]
In the alloyed hot-dip galvanized steel sheet, as a result of alloying reaction between the steel sheet and the zinc layer, the plated layer changes to a Zn—Fe-based intermetallic compound called ζ phase, δ1 phase, and Γ phase. While these alloy phases improve paintability, paint adhesion, and weldability, the alloy layer itself has high hardness, and the Γ phase is particularly fragile. It becomes easy to produce what is called a powdering phenomenon which peels. In addition to impairing the soundness of the plating, powdering causes the peeled-off powder-like plating to accumulate on the press mold and significantly deteriorate the appearance of the pressed product. In recent years, for the purpose of strengthening the rust prevention performance of automobile bodies, thick alloyed hot dip galvanized steel sheets are becoming popular. However, the above-mentioned powdering phenomenon is more likely to occur as the amount of plated coating increases. There is a strong demand for improvement of sex.
[0004]
On the other hand, as the car body shape becomes more complex, the demands on the formability of steel sheets have become more severe. Steel sheets with excellent formability, such as deep drawability, have been transformed into galvannealed steel sheets. Is also required. In order to obtain such workability, the steel is typically steel added with Ti after being reduced to a very low level, or steel combined with Ti and Nb. However, these steels have a problem that the alloying rate in hot galvanizing alloying is so high that the alloying proceeds too much and the Γ phase grows thick and the powdering performance tends to deteriorate. For such steels, countermeasures from the operational aspect such as lowering the plating bath temperature, increasing the Al concentration in the plating bath, lowering the alloying temperature and increasing the heating time have been attempted. Insufficient alloying tends to cause strip-like plating peeling called flaking, so that stable plating adhesion is not always obtained. Moreover, since these changes in operating conditions are accompanied by a stop of the production line, productivity is lowered and costs are increased.
[0005]
As a method for producing an alloyed hot-dip galvanized steel sheet having excellent powdering resistance, Japanese Patent Application Laid-Open No. 2-310352 and Japanese Patent Application Laid-Open No. 2-310353 disclose soaking heat treatment after alloying together with alloying heat treatment conditions and cooling conditions. A technique for defining the conditions has been proposed, but since soaking for a long time is required, the productivity of the plating line is lowered, which is not economical. Further, as a method for producing an alloyed hot-dip galvanized steel sheet having excellent deep drawability and plating adhesion, in JP-A-5-331612, the composition of the steel sheet, hot rolling conditions and cooling conditions, annealing conditions after cold rolling In addition to the above, a technique for limiting the relational expression between the P and Ti contents of the steel sheet and the effective Al concentration in the plating bath has been proposed. In JP-A-6-17142, the composition of the steel sheet and the hot rolling conditions are proposed. In addition to the annealing conditions after cold rolling, a technique for limiting the relational expression between the P and Ti contents of the steel sheet and the effective Al concentration in the plating bath has been proposed. However, in these methods, because the plating line operating conditions are changed or adjusted by controlling the Al concentration, the productivity of the plating line decreases and the cost increases.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a steel sheet for galvannealing that can simultaneously achieve excellent workability / formability and high plating adhesion.
[0007]
[Means for Solving the Problems]
As a result of various studies on means for improving the plating adhesion without reducing the workability of the steel sheet and the productivity of the hot dip galvanizing line, the inventor has added Al to the steel sheet to be plated with reduced C, P, N, etc. By controlling the mass, it was found that the workability and plating adhesion of the steel sheet can be achieved, and the present invention has been achieved.
[0008]
That is, the gist of the present invention is as follows.
[0009]
(1) In mass%,
C: 0.0001 to 0.004%,
Si: 0.001 to 0.10%,
Mn: 0.01 to 0.50%,
P: 0.001 to 0.015%,
S: 0.015% or less,
Al: 0.12 to 0.50%,
Ti: 0.002 to 0.10%,
N: 0.0005 to 0.004%,
A steel sheet for alloying hot dip galvanizing, characterized by comprising the remainder Fe and inevitable impurities.
[0010]
(2) The steel sheet for galvannealing according to the item (1), wherein the steel sheet further contains Nb: 0.002 to 0.1% by mass% as an additional component.
[0011]
(3) The Ti content in the steel satisfies the conditions given by the following formulas (1) to (2) (where [% X] is the content of alloy element X expressed in mass%). The steel sheet for galvannealing according to the item (1) or (2).
(4) The alloying and melting according to any one of (1) to (3) above, wherein the steel sheet further contains B: 0.0002 to 0.003% by mass% as an additional component. Galvanized steel sheet.
[0013]
(5) Al: 0.05 to 0.5 mass%, Fe: 7 to 15 mass%, the balance being Zn and the alloyed hot-dip galvanized steel sheet according to any one of (1) to (4) An alloyed hot-dip galvanized steel sheet having an alloyed hot-dip galvanized layer made of inevitable impurities.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. First, the reason why the range of each component is limited in the present invention will be described. In the present invention, “%” means “% by mass” unless otherwise specified.
[0015]
C: C is an element that increases the strength of the steel, and it is effective to contain 0.0001% or more. However, if it is excessively contained, the strength is excessively increased and the workability is lowered, so the upper limit content is 0.8. 004%. In particular, when high workability is required, the C content is preferably 0.003% or less, and more preferably 0.002% or less.
[0016]
Si: Si is also an element that improves the strength of the steel and contains 0.001% or more. However, if excessively contained, workability and hot dip galvanizing property are impaired, so the upper limit is made 0.1%. In particular, when high workability is required, the Si content is 0.05% or less.
[0017]
Mn: Since Mn is an element that increases the strength of steel while reducing workability, the upper limit content is set to 0.5%. The smaller the Mn, the better the workability, but in order to make it 0.01% or less, the scouring cost becomes large, so the lower limit content is made 0.01%.
[0018]
P: P is an element that increases the strength of the steel while decreasing the workability, so the upper limit content is set to 0.015%. The smaller the P, the better the workability, and more preferably 0.01% or less. On the other hand, in order to reduce the P content to less than 0.001%, the scouring cost becomes large, so the lower limit content is made 0.001%. From the balance of strength, workability and cost, the P content is more preferably 0.003 to 0.01%.
[0019]
S: Since S is an element that lowers the hot workability and corrosion resistance of steel, it is preferably as small as possible, and the upper limit content is 0.015%, more preferably 0.01% or less. However, since it takes cost to reduce the amount of S of the ultra-low carbon steel as in the present invention, it is not necessary to excessively reduce S from the viewpoint of workability and plating adhesion, What is necessary is just to reduce S to the required level from corrosion resistance etc.
[0020]
Al: Al is 0.005 to 0.10% as a deoxidizing element for steel, and to improve the material by suppressing the grain refinement of hot rolled material by AlN and the coarsening of crystal grains in a series of heat treatment steps. It is necessary to add, but by adding more, it becomes possible to control the alloying reaction between the hot-dip galvanized layer and the steel sheet, and to obtain an alloyed hot-dip galvanized steel sheet having good characteristics. When the Al content is increased, the alloying speed can be slowed without substantially increasing the strength of the steel sheet, so that the workability and plating adhesion of the steel sheet can be satisfied. Here, in order to suppress the formation of brittle intermetallic compounds represented by the Γ phase at the iron / plating interface and improve plating adhesion, the amount of Al added must be 0.12 % or more. However, if it exceeds 0.5%, not only will the cost be high, but the Al content should be 0.5% or less in order to degrade the surface properties.
From the balance of plating adhesion and cost, the Al content is more preferably 0.15 to 0.4%.
[0021]
From the balance of plating adhesion and cost, the Al content is more preferably 0.15 to 0.4%.
[0022]
Ti: In order to fix C and N in steel as carbides and nitrides, addition of 0.002% or more is necessary, and it is more preferable to contain 0.01% or more. On the other hand, even if added over 0.1%, the effect is no longer saturated, but the alloy addition cost only increases unnecessarily, so the upper limit content is made 0.1%. Since excessive solute Ti may impair the workability and surface quality of the steel sheet, it is more preferably 0.05% or less.
[0023]
N: N increases the strength of the steel while lowering the workability, so the upper limit is made 0.004%, and when high workability is particularly required, it is more preferably 0.003% or less. More preferably, the content is 0.002% or less. N is preferably as little as possible, but reducing it to less than 0.0005% requires excessive cost, so the lower limit content is made 0.0005%.
[0024]
In the present invention, in addition to the above, as an additional component, Nb can be added under the above Ti addition in order to fix C and N in the steel as carbides and nitrides. In order to fully exhibit the C and N fixing effect, addition of 0.002% or more is necessary, and more preferably 0.005% or more. Even if Nb is added in excess of 0.1%, the effect is no longer saturated, but the cost is unnecessarily increased. Therefore, the upper limit content is set to 0.1%. Excessive Nb addition increases the recrystallization temperature of the steel sheet and lowers the productivity of the hot dip galvanizing line, so it is more preferably 0.05% or less.
[0025]
In the present invention, when the formability and workability of the steel sheet are further increased, the Ti and Nb contents are set in a range satisfying the following expressions (1) and (2).
This is because, when the content of Ti and Nb is in the above range, C and N, which are elements that hinder workability, are effectively fixed by Ti or the combined effect of Ti and Nb, and the workability of the steel sheet is improved. However, when Nb alone is added, the effect of improving the workability is not sufficient, and when the Ti content is 0.009% or more, the combined effect of Ti and Nb becomes remarkable. When the contents of N and Nb satisfy the expression (1), C and N can be effectively fixed with Ti and Nb.
[0027]
In the present invention, the steel sheet may further contain 0.0002 to 0.003% of B as an additional component, and this is intended to improve secondary workability. If the B content is less than 0.0002%, the secondary workability improvement effect is not sufficient, and even if added over 0.003%, the effect is no longer saturated, and the moldability is reduced. Therefore, when adding B, the range is made 0.0002 to 0.003%. In particular, when high deep drawability is required, the amount of B added is more preferably 0.0015% or less.
[0028]
In the present invention, the reason why the Al composition of the galvannealed layer is limited to 0.05 to 0.5% by mass is that if it is less than 0.05% by mass, Zn-Fe alloying proceeds too much during the alloying treatment, This is because a brittle alloy layer develops too much at the iron interface and the plating adhesion deteriorates. If it exceeds 0.5 mass%, the Fe—Al—Zn-based barrier layer is formed too thick and alloying occurs during the alloying treatment. This is because the desired iron content plating cannot be obtained because it does not progress.
[0029]
The reason why the Fe composition is limited to 7 to 15% by mass is that if it is less than 7% by mass, a soft Zn—Fe alloy is formed on the plating surface and press formability is deteriorated. This is because a brittle alloy layer develops too much at the iron interface and the plating adhesion deteriorates.
[0030]
As a manufacturing process of the steel sheet of the present invention, a manufacturing process of a normal hot-rolled steel sheet (hot strip) or a cold-rolled steel sheet (cold strip) may be applied.
[0031]
In the present invention, O in the steel sheet is not particularly limited, but O generates oxide inclusions and impairs the workability and corrosion resistance of the steel. Therefore, the O content is desirably 0.004% or less, and the smaller the better.
[0032]
In addition to the above components, the steel sheet of the present invention may contain other alloy elements for the purpose of further improving the corrosion resistance and hot workability of the steel sheet itself, or as an inevitable impurity from secondary materials such as scrap. Even if other alloy elements are contained, it does not depart from the scope of the present invention. Such alloy elements include Cu, Ni, Cr, Mo, W, Co, Ca, rare earth elements (including Y), V, Zr, Ta, Hf, Pb, Sn, Zn, Mg, Ta, As, Sb, Bi. Is mentioned.
[0033]
Since the steel sheet of the present invention can be applied to a normal hot dip galvanized steel sheet production line to obtain an alloyed hot dip galvanized steel sheet having excellent workability, formability and plating adhesion, there are no particular restrictions on the manufacturing process. . A process may be selected as appropriate in consideration of cost and productivity.
[0034]
The steel sheet of the present invention is made of Pb, Sb, Si, Fe, Sn, Mg, Mn, Ni, Cr, Co, Ca, Cu, Li, Ti, Be, Bi, rare earth elements during hot dip galvanizing bath or during galvanizing. Even if one kind or two or more kinds are contained or mixed, the effects of the present invention are not impaired, and depending on the amount, the corrosion resistance may be improved. There are no particular restrictions on the amount of alloying hot dip galvanizing, but it is preferably 20 g / m 2 or more from the viewpoint of corrosion resistance and 150 g / m 2 or less from the viewpoint of economy.
[0035]
In the present invention, the method for producing a plated steel sheet is not particularly limited, and a normal non-oxidizing furnace type hot dipping method can be applied. Although the alloying treatment conditions are not particularly defined, a treatment temperature range of 460 to 550 ° C. and a treatment time range of 10 to 40 seconds is appropriate for actual operation.
[0036]
In the present invention, the thickness of the steel sheet does not impose any restrictions on the present invention, and the present invention can be applied as long as it is a commonly used sheet thickness. Furthermore, the steel sheet of the present invention is sufficiently effective whether it is a cold-rolled steel sheet or a hot-rolled steel sheet manufactured by a normal process, and the effect does not change greatly depending on the history of the steel sheet. . Moreover, the hot rolling conditions, the cold rolling conditions, the annealing conditions, etc. may be selected according to the dimensions of the steel sheet and the required strength, depending on the hot rolling conditions, the cold rolling conditions, the annealing conditions, etc. The effect of the steel sheet of the present invention is not impaired.
[0037]
Of course, it is of course possible to apply various types of upper plating, especially electroplating, on the galvannealed steel sheet obtained by using the steel sheet of the present invention in order to improve the paintability and weldability. And does not depart from the present invention. Further, it is of course possible to add various treatments to the alloyed hot-dip galvanized steel sheet obtained by the method of the present invention. For example, chromate treatment, phosphate treatment, and phosphate treatment properties can be achieved. Even if the treatment for improving, the lubricity improving treatment, the weldability improving treatment, the resin coating treatment, etc. are performed, it does not depart from the scope of the present invention, and various types are added depending on the required additional characteristics. Can be applied.
[0038]
As the strength of the steel sheet of the present invention, high-strength steel (300, 340, 400, 440 N / mm 2 grade) of 300 N / mm 2 or more from ordinary steel having a tensile strength of less than 300 N / mm 2 or a steel sheet for ultra deep drawing, etc. Is a wide range of.
[0039]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
[0040]
(Example 1)
First, test materials shown in Table 1 were prepared, and an alloyed hot-dip galvanized steel sheet was manufactured using an in-line annealing method of continuous hot-dip galvanizing equipment. In plating, the annealing atmosphere was 5% hydrogen + 95% nitrogen mixed gas, the annealing temperature was 800 to 840 ° C., and the annealing time was 90 seconds. The molten zinc bath was molten zinc containing 0.12% Al, and the basis weight of zinc was adjusted to 60 g / m 2 with a gas wiper. The alloying was heated using induction heating type heating equipment so that the Fe content in the alloyed hot dip galvanizing was 10 to 11%. However, the hot-rolled steel sheet was preheated to 90 ° C. (90 seconds) instead of annealing and cooling. The Al content during plating of the galvannealed steel sheet thus obtained was 0.15 to 0.25%.
[0041]
Samples were taken from each steel plate, and plating adhesion was evaluated by the V-bending method. That is, a test piece with adhesive tape (cellophane tape) on the compression side in advance is bent in a V shape so that the bending angle is 60 °, the adhesive tape is peeled off after bending back, and the degree of peeling of the plating Was visually observed and the plating adhesion was evaluated according to the following classification.
◎: Plating layer does not peel at all ○: Plating peeling is minor △: Plating is peeled to a certain extent ×: Plating is almost peeled off [0042]
In addition, as an index of workability, a tensile test was performed on each alloyed hot-dip galvanized steel sheet, and elongation and rankford values (r values: average r values of 0 °, 45 °, and 90 °, except for cold-rolled steel plates) Only), the cold-rolled sheet passed 48% or more and passed an r value of 1.5 or more, and the hot-rolled steel sheet passed 45% or more.
[0043]
The results are shown in Table 1. As is clear from Table 1, the symbols A to R, which are examples of the present invention, have excellent plating adhesion and excellent workability of the steel sheet, whereas the symbols S to V, which are comparative examples, X had poor plating adhesion, and symbol W had insufficient workability of the steel sheet.
[0044]
[Table 1]
(Example 2)
First, test materials shown in Table 1 were prepared, and an alloyed hot-dip galvanized steel sheet was manufactured using an in-line annealing method of continuous hot-dip galvanizing equipment. In plating, the annealing atmosphere was 5% hydrogen + 95% nitrogen mixed gas, the annealing temperature was 800 to 840 ° C., and the annealing time was 90 seconds. The molten zinc bath was made of molten zinc containing Al, and the basis weight of zinc was adjusted to 60 g / m 2 with a gas wiper. Heating for alloying was performed using induction heating type heating equipment so that the Fe content in the alloyed hot dip galvanizing became the value shown in Table 2. The Al concentration in the plating bath was variously changed so that the Al content in the alloyed hot dip galvanizing became the value shown in Table 2.
[0046]
The obtained plated steel sheet was examined for press formability and plating adhesion.
[0047]
For press formability, a bead pull-out test was performed in order to examine the galling of the plating in press working. Test conditions are shown below.
・ Sample drawing width: 30mm
・ Mold: Convex mold with φ4mm on one side and shoulder R2mmR on the other side ・ Pressing load: 900kg
・ Pullout speed: 200mm / min
-Oil coating: In the evaluation of press formability with rust-preventing oil coating, the test piece that was galling and the test piece was broken was rejected, and the test piece was rejected.
[0048]
For plating adhesion, the test piece with adhesive tape (cellophane tape) on the compression side is bent in a V shape so that the bending angle is 60 °, and the adhesive tape is peeled off after bending back. The degree of peeling was visually observed and evaluated according to the following classification.
◎: Plating layer does not peel at all ○: Plating peeling is slight △: Plating is peeled to a certain extent ×: Plating is almost peeled off [0049]
The evaluation results are as shown in Table 2. For No. 1, the Fe content during plating was outside the scope of the present invention, so the press formability was rejected. In No. 6, since the Fe content during plating was out of the range of the present invention, the plating adhesion was rejected. In No. 7, since the Al content during plating was outside the range of the present invention, the plating adhesion was rejected. In No. 9, since the Al content during plating was outside the range of the present invention, a sufficient Fe content could not be ensured, and the press formability was rejected. The products of the present invention other than these were alloyed hot-dip galvanized steel sheets having good press formability and plating adhesion.
[0050]
[Table 2]
【The invention's effect】
As described above, the present invention makes it possible to provide a steel sheet to be plated that can produce an alloyed hot-dip galvanized steel sheet that is excellent in all of workability, formability, and plating adhesion. The place that contributes to is extremely large.
Claims (5)
Ｃ： ０．０００１〜０．００４％，
Ｓｉ：０．００１〜０．１０％，
Ｍｎ：０．０１〜０．５０％，
Ｐ： ０．００１〜０．０１５％，
Ｓ： ０．０１５％以下，
Ａｌ：０．１２〜０．５０％，
Ｔｉ：０．００２〜０．１０％，
Ｎ： ０．０００５〜０．００４％，
を含有し，残部Ｆｅおよび不可避不純物からなることを特徴とする合金化溶融亜鉛めっき用鋼板．% By mass
C: 0.0001 to 0.004%,
Si: 0.001 to 0.10%,
Mn: 0.01 to 0.50%,
P: 0.001 to 0.015%,
S: 0.015% or less,
Al: 0.12 to 0.50%,
Ti: 0.002 to 0.10%,
N: 0.0005 to 0.004%,
A steel sheet for alloying hot dip galvanizing, characterized by comprising the remainder Fe and inevitable impurities.
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