JP2018502989A - 表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板及びその製造方法 - Google Patents
表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板及びその製造方法 Download PDFInfo
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- JP2018502989A JP2018502989A JP2017530129A JP2017530129A JP2018502989A JP 2018502989 A JP2018502989 A JP 2018502989A JP 2017530129 A JP2017530129 A JP 2017530129A JP 2017530129 A JP2017530129 A JP 2017530129A JP 2018502989 A JP2018502989 A JP 2018502989A
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- steel sheet
- dip galvanized
- hot
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- galvanized steel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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- B32B15/00—Layered products comprising a layer of metal
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Abstract
Description
炭素(C)は、鋼を強化させるのに有効な元素であって、本発明では、残留オーステナイトの安定化及び強度確保のために添加される重要元素である。上記Cの含量は、上記のような目的を達成するために、0.1重量%以上添加されることが好ましいが、その含量が0.3重量%を超える場合には、鋳片欠陥が発生する恐れが増加するだけでなく、溶接性も著しく低下するという問題がある。したがって、本発明において上記Cの含量は0.1〜0.3重量%に制限することが好ましい。
シリコン(Si)は、フェライト内における炭化物の析出を抑制し、フェライト中の炭素がオーステナイトに拡散することを助長することにより、結果的に残留オーステナイトの安定化に寄与する元素である。上記Siの含量は、上記のような目的を達成するために0.1重量%以上添加されることが好ましい。その含量が2.0重量%を超える場合には、熱間及び冷間圧延性が非常に劣り、鋼表面に酸化物を形成して、めっき性を阻害するという問題がある。したがって、本発明において上記Siの含量は0.1〜2.0重量%に制限することが好ましい。
アルミニウム(Al)は、鋼中の酸素と結合して脱酸作用をする元素であって、そのためには、その含量が0.005重量%以上を維持することが好ましい。また、Alは、上記Siと同様に、フェライト内で炭化物の生成を抑制することで、残留オーステナイトの安定化に寄与する。但し、上記Alの含量が1.5重量%を超える場合には、鋳造時にモールドフラックスと反応することにより健全なスラブの製造が困難となり、Siと同様に表面酸化物を形成するため、めっき性を阻害するという問題がある。したがって、本発明において上記Alの含量は0.005〜1.5重量%に制限することが好ましい。
マンガン(Mn)は、フェライトの変態を制御し、且つ残留オーステナイトの形成及び安定化に有効な元素である。上記Mnの含量が1.5重量%未満である場合には、フェライトの変態が多量発生するため、製造された鋼板の強度を所望通りに確保することが困難になるという問題がある。また、上記Mnの含量が3.5重量%を超える場合には、本発明の二次焼鈍工程における熱処理時の相変態が非常に遅れ、これによってマルテンサイトが多量形成されることで、製造された鋼板の軟性を意図通りに確保することが困難になるという問題がある。したがって、本発明において上記Mnの含量は1.5〜3.5重量%に制限することが好ましい。
リン(P)は、固溶強化の効果を得ることができる元素であるが、その含量が0.04重量%を超える場合には、溶接性が低下し、鋼の脆性が低下する恐れが大きくなるという問題がある。したがって、上記Pの上限は、0.04重量%以下に制限することが好ましく、0.02重量%以下に制限することがより好ましい。
硫黄(S)は、鋼中に不可避に含有される不純物元素であって、その含量をできる限り抑えることが好ましい。理論上Sの含量は0%に制限することが有利であるが、製造工程上、必然的に含有されざるを得ない。したがって、上限を管理することが重要であり、その含量が0.015重量%を超える場合には、鋼板の軟性及び溶接性を阻害する可能性が高い。したがって、本発明では上記Sの上限を0.015重量%以下に制限することが好ましい。
窒素(N)は、オーステナイトの安定化に有効な作用をする元素であるが、その含量が0.02重量%を超える場合には、鋼の脆性が低下する恐れが増加し、Alと反応してAlNが過多に析出されることにより、連鋳品質が低下するという問題がある。したがって、本発明ではNの上限を0.02重量%以下に制限することが好ましい。
ニオブ(Nb):0.005〜0.1重量%
バナジウム(V):0.005〜0.1重量%
ジルコニウム(Zr):0.005〜0.1重量%
タングステン(W):0.005〜0.5重量%
ニッケル(Ni):1重量%以下(0は除く)
銅(Cu):0.5重量%以下(0は除く)
クロム(Cr):1重量%以下(0は除く)
ボロン(B):0.01%以下(0%は除く)
重量%で、炭素(C):0.1〜0.3%、シリコン(Si):0.1〜2.0%、アルミニウム(Al):0.005〜1.5%、マンガン(Mn):1.5〜3.5%、リン(P):0.04%以下(0%は除く)、硫黄(S):0.015%以下(0%は除く)、窒素(N):0.02%以下(0は除く)、残部のFe、及びその他の不可避不純物を含み、ビスマス(Bi)、スズ(Sn)及びアンチモン(Sb)からなる群から選択された1種以上を0.01重量%〜0.07重量%含むスラブを準備する。
上記スラブを再加熱する。
上記再加熱されたスラブを熱間圧延して熱延鋼板を製造する。
上記のような熱延鋼板を巻き取る。
上記巻き取られた熱延鋼板を冷間圧延する。
本発明による溶融亜鉛めっき鋼板の微細組織は、面積分率で、ポリゴナルフェライト5%以下、針状フェライト70%以下、針状の残留オーステナイト25%以下(0%は除く)、及び残部のマルテンサイトを含むことを特徴とする。このような溶融亜鉛めっき鋼板を製造するためには、一次焼鈍工程及び後述の二次焼鈍工程の制御が非常に重要である。
選択的に、本発明による溶融亜鉛めっき鋼板の製造方法は、一次焼鈍段階の後に酸洗処理する段階をさらに含むことができる。
上記一次焼鈍工程及び選択的に酸洗工程を完了した後、二次焼鈍工程を行う。上記二次焼鈍工程は、熱処理、冷却及び再加熱処理する方法により行われることができる。
上記のような方法により二次焼鈍が完了した鋼板に溶融亜鉛めっきを行う。
必要に応じて、本発明の製造方法は、上記溶融亜鉛めっきする段階の後に合金化処理する段階をさらに含むことができる。
下記表1及び表2に記載の成分及び含量の鋼種A〜Iを用いて、真空溶解により厚さ90mm、幅175mmのインゴットに製造した後、1200℃で1時間再加熱して均質化処理した後、Ar3以上である900℃で熱間仕上圧延することで、熱延鋼板を製造した。
Ms=539−423C−30.4Mn−12.1Cr−17.7Ni−7.5Mo
Ac1=723−10.7Mn−16.9Ni+29.1Si+16.9Cr+290As+6.38W
Ac3=910−203vC−15.2Ni+44.7Si+104V+31.5Mo+13.1W−30Mn−11Cr−0Cu+700P+400Al+120As+400Ti
‐二次焼鈍前の微細組織が冷延組織である場合は、一次焼鈍工程を行っていない場合である。
‐二次焼鈍条件のうち、Ms〜Mf範囲内の冷却温度及び再加熱温度が「none」と表現されたものは、Q&P工程でなく一般焼鈍工程が適用されたものであって、過時効温度として記載された数値で熱処理を行う。このとき、Q&P工程を行った場合は、過時効温度を「none」と表示して区別した。
発明例1〜21及び比較例1〜18により製造された溶融亜鉛めっき鋼板に対して、降伏強度、引張強度及び延伸率を測定し、下記表6に示した。
発明例1〜21及び比較例1〜18により製造された溶融亜鉛めっき鋼板において、素地鋼板の表層部におけるBi、Sb及び/またはSnの濃化を観察するために、断面をFIB(集束イオンビーム)で加工して3‐D APT(原子プローブトポグラフィー)の組成プロファイルを行った。このとき、素地鋼板と亜鉛めっき層の界面から素地鋼板の方向に0.05μm地点でBi、Sb及び/またはSnの含量を測定し、0.25μm地点でBi、Sb及び/またはSnの含量を測定した後、0.25μm地点のBi、Sb及び/またはSnの含量に対する0.05μm地点のBi、Sb及び/またはSnの含量の割合を計算し、下記表6に示した。
発明例1〜21及び比較例1〜18により製造された溶融亜鉛めっき鋼板を、1mmの曲率半径を有するダイを用いて内角90°に曲げた後、クラックの発生有無を確認して下記表7に示した。
発明例1〜21及び比較例1〜18により製造された溶融亜鉛めっき鋼板に対して、表面の未めっき部位の存在有無及び程度を目視及び光学顕微鏡で観察し、その結果を下記表7に示した。評価基準は下記のとおりである。
○優秀(直径0.2mm未満サイズの未めっきが100cm2内で観察される鋼板)
△良好(直径0.2mm〜1mmサイズの未めっきが100cm2内で観察される鋼板)
×極めて不良(直径1mmを超えるサイズの未めっきが100cm2内で観察される鋼板)
発明例1〜21及び比較例1〜18により製造された溶融亜鉛めっき鋼板の表面に自動車構造用接着剤を塗布して乾燥してから、内角90°に曲げた後、めっき層が接着剤によって剥離されるか否かを観察し、結果を下記表7に示した。評価基準は下記の通りである。
Claims (23)
- 重量%で、炭素(C):0.1〜0.3%、シリコン(Si):0.1〜2.0%、アルミニウム(Al):0.005〜1.5%、マンガン(Mn):1.5〜3.5%、リン(P):0.04%以下(0%は除く)、硫黄(S):0.015%以下(0%は除く)、窒素(N):0.02%以下(0は除く)、残部のFe、及びその他の不可避不純物を含み、
ビスマス(Bi)、スズ(Sn)及びアンチモン(Sb)からなる群から選択された1種以上を0.01重量%〜0.07重量%含む、表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。 - 前記Si及びAl成分の和が1.0重量%以上である、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 溶融亜鉛めっき鋼板の微細組織は、面積分率で、ポリゴナルフェライト5%以下、針状フェライト70%以下、針状の残留オーステナイト25%以下(0%は除く)、及び残部のマルテンサイトを含む、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 素地鋼板と、前記素地鋼板の表面に形成された亜鉛めっき層と、を含む溶融亜鉛めっき鋼板であって、
前記素地鋼板と亜鉛めっき層の界面から素地鋼板の方向に0〜0.1μmの深さにおけるBi、Sn及びSbからなる群から選択された1種以上の濃化度が、素地鋼板の方向に0.2μm以上の深さと比べて2〜20倍である、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。 - 前記亜鉛めっき層のFe含量が7重量%〜13重量%である、請求項4に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 前記溶融亜鉛めっき鋼板の引張強度が780MPa以上である、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 重量%で、チタン(Ti):0.005〜0.1%、ニオブ(Nb):0.005〜0.1%、バナジウム(V):0.005〜0.1%、ジルコニウム(Zr):0.005〜0.1%、及びタングステン(W):0.005〜0.5%からなる群から選択された1種以上をさらに含む、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 重量%で、モリブデン(Mo):1%以下(0%は除く)、ニッケル(Ni):1%以下(0%は除く)、銅(Cu):0.5%以下(0%は除く)、及びクロム(Cr):1%以下(0%は除く)からなる群から選択された1種以上をさらに含む、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 重量%で、カルシウム(Ca):0.01%以下(0%は除く)、及びボロン(B):0.01%以下(0%は除く)からなる群から選択された1種以上をさらに含む、請求項1に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板。
- 重量%で、炭素(C):0.1〜0.3%、シリコン(Si):0.1〜2.0%、アルミニウム(Al):0.005〜1.5%、マンガン(Mn):1.5〜3.5%、リン(P):0.04%以下(0%は除く)、硫黄(S):0.015%以下(0%は除く)、窒素(N):0.02%以下(0は除く)、残部のFe、及びその他の不可避不純物を含み、ビスマス(Bi)、スズ(Sn)及びアンチモン(Sb)からなる群から選択された1種以上を0.01重量%〜0.07重量%含むスラブを準備する段階と、
前記スラブを1000℃〜1300℃で再加熱する段階と、
前記再加熱されたスラブを800℃〜950℃の仕上圧延温度で熱間圧延する段階と、
前記熱間圧延された熱延鋼板を750℃以下の温度で巻き取る段階と、
前記巻き取られた熱延鋼板を冷間圧延する段階と、
前記冷間圧延された冷延鋼板を、露点が−45℃以下、H2‐N2ガス雰囲気下で、Ac3以上の温度で加熱してから維持した後、冷却処理する一次焼鈍段階と、
前記一次焼鈍処理された鋼板を、露点が−20℃〜−60℃、H2‐N2ガス雰囲気下で、Ac1〜Ac3の温度範囲で加熱してから維持し、Ms(マルテンサイト変態開始温度)〜Mf(マルテンサイト変態完了温度)の温度範囲内で20℃/s以上の平均冷却速度で冷却した後、前記Ms以上の温度で再加熱して1秒以上維持する二次焼鈍段階と、
前記二次焼鈍処理された鋼板を溶融亜鉛めっきする段階と、を含む、表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。 - 前記冷間圧延する段階は、25%以上の圧下量で行われる、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記一次焼鈍段階でのH2‐N2雰囲気ガスは、2vol%以上の水素が含まれたものである、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記一次焼鈍段階を行った後の前記冷延鋼板の微細組織は、面積分率で、ベイナイト及びマルテンサイトからなる群から選択された1種以上を90%以上含む、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記一次焼鈍段階の後に酸洗処理する段階をさらに含む、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記二次焼鈍段階でのH2‐N2雰囲気ガスは、3vol%以上の水素が含まれたものである、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記二次焼鈍段階でMs以上の温度で再加熱する段階は、500℃以下の温度範囲で行われる、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記溶融亜鉛めっきする段階は、0.1重量%〜0.3重量%のAl、残部のZn、及びその他の不可避不純物を含み、450℃〜500℃温度範囲のめっき槽に浸漬させる方法により行われる、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記スラブのSi及びAl成分の和が1.0重量%以上である、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記スラブは、重量%で、チタン(Ti):0.005〜0.1%、ニオブ(Nb):0.005〜0.1%、バナジウム(V):0.005〜0.1%、ジルコニウム(Zr):0.005〜0.1%、及びタングステン(W):0.005〜0.5%からなる群から選択された1種以上をさらに含む、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記スラブは、重量%で、モリブデン(Mo):1%以下(0%は除く)、ニッケル(Ni):1%以下(0%は除く)、銅(Cu):0.5%以下(0%は除く)、及びクロム(Cr):1%以下(0%は除く)からなる群から選択された1種以上をさらに含む、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記スラブは、重量%で、カルシウム(Ca):0.01%以下(0%は除く)、及びボロン(B):0.01%以下(0%は除く)からなる群から選択された1種以上をさらに含む、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記溶融亜鉛めっきする段階の後に、500℃〜600℃の温度範囲で加熱して前記溶融亜鉛めっき鋼板を合金化処理する段階をさらに含む、請求項10に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
- 前記合金化処理する段階後の合金化溶融亜鉛めっき層のFe含量が、7重量%〜13重量%である、請求項22に記載の表面品質及びめっき密着性に優れた超高強度溶融亜鉛めっき鋼板の製造方法。
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JP2011231367A (ja) * | 2010-04-27 | 2011-11-17 | Sumitomo Metal Ind Ltd | 溶融亜鉛めっき鋼板およびその製造方法 |
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EP3231887B1 (en) | 2020-03-11 |
EP3231887A1 (en) | 2017-10-18 |
US20170369974A1 (en) | 2017-12-28 |
JP6546280B2 (ja) | 2019-07-17 |
CN107002207B (zh) | 2019-03-29 |
KR101630976B1 (ko) | 2016-06-16 |
EP3231887A4 (en) | 2017-11-22 |
WO2016093598A8 (ko) | 2016-08-18 |
CN107002207A (zh) | 2017-08-01 |
US10344361B2 (en) | 2019-07-09 |
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