JP4171232B2 - Hot-dip galvanized steel with excellent surface smoothness - Google Patents
Hot-dip galvanized steel with excellent surface smoothness Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、めっき鋼板に係わり、更に詳しくは優れた表面平滑性を有し、種々の用途、例えば家電用や自動車用、建材用鋼板として適用できるめっき鋼材に関するものである。
【０００２】
【従来の技術】
耐食性の良好なめっき鋼材として最も使用されるものに亜鉛系めっき鋼板がある。この亜鉛系めっき鋼板は自動車、家電、建材分野など種々の製造業において使用されている。また、それ以外にも、めっき鋼線やどぶづけめっきなど種々の分野でめっき鋼材が使用されている。
【０００３】
上記亜鉛系めっき鋼板の耐食性を向上させることを目的として本発明者らは、特許第３１７９４４６号において溶融Ｚｎ−Ａｌ−Ｍｇ−Ｓｉめっき鋼板を提案した。また、本発明者らは特開２０００−０６４０６１号公報においてこの溶融Ｚｎ−Ａｌ−Ｍｇ−Ｓｉめっき鋼板にＣａ、Ｂｅ、Ｔｉ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒ、Ｍｎの一種または二種以上を添加することにより、さらに耐食性の優れた塗装鋼板が得られることを明らかにした。
【０００４】
また、特開２００１−２９５０１５号公報においては、溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板にＴｉ、Ｂ、Ｓｉを添加することにより表面外観が良好になることが開示されている。
【０００５】
【発明が解決しようとする課題】
しかしながら、上記及びその他これまで開示されためっき鋼板では、表面平滑性が十分に確保されていない。
【０００６】
Ｚｎ−Ｍｇ−Ａｌの三元系合金は３質量％Ｍｇ−４質量％Ａｌ−９３質量％Ｚｎに３元共晶点を持ち、それよりＡｌ濃度が高い場合、初晶としてＡｌ相が晶出する。溶融めっき時のめっき凝固速度が十分に確保されている場合、Ａｌ相が大きく成長しないうちにめっきが凝固するため表面平滑性は問題とならないが、めっき凝固速度が小さい場合、このＡｌ相が先に大きく成長することによってめっき表面に凸凹が形成され、表面平滑性が劣化するという問題点を有している。
【０００７】
しかし、前記特許第３１７９４４６号に開示される技術では、表面平滑性が劣化するという問題は考慮されていない．また、前記特開２０００−０６４０６１号公報に開示される技術では、塗装後耐食性向上を目的としてＣａ、Ｂｅ、Ｔｉ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒ、Ｍｎの一種または二種以上を添加しているが、表面平滑性が劣化するという問題は考慮されておらず、金属間化合物についても言及されていない。また、前記特開２００１−２９５０１５号公報に開示される技術では、表面外観を劣化させるＺｎ11Ｍｇ2相の生成・成長を抑制する目的としてＴｉとＢを添加しているが、表面平滑性が劣化するという問題は考慮されておらず、金属間化合物についても言及されていない。
【０００８】
そこで、本発明は、上記問題点に鑑みなされたものであり、４質量％を超えるような高Ａｌ濃度の場合でも十分な表面平滑性が優れためっき鋼材を提供することを目的としている。
【０００９】
【課題を解決するための手段】
本発明者らは、表面平滑性が優れためっき鋼板の開発について鋭意研究を重ねた結果、Ａｌ：２０質量％以下、Ｍｇ：１〜１０質量％を含有する高Ａｌ含有めっき鋼板であっても、Ｚｎ−Ａｌ−Ｍｇ系の母相に、融点が６００℃以上の金属間化合物を０．００１〜０．５質量％含有させることにより表面平滑性が向上させることが出来るという新たな知見を見出し、本発明を完成するに至ったものである。
【００１０】
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。
【００１１】
（１１） 質量％で、Ａｌ：２０％以下、Ｍｇ：１〜１０％を含有し、残部がＺｎおよび不可避不純物からなり、かつ、〔Ａｌ／Ｚｎ／Ｚｎ 2 Ｍｇの三元共晶組織〕の素地中に〔Ｚｎ相〕、〔Ａｌ相〕、〔Ｚｎ 2 Ｍｇ相〕の１つ以上を含む金属組織からなるＺｎ−Ａｌ−Ｍｇ系の母相に、融点が６００℃以上の金属間化合物を０．００１〜０．５質量％含有するめっき層を表面に有することを特徴とする表面平滑性に優れる溶融めっき鋼材。
【００１２】
（２） 質量％で、Ａｌ：２０％以下、Ｍｇ：１〜１０％、Ｓｉ：０．０１〜２％を含有し、残部がＺｎおよび不可避不純物からなり、かつ、Ａｌ／Ｚｎ／Ｚｎ 2 Ｍｇの三元共晶組織〕の素地中に〔Ｚｎ相〕、〔Ａｌ相〕、〔Ｚｎ 2 Ｍｇ相〕、〔Ｓｉ相〕、〔Ｍｇ 2 Ｓｉ相〕の１つ以上を含む金属組織からなるＺｎ−Ａｌ−Ｍｇ−Ｓｉ系の母相に、融点が６００℃以上の金属間化合物を０．００１〜０．５質量％含有するめっき層を表面に有することを特徴とする表面平滑性に優れる溶融めっき鋼材。
【００１３】
（３） 前記（１）または（２）のいずれかに記載の金属間化合物が、ＴｉＡｌ3、ＮｉＡｌ3、Ｃｏ2Ａｌ9、Ｃｏ4Ａｌ13、ＣｒＡｌ4、ＣｒＡｌ7、Ｃｒ2Ａｌ11、Ｍｎ4Ａｌ11、ＭｎＡｌ6、Ａｌ11Ｃｅ3、ＣｅＺｎ2Ａｌ2、Ａｌ9Ｉｒ2、Ａｌ11Ｌａ3、Ａｌ12Ｍｏ、ＮｂＡｌ3、Ａｌ2Ｓｅ3、ＴａＡｌ3、ＺｒＡｌ3、Ｚｒ2ＺｎＡｌ3、Ａｌ2Ｃａ、Ｔｉ7Ａｌ5Ｓｉ12、ＦｅＮｉＡｌ9、Ｆｅ3ＮｉＡｌ10、ＴｉＡｌ2、ＴｉＡｌ、Ｎｉ2Ａｌ3、ＮｉＡｌの１種または２種以上であることを特徴とする表面平滑性に優れる溶融めっき鋼材。
【００１４】
【発明の実施形態】
以下に本発明を詳細に説明する。
【００１５】
本発明の溶融めっき鋼材は、Ａｌ：２０質量％以下、Ｍｇ：１〜１０質量％、残部がＺｎおよび不可避不純物からなるめっき層中にＺｎ−Ａｌ−Ｍｇ系の母相と融点が６００℃以上の金属間化合物を０．００１〜０．５質量％含有することを特徴とするめっき鋼材、及び、Ａｌ：２０質量％以下、Ｍｇ：１〜１０質量％、Ｓｉ：０．０１〜２質量％、残部がＺｎおよび不可避不純物からなるめっき層中にＺｎ−Ａｌ−Ｍｇ−Ｓｉ系の母相と融点が６００℃以上の金属間化合物を０．００１〜０．５質量％含有することを特徴とするめっき鋼材である。
【００１６】
Ａｌの含有量を２０質量％以下に限定した理由は、２０質量％を超えると耐食性を向上させる効果が飽和するためである。
【００１７】
Ｍｇの含有量を１〜１０質量％に限定した理由は、１質量％未満では耐食性を向上させる効果が不十分であるためであり、１０質量％を超えるとめっき層が脆くなって密着性が低下するためである。
【００１８】
本発明において、Ｚｎ−Ｍｇ−Ａｌ系の母相とは、〔Ａｌ／Ｚｎ／Ｚｎ2Ｍｇの三元共晶組織〕の素地中に〔Ｚｎ相〕、〔Ａｌ相〕、〔Ｚｎ2Ｍｇ相〕の１つ以上を含む金属組織のことである。また、Ｚｎ−Ｍｇ−Ａｌ−Ｓｉ系の母相とは、〔Ａｌ／Ｚｎ／Ｚｎ2Ｍｇの三元共晶組織〕の素地中に〔Ｚｎ相〕、〔Ａｌ相〕、〔Ｚｎ2Ｍｇ相〕、〔Ｓｉ相〕、〔Ｍｇ2Ｓｉ相〕の１つ以上を含む金属組織のことである。
【００１９】
ここで、〔Ａｌ／Ｚｎ／Ｚｎ2Ｍｇの三元共晶組織〕とは、Ａｌ相と、Ｚｎ相と、金属間化合物Ｚｎ2Ｍｇ相との三元共晶組織であり、この三元共晶組織を形成しているＡｌ相は例えばＡｌ−Ｚｎ−Ｍｇの三元系平衡状態図における高温での「Ａｌ”相」（Ｚｎを固溶するＡｌ固溶体であり、少量のＭｇを含む）に相当するものである。この高温でのＡｌ”相は常温では通常は微細なＡｌ相と微細なＺｎ相に分離して現れる。また、該三元共晶組織中のＺｎ相は少量のＡｌを固溶し、場合によってはさらに少量のＭｇを固溶したＺｎ固溶体である。この三元共晶組織中のＺｎ2Ｍｇ相は、Ｚｎ−Ｍｇの二元系平衡状態図のＺｎ：約８４質量％の付近に存在する金属間化合物相である。状態図で見る限りそれぞれの相にはＳｉが固溶しているかいないか、固溶していても極微量であると考えられるがその量は通常の分析では明確に区別できないため、この３つの相からなる三元共晶組織を本明細書では〔Ａｌ／Ｚｎ／Ｚｎ2Ｍｇの三元共晶組織〕と表す。
【００２０】
また、〔Ａｌ相〕とは、前記の三元共晶組織の素地中に明瞭な境界をもって島状に見える相であり、これは例えばＡｌ−Ｚｎ−Ｍｇの三元系平衡状態図における高温での「Ａｌ”相」（Ｚｎを固溶するＡｌ固溶体であり、少量のＭｇを含む）に相当するものである。この高温でのＡｌ”相はめっき浴のＡｌやＭｇ濃度応じて固溶するＺｎ量やＭｇ量が相違する。この高温でのＡｌ”相は常温では通常は微細なＡｌ相と微細なＺｎ相に分離するが、常温で見られる島状の形状は高温でのＡｌ”相の形骸を留めたものであると見てよい。状態図で見る限りこの相にはＳｉが固溶しているかいないか、固溶していても極微量であると考えられるが通常の分析では明確に区別できないため、この高温でのＡｌ”相（Ａｌ初晶と呼ばれる）に由来し且つ形状的にはＡｌ”相の形骸を留めている相を本明細書では〔Ａｌ相〕と呼ぶ。この〔Ａｌ相〕は前記の三元共晶組織を形成しているＡｌ相とは顕微鏡観察において明瞭に区別できる。
【００２１】
また、〔Ｚｎ相〕とは、前記の三元共晶組織の素地中に明瞭な境界をもって島状に見える相であり、実際には少量のＡｌさらには少量のＭｇを固溶していることもある。状態図で見る限りこの相にはＳｉが固溶しているかいないか、固溶していても極微量であると考えられる。この〔Ｚｎ相〕は前記の三元共晶組織を形成しているＺｎ相とは顕微鏡観察において明瞭に区別できる。
【００２２】
また、〔Ｚｎ2Ｍｇ相〕とは、前記の三元共晶組織の素地中に明瞭な境界をもって島状に見える相であり、実際には少量のＡｌを固溶していることもある。状態図で見る限りこの相にはＳｉが固溶しているかいないか、固溶していても極微量であると考えられる。この〔Ｚｎ2Ｍｇ相〕は前記の三元共晶組織を形成しているＺｎ2Ｍｇ相とは顕微鏡観察において明瞭に区別できる。
【００２３】
また、〔Ｓｉ相〕とは、めっき層の凝固組織中に明瞭な境界をもって島状に見える相であり、例えばＺｎ−Ｓｉの二元系平衡状態図における初晶Ｓｉに相当する相である。実際には少量のＡｌ固溶していることもあり、状態図で見る限りＺｎ、Ｍｇは固溶していないか、固溶していても極微量であると考えられる。この〔Ｓｉ相〕はめっき中では顕微鏡観察において明瞭に区別できる。
【００２４】
また、〔Ｍｇ2Ｓｉ相〕とは、めっき層の凝固組織中に明瞭な境界をもって島状に見える相であり、例えばＡｌ−Ｍｇ−Ｓｉの三元系平衡状態図における初晶Ｍｇ2Ｓｉに相当する相である。状態図で見る限りＺｎ、Ａｌは固溶していないか、固溶していても極微量であると考えられる。この〔Ｍｇ2Ｓｉ相〕はめっき中では顕微鏡観察において明瞭に区別できる。
【００２５】
以上、述べためっき層凝固組織の一例を図１に示す。図１の上段の図１（ａ）は、本発明におけるめっき鋼材のめっき層の顕微鏡写真（倍率２５００倍）であり、該写真中の各組織の分布状態を図示したものが下段の図１（ｂ）である。この図からも判るように、本発明におけるめっき鋼材のめっき層の顕微鏡写真によって明確に各組織を特定することが出来る。
【００２６】
本発明では、表面平滑性を向上させるためにこのＺｎ−Ｍｇ−Ａｌ系の母相、または、Ｚｎ−Ｍｇ−Ａｌ−Ｓｉ系の母相に融点が６００℃以上の金属間化合物を０．００１〜０．５質量％含有させる。融点が６００℃以上の金属間化合物を含有させて表面平滑性が向上する理由は、高融点の金属間化合物が結晶の核となり〔Ａｌ相〕の結晶が数多く晶出し、結果的に〔Ａｌ相〕の結晶成長が抑制されるためだと考えられる。
【００２７】
ここで表面平滑性の悪いめっきとは、めっき表面に数百μｍ〜数ｍｍ間隔の凸凹が形成された状態を示し、目視でも十分確認できる。断面を光学顕微鏡で確認するとめっきが厚い部分と薄い部分に分かれており、極端な場合、薄い部分が厚い部分の半分以下となることもある。
【００２８】
本発明において、めっき中に含有する金属間化合物の融点を６００℃以上に限定した理由は、めっき浴温より低い融点では表面平滑性を向上させることができないためである。
【００２９】
金属間化合物の含有量を０．００１〜０．５質量％に限定した理由は、０．００１質量％未満では表面平滑性を向上させる効果が不十分であるためであり、０．５質量％を超えると金属間化合物自身がめっき後の外観を悪化させるためである。
【００３０】
金属間化合物の添加方法については特に限定するところはなく、金属間化合物の微粉末を浴中に混濁させる方法や、金属間化合物を浴に溶解させる方法等が適用できる。特にＴｉ、Ｎｉ、Ｃｏ、Ｃｒ、Ｍｎ、Ｃｅ、Ｉｒ、Ｌａ、Ｍｏ、Ｎｂ、Ｓｅ、Ｔａ、Ｚｒ、Ｃａ等、４００〜６００℃のＺｎ−Ａｌ合金液体に微量溶解し、凝固時、Ａｌ相が晶出する前に金属間化合物として晶出する元素を添加した浴は表面平滑性を向上させる効果が大きい。
【００３１】
上記のような性質を持つ元素を添加した浴を使用して溶融めっきしためっき層中には、Ｚｎ−Ｍｇ−Ａｌ系の母相、または、Ｚｎ−Ｍｇ−Ａｌ−Ｓｉ系の母相とＴｉＡｌ3、ＮｉＡｌ3、Ｃｏ2Ａｌ9、Ｃｏ4Ａｌ13、ＣｒＡｌ4、ＣｒＡｌ7、Ｃｒ2Ａｌ11、Ｍｎ4Ａｌ11、ＭｎＡｌ6、Ａｌ11Ｃｅ3、ＣｅＺｎ2Ａｌ2、Ａｌ9Ｉｒ2、Ａｌ11Ｌａ3、Ａｌ12Ｍｏ、ＮｂＡｌ3、Ａｌ2Ｓｅ3、ＴａＡｌ3、ＺｒＡｌ3、Ｚｒ2ＺｎＡｌ3、Ａｌ2Ｃａ、Ｔｉ7Ａｌ5Ｓｉ12、ＦｅＮｉＡｌ9、Ｆｅ3ＮｉＡｌ10、ＴｉＡｌ2、ＴｉＡｌ、Ｎｉ2Ａｌ3、ＮｉＡｌの１種または２種以上の金属間化合物を含有することになる。
【００３２】
これらの金属間化合物もめっき層の凝固組織中に明瞭な境界をもって島状に見える。また、Ｚｎ−Ｍｇ−Ａｌ−Ｓｉ系の浴から晶出させた場合には少量のＳｉを固溶していることもある。
【００３３】
めっき層中には、これ以外にＦｅ、Ｓｂ、Ｐｂ、Ｓｎを単独あるいは複合で０．５質量％以内含有してもよい。また、Ｐ、Ｂ、Ｂｉ、３族元素を合計で０．５質量％以下含有しても本発明の効果を損なわず、その量によってはさらに耐食性が改善される等好ましい場合もある。
【００３４】
本発明の下地鋼材としては、鋼板のみならず、線材、形鋼、条鋼、鋼管など種々の鋼材が使用できる。鋼板としては、熱延鋼板、冷延鋼板共に使用でき、鋼種もＡｌキルド鋼、Ｔｉ、Ｎｂ等を添加した極低炭素鋼板、およびこれらにＰ、Ｓｉ、Ｍｎ等の強化元素を添加した高強度鋼、ステンレス鋼等種々のものが適用できる。
【００３５】
本発明品の製造方法については、特に限定することなく鋼板の連続めっき、鋼材や線材のどぶづけめっき法など種々の方法が適用できる。下層としてＮｉプレめっきを施す場合でも通常行われているプレめっき方法を適用すれば良い。本発明品は冷却速度が小さい場合でも表面平滑性が良好なめっきが得られるため、大きな冷却速度が取りにくいドブ漬けめっきや、板厚の厚い材料への溶融めっきにおいてその効果が顕著となる。
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１０ｇ／ｍ2以上、加工性の観点から３５０ｇ／ｍ2以下で有ることが望ましい。
【００３６】
【実施例】
以下、実施例により本発明を具体的に説明する。
まず、厚さ２．０ｍｍの冷延鋼板を準備し、これに４００〜６００℃で浴中の添加元素量を変化させたＺｎ合金めっき浴で３秒溶融めっきを行い、Ｎ2ワイピングでめっき付着量を１４０ｇ／ｍ2に調整し、冷却速度１０℃／ｓ以下で冷却した。得られためっき鋼板のめっき組成を表１に示す。
【００３７】
平滑性は波長領域２００μｍ以上の粗度を測定し、１μｍ以下のものを合格とした。
【００３８】
評価結果を表１に示す。番号１、２３はめっき層中に金属間化合物を含有しないため平滑性が不合格となった。これら以外はいずれも良好な平滑性を示した。
【００３９】
【表１】
【発明の効果】
以上述べてきたように、本発明により、めっき凝固速度が小さい場合でも表面に凸凹が形成されず表面平滑性が優れためっき鋼板を製造することが可能となり、工業上極めて優れた効果を奏することができる。
【図面の簡単な説明】
【図１】めっき層凝固組織の一例を示す図で、（ａ）は、本発明におけるめっき鋼材のめっき層の顕微鏡写真（倍率２５００倍）であり、（ｂ）は該写真中の各組織の分布状態を示した図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plated steel sheet, and more particularly, to a plated steel material that has excellent surface smoothness and can be applied as a steel sheet for various uses such as home appliances, automobiles, and building materials.
[0002]
[Prior art]
Zinc-based plated steel sheets are the most used as plated steel materials with good corrosion resistance. This zinc-based plated steel sheet is used in various manufacturing industries such as automobiles, home appliances, and building materials. In addition, plated steel materials are used in various fields such as plated steel wires and dodging plating.
[0003]
In order to improve the corrosion resistance of the galvanized steel sheet, the present inventors proposed a molten Zn—Al—Mg—Si plated steel sheet in Japanese Patent No. 3179446. In addition, the inventors added one or more of Ca, Be, Ti, Cu, Ni, Co, Cr, and Mn to the molten Zn—Al—Mg—Si plated steel sheet in Japanese Patent Application Laid-Open No. 2000-064061. As a result, it was clarified that a coated steel sheet having further excellent corrosion resistance can be obtained.
[0004]
Japanese Patent Laid-Open No. 2001-295015 discloses that the surface appearance is improved by adding Ti, B, and Si to a molten Zn—Al—Mg plated steel sheet.
[0005]
[Problems to be solved by the invention]
However, in the above and other plated steel sheets disclosed so far, the surface smoothness is not sufficiently ensured.
[0006]
The Zn-Mg-Al ternary alloy has a ternary eutectic point in 3 mass% Mg-4 mass% Al-93 mass% Zn, and when the Al concentration is higher than that, an Al phase is crystallized as the primary crystal. To do. If the plating solidification rate at the time of hot dipping is sufficiently secured, the surface smoothness does not matter because the plating solidifies before the Al phase grows greatly, but if the plating solidification rate is low, this Al phase However, there is a problem that unevenness is formed on the plating surface and the surface smoothness deteriorates.
[0007]
However, the technique disclosed in the above-mentioned Japanese Patent No. 3179446 does not consider the problem that the surface smoothness deteriorates. Moreover, in the technique disclosed in the Japanese Patent Application Laid-Open No. 2000-064061, one or more of Ca, Be, Ti, Cu, Ni, Co, Cr, and Mn are added for the purpose of improving post-coating corrosion resistance. However, the problem that surface smoothness deteriorates is not taken into consideration, and an intermetallic compound is not mentioned. Further, in the technique disclosed in Japanese Patent Laid-Open No. 2001-295015, Ti and B are added for the purpose of suppressing the formation and growth of a Zn 11 Mg 2 phase that deteriorates the surface appearance. The problem of deterioration is not taken into account, and no mention is made of intermetallic compounds.
[0008]
Then, this invention is made | formed in view of the said problem, and it aims at providing the plated steel material which was excellent in sufficient surface smoothness also in the case of the high Al concentration which exceeds 4 mass%.
[0009]
[Means for Solving the Problems]
As a result of intensive studies on the development of a plated steel sheet having excellent surface smoothness, the present inventors have found that even if it is a high Al-containing plated steel sheet containing Al: 20% by mass or less and Mg: 1-10% by mass. , Discovered that the surface smoothness can be improved by adding 0.001 to 0.5% by mass of an intermetallic compound having a melting point of 600 ° C. or higher in the Zn—Al—Mg matrix. The present invention has been completed.
[0010]
That is, the gist of the present invention is as follows.
[0011]
(11) By mass%, Al: 20% or less, Mg: 1 to 10%, the balance consisting of Zn and inevitable impurities, and [Al / Zn / Zn 2 Mg ternary eutectic structure] An intermetallic compound having a melting point of 600 ° C. or higher is added to a Zn—Al—Mg based matrix composed of a metal structure containing one or more of [Zn phase], [Al phase], and [Zn 2 Mg phase] in the substrate. A hot-dip plated steel material having excellent surface smoothness, comprising a plating layer containing 0.001 to 0.5% by mass on the surface.
[0012]
(2) By mass%, Al: 20% or less, Mg: 1 to 10%, Si: 0.01 to 2%, the balance is made of Zn and inevitable impurities, and Al / Zn / Zn 2 Mg Zn composed of a metal structure containing at least one of [Zn phase], [Al phase], [Zn 2 Mg phase], [Si phase], and [Mg 2 Si phase] in the substrate of Melting with excellent surface smoothness characterized by having a plating layer containing 0.001 to 0.5% by mass of an intermetallic compound having a melting point of 600 ° C. or higher on the surface of an Al—Mg—Si matrix. Plated steel.
[0013]
(3) The intermetallic compound according to either (1) or (2) is TiAl 3 , NiAl 3 , Co 2 Al 9 , Co 4 Al 13 , CrAl 4 , CrAl 7 , Cr 2 Al 11 , Mn 4 Al 11 , MnAl 6 , Al 11 Ce 3 , CeZn 2 Al 2 , Al 9 Ir 2 , Al 11 La 3 , Al 12 Mo, NbAl 3 , Al 2 Se 3 , TaAl 3 , ZrAl 3 , Zr 2 ZnAl 3 , Melting with excellent surface smoothness, characterized by being one or more of Al 2 Ca, Ti 7 Al 5 Si 12 , FeNiAl 9 , Fe 3 NiAl 10 , TiAl 2 , TiAl, Ni 2 Al 3 , NiAl Plated steel.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0015]
The hot-dip plated steel material of the present invention has a melting point of 600 ° C. or higher with a Zn—Al—Mg matrix in the plating layer comprising Al: 20 mass% or less, Mg: 1-10 mass%, the balance being Zn and inevitable impurities. A plated steel material containing 0.001 to 0.5% by mass of an intermetallic compound, and Al: 20% by mass or less, Mg: 1 to 10% by mass, Si: 0.01 to 2% by mass Further, the plating layer comprising Zn and inevitable impurities in the balance contains Zn-Al-Mg-Si base phase and 0.001 to 0.5 mass% of an intermetallic compound having a melting point of 600 ° C or higher. It is a plated steel material.
[0016]
The reason why the content of Al is limited to 20% by mass or less is that when it exceeds 20% by mass, the effect of improving the corrosion resistance is saturated.
[0017]
The reason why the content of Mg is limited to 1 to 10% by mass is that if it is less than 1% by mass, the effect of improving the corrosion resistance is insufficient, and if it exceeds 10% by mass, the plating layer becomes brittle and adhesion is improved. It is because it falls.
[0018]
In the present invention, the Zn—Mg—Al-based parent phase refers to [Zn phase], [Al phase], [Zn 2 Mg phase] in the [Al / Zn / Zn 2 Mg ternary eutectic structure] substrate. ] Is a metal structure containing one or more of the following. In addition, the Zn—Mg—Al—Si-based matrix is a [Zn phase], [Al phase], [Zn 2 Mg phase] in a [Al / Zn / Zn 2 Mg ternary eutectic structure] substrate. ], [Si phase] and [Mg 2 Si phase].
[0019]
Here, [Al / Zn / Zn 2 Mg ternary eutectic structure] is a ternary eutectic structure of an Al phase, a Zn phase, and an intermetallic compound Zn 2 Mg phase. The Al phase forming the crystal structure is, for example, an “Al” phase ”(Al solid solution in which Zn is solid-solved and containing a small amount of Mg) in the ternary equilibrium diagram of Al—Zn—Mg. It is equivalent. The Al "phase at high temperature usually appears separated into a fine Al phase and a fine Zn phase at room temperature. The Zn phase in the ternary eutectic structure dissolves a small amount of Al, and in some cases The Zn 2 Mg phase in the ternary eutectic structure exists in the vicinity of Zn: about 84% by mass in the Zn-Mg binary equilibrium diagram. As seen from the phase diagram, Si is not dissolved in each phase, or even if it is dissolved in each phase, it is considered that the amount is very small, but the amount is clearly determined by ordinary analysis. Since it cannot be distinguished, the ternary eutectic structure composed of these three phases is expressed as [Al / Zn / Zn 2 Mg ternary eutectic structure] in this specification.
[0020]
In addition, the [Al phase] is a phase that looks like an island with a clear boundary in the ternary eutectic structure, which is, for example, at a high temperature in an Al—Zn—Mg ternary equilibrium diagram. "Al" phase (which is an Al solid solution in which Zn is dissolved, and contains a small amount of Mg). The Al "phase at this high temperature differs in the amount of Zn and Mg dissolved depending on the Al and Mg concentrations in the plating bath. The Al" phase at this high temperature is usually a fine Al phase and a fine Zn phase. However, it can be seen that the island-like shape seen at room temperature retains the shape of the Al "phase at high temperature. As far as the phase diagram shows, this phase does not contain Si in solid solution. Although it is considered to be a trace amount even if it is dissolved, it cannot be clearly distinguished by ordinary analysis. Therefore, it originates from the Al "phase (called Al primary crystal) at this high temperature and is Al" in shape. In the present specification, the phase holding the form of the phase is referred to as [Al phase], which can be clearly distinguished from the Al phase forming the ternary eutectic structure by microscopic observation.
[0021]
In addition, the [Zn phase] is a phase that looks like an island with a clear boundary in the ternary eutectic structure, and actually contains a small amount of Al and a small amount of Mg as a solid solution. There is also. As far as the phase diagram is concerned, it is considered that Si is in a solid solution in this phase, or a very small amount even if it is dissolved. This [Zn phase] can be clearly distinguished from the Zn phase forming the ternary eutectic structure by microscopic observation.
[0022]
The [Zn 2 Mg phase] is a phase that looks like an island with a clear boundary in the ternary eutectic structure, and a small amount of Al may be actually dissolved. As far as the phase diagram is concerned, it is considered that Si is in a solid solution in this phase, or a very small amount even if it is dissolved. This [Zn 2 Mg phase] can be clearly distinguished from the Zn 2 Mg phase forming the ternary eutectic structure by microscopic observation.
[0023]
Further, the [Si phase] is a phase that looks like an island with a clear boundary in the solidified structure of the plating layer, and is a phase corresponding to, for example, primary Si in the Zn-Si binary equilibrium diagram. Actually, a small amount of Al may be dissolved, and as seen from the phase diagram, Zn and Mg are not dissolved or are considered to be extremely small even if dissolved. This [Si phase] can be clearly distinguished by microscopic observation during plating.
[0024]
The [Mg 2 Si phase] is a phase that looks like an island with a clear boundary in the solidified structure of the plating layer. For example, the primary Mg 2 Si in the ternary equilibrium diagram of Al—Mg—Si Corresponding phase. As far as the phase diagram is concerned, it is considered that Zn and Al are not dissolved, or even if they are dissolved. This [Mg 2 Si phase] can be clearly distinguished in microscopy in the plating.
[0025]
An example of the plated layer solidified structure described above is shown in FIG. FIG. 1A in the upper part of FIG. 1 is a micrograph (magnification 2500 times) of the plating layer of the plated steel material in the present invention, and the distribution state of each structure in the photograph is shown in FIG. b). As can be seen from this figure, each structure can be clearly identified by a micrograph of the plated layer of the plated steel material in the present invention.
[0026]
In the present invention, in order to improve surface smoothness, an intermetallic compound having a melting point of 600 ° C. or higher is added to the Zn—Mg—Al-based matrix or the Zn—Mg—Al—Si-based matrix. -0.5 mass% is contained. The reason why the surface smoothness is improved by including an intermetallic compound having a melting point of 600 ° C. or higher is that the high melting point intermetallic compound becomes the nucleus of the crystal, and a large number of [Al phase] crystals are formed. It is thought that this is because the crystal growth of
[0027]
Here, plating with poor surface smoothness refers to a state in which unevenness with an interval of several hundred μm to several mm is formed on the plating surface, which can be sufficiently confirmed visually. When the cross section is confirmed with an optical microscope, the plating is divided into a thick part and a thin part. In an extreme case, the thin part may be less than half of the thick part.
[0028]
In the present invention, the reason why the melting point of the intermetallic compound contained in the plating is limited to 600 ° C. or more is that the surface smoothness cannot be improved at a melting point lower than the plating bath temperature.
[0029]
The reason why the content of the intermetallic compound is limited to 0.001 to 0.5% by mass is that the effect of improving the surface smoothness is insufficient at less than 0.001% by mass, and 0.5% by mass. This is because the intermetallic compound itself deteriorates the appearance after plating when the amount exceeds.
[0030]
There are no particular limitations on the method of adding the intermetallic compound, and a method of making the intermetallic compound fine powder turbid in the bath, a method of dissolving the intermetallic compound in the bath, or the like can be applied. In particular, Ti, Ni, Co, Cr, Mn, Ce, Ir, La, Mo, Nb, Se, Ta, Zr, Ca, etc., are dissolved in a small amount in a Zn-Al alloy liquid at 400 to 600 ° C. A bath to which an element that crystallizes as an intermetallic compound is added before crystallization of crystal has a great effect of improving the surface smoothness.
[0031]
In a plating layer that is hot-dip plated using a bath to which an element having the above properties is added, a Zn-Mg-Al-based matrix, or a Zn-Mg-Al-Si-based matrix and TiAl 3 , NiAl 3 , Co 2 Al 9 , Co 4 Al 13 , CrAl 4 , CrAl 7 , Cr 2 Al 11 , Mn 4 Al 11 , MnAl 6 , Al 11 Ce 3 , CeZn 2 Al 2 , Al 9 Ir 2 , Al 11 La 3 , Al 12 Mo, NbAl 3 , Al 2 Se 3 , TaAl 3 , ZrAl 3 , Zr 2 ZnAl 3 , Al 2 Ca, Ti 7 Al 5 Si 12 , FeNiAl 9 , Fe 3 NiAl 10 , TiAl 2 , TiAl , Ni 2 Al 3 , NiAl, or one or more intermetallic compounds.
[0032]
These intermetallic compounds also appear as islands with clear boundaries in the solidified structure of the plating layer. In addition, when crystallizing from a Zn-Mg-Al-Si bath, a small amount of Si may be dissolved.
[0033]
In addition to this, the plating layer may contain Fe, Sb, Pb, and Sn alone or in combination within 0.5% by mass. Moreover, even if it contains 0.5 mass% or less of P, B, Bi, and a 3 group element in total, the effect of this invention is not impaired, and depending on the quantity, corrosion resistance may improve further, and it may be preferable.
[0034]
As the base steel material of the present invention, not only a steel plate but also various steel materials such as a wire, a shape steel, a steel bar, and a steel pipe can be used. As steel plates, both hot-rolled steel plates and cold-rolled steel plates can be used, and the steel types are ultra-low carbon steel plates to which Al killed steel, Ti, Nb, etc. are added, and high strength to which reinforcing elements such as P, Si, Mn are added. Various materials such as steel and stainless steel can be applied.
[0035]
There are no particular limitations on the method for producing the product of the present invention, and various methods such as continuous plating of steel plates and dip plating of steel materials and wires can be applied. Even when Ni pre-plating is applied as the lower layer, a conventional pre-plating method may be applied. Since the product of the present invention can obtain a plating having a good surface smoothness even when the cooling rate is low, the effect is remarkable in dove dipping plating in which a large cooling rate cannot be easily obtained and hot dipping on a material having a large plate thickness.
There are no particular restrictions on the amount of plating deposited, but it is preferably 10 g / m 2 or more from the viewpoint of corrosion resistance and 350 g / m 2 or less from the viewpoint of workability.
[0036]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
First, a cold-rolled steel sheet having a thickness of 2.0 mm is prepared, and this is subjected to hot-dip plating for 3 seconds in a Zn alloy plating bath in which the amount of additive elements in the bath is changed at 400 to 600 ° C., and then plated by N 2 wiping. The amount was adjusted to 140 g / m 2 and cooled at a cooling rate of 10 ° C./s or less. Table 1 shows the plating composition of the obtained plated steel sheet.
[0037]
For smoothness, the roughness of a wavelength region of 200 μm or more was measured, and a roughness of 1 μm or less was accepted.
[0038]
The evaluation results are shown in Table 1. Numbers 1 and 23 did not contain an intermetallic compound in the plating layer, so the smoothness was rejected. Except for these, all showed good smoothness.
[0039]
[Table 1]
【The invention's effect】
As described above, according to the present invention, even when the plating solidification rate is low, it is possible to produce a plated steel sheet having excellent surface smoothness without forming irregularities on the surface, and exhibiting an extremely excellent effect in industry. Can do.
[Brief description of the drawings]
FIG. 1 is a view showing an example of a solidified structure of a plating layer, in which (a) is a micrograph (magnification 2500 times) of a plating layer of a plated steel material in the present invention, and (b) is a diagram of each structure in the photograph. It is the figure which showed the distribution state.
Claims (3)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002064303A JP4171232B2 (en) | 2002-03-08 | 2002-03-08 | Hot-dip galvanized steel with excellent surface smoothness |
| CNB03805566XA CN100540719C (en) | 2002-03-08 | 2003-01-09 | The highly corrosion-resistant hot dip steel that surface smoothing is good |
| US10/507,148 US7238431B2 (en) | 2002-03-08 | 2003-01-09 | Highly corrosion-resistant hot dip plated steel material excellent in surface smoothness |
| EP03701043A EP1489195A4 (en) | 2002-03-08 | 2003-01-09 | Highly corrosion-resistant hot dip metal plated steel product excellent in surface smoothness |
| KR1020047014047A KR100728893B1 (en) | 2002-03-08 | 2003-01-09 | Highly corrosion-resistant hot dip metal plated steel product excellent in surface smoothness |
| PCT/JP2003/000129 WO2003076679A1 (en) | 2002-03-08 | 2003-01-09 | Highly corrosion-resistant hot dip metal plated steel product excellent in surface smoothness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002064303A JP4171232B2 (en) | 2002-03-08 | 2002-03-08 | Hot-dip galvanized steel with excellent surface smoothness |
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| JP2003268517A JP2003268517A (en) | 2003-09-25 |
| JP4171232B2 true JP4171232B2 (en) | 2008-10-22 |
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| JP2002064303A Expired - Lifetime JP4171232B2 (en) | 2002-03-08 | 2002-03-08 | Hot-dip galvanized steel with excellent surface smoothness |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4102035B2 (en) * | 2000-04-18 | 2008-06-18 | 新日本製鐵株式会社 | Plating product with excellent corrosion resistance and manufacturing method thereof |
| JP4374263B2 (en) * | 2004-03-11 | 2009-12-02 | 新日本製鐵株式会社 | High corrosion resistance hot-dip galvanized steel sheet with excellent abrasion resistance and manufacturing method thereof |
| JP4528149B2 (en) * | 2004-04-09 | 2010-08-18 | 新日本製鐵株式会社 | Hot-dip plated steel and coated steel plate with excellent corrosion resistance |
| JP4374281B2 (en) * | 2004-05-26 | 2009-12-02 | 新日本製鐵株式会社 | Hot-dip galvanized steel with excellent corrosion resistance |
| JP4546884B2 (en) * | 2004-07-07 | 2010-09-22 | 新日本製鐵株式会社 | Surface treated galvanized steel sheet with excellent corrosion resistance |
| JP4374289B2 (en) * | 2004-07-07 | 2009-12-02 | 新日本製鐵株式会社 | Surface treated steel plate with excellent corrosion resistance |
| JP2006193776A (en) * | 2005-01-12 | 2006-07-27 | Nisshin Steel Co Ltd | STEEL SHEET PLATED WITH Zn-Al-Mg ALLOY SUPERIOR IN SLIDABILITY, AND SLIDING MEMBER |
| JP4528187B2 (en) * | 2005-04-01 | 2010-08-18 | 新日本製鐵株式会社 | Hot-dip steel sheet with good appearance |
| JP5200851B2 (en) * | 2008-10-23 | 2013-06-05 | 新日鐵住金株式会社 | Zn-Al-Mg-based plated steel sheet and method for producing the same |
| CN102115860B (en) * | 2011-04-21 | 2012-07-04 | 淄博凤阳彩钢板有限公司 | Hot dip galvanizing melt and production process thereof |
| JP6366340B2 (en) * | 2014-04-28 | 2018-08-01 | 宝菱産業株式会社 | Tunnel interior board with tiles attached to a steel plate substrate |
| WO2017073579A1 (en) * | 2015-10-26 | 2017-05-04 | 新日鐵住金株式会社 | Plated steel sheet |
| CN108913949A (en) * | 2018-07-11 | 2018-11-30 | 江苏麟龙新材料股份有限公司 | It is a kind of for preplating alloy-steel plate without silicon multicomponent alloy coating material and its manufacturing method |
| JP7381864B2 (en) * | 2019-11-29 | 2023-11-16 | 日本製鉄株式会社 | Zn-Al-Mg hot-dipped steel sheet |
| CN114729437A (en) * | 2019-11-29 | 2022-07-08 | 日本制铁株式会社 | Zn-Al-Mg hot-dip coated steel sheet |
| JP7381865B2 (en) * | 2019-11-29 | 2023-11-16 | 日本製鉄株式会社 | Zn-Al-Mg hot-dipped steel sheet |
| JP7417102B2 (en) | 2020-06-09 | 2024-01-18 | 日本製鉄株式会社 | Hot-dip Zn-Al-Mg plated steel |
| JP7436840B2 (en) | 2020-06-09 | 2024-02-22 | 日本製鉄株式会社 | Hot-dip Zn-Al-Mg plated steel |
| JP7417103B2 (en) | 2020-06-09 | 2024-01-18 | 日本製鉄株式会社 | Hot-dip Zn-Al-Mg plated steel material |
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| US4401727A (en) * | 1982-06-23 | 1983-08-30 | Bethlehem Steel Corporation | Ferrous product having an alloy coating thereon of Al-Zn-Mg-Si Alloy, and method |
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| JP3287351B2 (en) * | 2000-03-15 | 2002-06-04 | 住友金属工業株式会社 | Hot-dip Zn-Al-based alloy plated steel sheet excellent in workability and method for producing the same |
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