JP2015054990A - 外観性とめっき密着性に優れる溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板ならびにそれらの製造方法 - Google Patents
外観性とめっき密着性に優れる溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板ならびにそれらの製造方法 Download PDFInfo
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Abstract
【解決手段】mass%で、C:0.08〜0.20%、Si:0.1〜3.0%、Mn:0.5〜3.0%、P:0.001%〜0.10%、Al:0.01%〜3.00%、S:0.200%以下を含有し、残部Fe及び不可避的不純物からなる成分組成を有し、地鉄と亜鉛めっき層との界面から地鉄側に5μm以下の厚さの内部酸化層、及び、地鉄と亜鉛めっき層との界面から地鉄側に20μm以下の厚さの脱炭層を有し、更に前記内部酸化層はFe2XMn2−2XSiOYで表されるFe及び/又はMnを含むSi酸化物を面積率で50%以上を含むことを特徴とする外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
【選択図】図2
Description
ここで、形成された外部酸化物は、後の焼鈍中に還元されて還元Fe層を鋼板表面に形成するため、Znめっきとの濡れ性を改善し、不めっきを抑制する効果がある。また、SiO2やFeおよび/またはMnを含むSi酸化物などの内部酸化物は、鋼中のSi活量を下げるため、焼鈍中のSi表面濃化を抑制し、不めっきを抑制する効果がある。
本発明では、酸素ポテンシャルの低下に伴い、SiO2からFeおよび/またはMnを含むSi酸化物への反応が促進される。Feおよび/またはMnを含むSi酸化物は、SiO2に比べて溶融亜鉛との濡れ性が良いため、表面に露出した場合も不めっきの起点となり難い。
[1]mass%で、C:0.08%以上0.20%未満、Si:0.1〜3.0%、Mn:0.5〜3.0%、P:0.001%〜0.10%、Al:0.01%〜3.00%、S:0.200%以下を含有し、残部Feおよび不可避的不純物からなる成分組成を有し、地鉄と亜鉛めっき層との界面から地鉄側に5μm以下の厚さの内部酸化層、および、地鉄と亜鉛めっき層との界面から地鉄側に20μm以下の厚さの脱炭層を有し、さらに前記内部酸化層はFe2XMn2−2XSiOYで表されるFeおよび/またはMnを含むSi酸化物を面積率で50%以上を含むことを特徴とする外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
[2]さらに、mass%で、Mo:0.01〜1.00%および/またはCr:0.01〜1.00%を含有することを特徴とする[1]に記載の外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
[3]さらに、mass%で、Nb:0.005〜0.20%、Ti:0.005〜0.20%、Cu:0.01〜0.50%、Ni:0.01〜1.00%、B:0.0005〜0.010%の少なくとも1種以上を含有することを特徴とする[1]または[2]に記載の外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
[4]亜鉛めっき層が合金化亜鉛めっき層であることを特徴とする[1]〜[3]のいずれか1項に記載の合金化溶融亜鉛めっき鋼板。
[5][1]〜[3]のいずれか1項に記載の成分組成を有する鋼を熱間圧延した後、冷間圧延し、次いで、直火バーナーを備えた直火加熱型の加熱炉で、COおよび炭化水素ガスの合計濃度60vol%以下を含み残部H2、N2及び不可避的不純物である可燃性ガスと、O2濃度が20〜50vol%を含み残部N2及び不可避的不純物である支燃性ガスとを燃焼させて、鋼板表面の到達温度を600〜800℃の範囲に加熱する熱処理を行った後、水素濃度3〜25vol%および水蒸気濃度0.070vol%以下を含み残部N2及び不可避的不純物である雰囲気において均熱温度630〜850℃で鋼板を加熱した後、溶融亜鉛めっき処理を施すことを特徴とする外観性とめっき密着性に優れる溶融亜鉛めっき鋼板の製造方法。
[6]溶融亜鉛めっき処理後、亜鉛めっきを合金化処理することを特徴とする[5]に記載の外観性とめっき密着性に優れる合金化溶融亜鉛めっき鋼板の製造方法。
まず、本発明に用いる鋼板の成分組成について説明する。なお、成分の量を表す%は、特に断らない限りmass%を意味する。
脱炭反応による酸素ポテンシャルの低下によりFeおよび/またはMnを含むSi酸化物の形成を十分に促進させるためには、Cは0.08%以上含有する必要がある。一方、Cが0.20%未満にすることにより、加工性に優れる。そのため、Cは0.08〜0.20%未満とする。なお、Cは0.08%以上が好ましく、0.10%以上がさらに好ましい。
Siは鋼板の機械的特性を改善する上で最重要な元素であるため、0.1%以上含有する必要がある。ただし、Siが3.0%を超えると地鉄と酸化物との界面におけるSiO2系酸化物の生成抑制が困難になり、不めっき抑制に必要な酸化物量を確保することが困難になる。そのため、Siは0.1〜3.0%とする。
Mnは固溶強化元素であり、鋼板の高強度化を図るために効果的であるため、0.5%以上含有する必要がある。一方、Mnは3.0%を超えると溶接性やめっき密着性が低下し、さらに強度延性バランスの確保が困難になる。そのため、Mnは0.5〜3.0%とする。
Pはセメンタイトの析出を遅延させて相変態の進行を遅らせるため、0.001%以上とする。一方、Pが0.10%を超えると溶接性およびめっき密着性が劣化する。さらに、合金化を遅延させるため、合金化温度が上昇し、延性が劣化する。そのため、Pは0.001〜0.10%とする。
AlはSiと補完的に添加される元素である。Alは製鋼過程で不可避的に混入するため、Alの下限値は0.01%である。一方、Alが3.00%を超えると外部酸化物の生成抑制が困難になり、めっき層の密着性が低下する。そのため、Alは0.01〜3.00%とする。
Sは製鋼過程で不可避的に含有される元素である。しかしながら、多量に含有すると溶接性が劣化する。そのため、Sは0.200%以下とする。
Moは強度と延性とのバランスを制御する元素であり、0.01%以上含有することができる。また、MoはSi、Alの内部酸化を促進し、表面濃化を抑制する効果がある。一方で、Moが1.00%を超えるとコストアップを招く場合がある。そのため、Moを含有する場合、0.01〜1.00%が好ましい。
Crは強度と延性とのバランスを制御する元素であり、0.01%以上含有することができる。また、CrはMoと同様に、Si、Alの内部酸化を促進し、表面濃化を抑制する効果がある。一方で、Cr濃度が1.00%を超えると、Crが鋼板表面に濃化するため、めっき密着性および溶接性が劣化する。そのため、Crを含有する場合、0.01〜1.00%が好ましい。
Nbは強度と延性とのバランスを制御する元素であり、0.005%以上含有することができる。一方で、Nbが0.20%を超えるとコストアップを招く場合がある。そのため、Nbを含有する場合、0.005〜0.20%が好ましい。
Tiは強度と延性とのバランスを制御する元素であり、0.005%以上含有することができる。一方で、Tiが0.20%を超えるとめっき密着性を低下させる場合がある。そのため、Tiを含有する場合、0.005〜0.20%が好ましい。
Cuは残留γ相形成を促進する元素であり、0.01%以上含有することができる。一方で、Cuが0.5%を超えるとコストアップを招く場合がある。そのため、Cuを含有する場合、0.01〜0.50%が好ましい。
Niは残留γ相形成を促進する元素であり、0.01%以上含有することができる。一方で、Niが1.00%を超えるとコストアップを招く場合がある。そのため、Niを含有する場合、0.01〜1.00%が好ましい。
Bは残留γ相形成を促進する元素であり、0.0005%以上含有することができる。一方で、Bが0.010%を超えるとめっき密着性が劣化する場合がある。そのため、Bを含有する場合、0.0005〜0.010%が好ましい。
通常、行われる条件にて行うことができる。
熱間圧延後は酸洗処理を行うのが好ましい。酸洗工程で表面に生成した黒皮スケールを除去し、しかる後冷間圧延する。なお、酸洗条件は特に限定しない。
30〜90%以下の圧下率で行うことが好ましい。圧下率が30%未満では再結晶が遅延するため、機械特性が劣化しやすい。一方、圧下率が90%超えでは圧延コストがアップするだけでなく、焼鈍時の表面濃化が増加するため、めっき特性が劣化する。
本発明では、冷間圧延後、直火型加熱炉で鋼板を加熱する。具体的には、直火バーナーを備えた直火加熱型の加熱炉により鋼板表面を加熱する。このとき、鋼板表面の到達温度を600〜800℃の範囲になるように加熱する。鋼板表面の到達温度が600℃以下では、不めっき抑制に必要な酸化物量が不足する。一方、800℃以上では酸化物量が過多となり押し疵と呼ばれる欠陥を表面に生じる。そのため、鋼板表面の到達温度を600〜800℃とする。
また、直火型加熱炉で加熱する際、低炭素および低酸素ポテンシャル雰囲気下で行う。具体的には、直火バーナーを備えた直火加熱型の加熱炉で、COおよび炭化水素ガスの合計濃度60vol%以下を含み残部H2、N2及び不可避的不純物である可燃性ガスと、O2濃度20〜50vol%を含み残部N2及び不可避的不純物である支燃性ガスとを燃焼させて、加熱する。上記の条件から外れると、脱炭反応による地鉄と酸化物との界面の酸素ポテンシャルの低下を十分に促進することができない。
次に、直火バーナーでの加熱後、水素濃度3〜25vol%および水蒸気濃度0.070vol%以下を含み残部N2及び不可避的不純物である雰囲気において均熱温度630〜850℃で鋼板を加熱(焼鈍)する。これは、鋼板表面を還元処理するために行うものである。十分な還元能力を得るためには、水素濃度は3vol%以上必要である。一方、水素濃度が25vol%以上では操業コストが高くなる。また、水蒸気濃度が0.070vol%以上では、H2Oによる脱炭反応が焼鈍中に促進するため、脱炭層の厚さが20μmよりもさらに厚くなる。脱炭層が厚くなりすぎると、残留γ相が形成しづらくなり、Si添加による利点を損なう。以上より、焼鈍雰囲気は水素濃度3〜25vol%および水蒸気濃度0.070vol%以下の雰囲気とする。
上記の雰囲気下で、均熱温度630〜850℃で鋼板を加熱し還元焼鈍する。鋼板の到達温度が630℃以下では、再結晶が遅延するため機械的特性が劣化する。鋼板の到達温度が850℃超えでは、Si等の表面濃化が促進されるため不めっきが発生する。
(1)表面外観
表面外観は、300×300mmの範囲を目視し、下記基準に照らして評価した。
○:不めっきまたは押し疵がない
△:概ね良好だが、低頻度で不めっき又は押し疵がある
×:不めっきまたは押し疵があり外観不良
(2)めっき密着性
めっき表面にセロハンテープを貼り、テープ面を90℃曲げおよび曲げ戻しをし、加工部の内側(圧縮加工側)に、曲げ加工部と平行に巾24mmのセロハンテープを押し当てて引き離し、セロハンテープの長さ40mmの部分に付着した亜鉛量を単位長さ(1m)辺りの剥離量を、Znカウント数として蛍光X線法により測定し、下記基準に照らして評価した。なお、この時のマスク径は30mm、蛍光X線の加速電圧は50kV、加速電流は50mA、測定時間は20秒である。
○:Znカウント数0〜5000未満
△:Znカウント数5000以上〜10000未満
×:Znカウント数10000以上
得られた結果を表2に示す。
Claims (6)
- mass%で、C:0.08%以上0.20%未満、Si:0.1〜3.0%、Mn:0.5〜3.0%、P:0.001%〜0.10%、Al:0.01%〜3.00%、S:0.200%以下を含有し、残部Feおよび不可避的不純物からなる成分組成を有し、地鉄と亜鉛めっき層との界面から地鉄側に5μm以下の厚さの内部酸化層、および、地鉄と亜鉛めっき層との界面から地鉄側に20μm以下の厚さの脱炭層を有し、さらに前記内部酸化層はFe2XMn2−2XSiOYで表されるFeおよび/またはMnを含むSi酸化物を面積率で50%以上を含むことを特徴とする外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
- さらに、mass%で、Mo:0.01〜1.00%および/またはCr:0.01〜1.00%を含有することを特徴とする請求項1に記載の外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
- さらに、mass%で、Nb:0.005〜0.20%、Ti:0.005〜0.20%、Cu:0.01〜0.50%、Ni:0.01〜1.00%、B:0.0005〜0.010%の少なくとも1種以上を含有することを特徴とする請求項1または2に記載の外観性とめっき密着性に優れる溶融亜鉛めっき鋼板。
- 亜鉛めっき層が合金化亜鉛めっき層であることを特徴とする請求項1〜3のいずれか1項に記載の合金化溶融亜鉛めっき鋼板。
- 請求項1〜3のいずれか1項に記載の成分組成を有する鋼を熱間圧延した後、
冷間圧延し、
次いで、直火バーナーを備えた直火加熱型の加熱炉で、COおよび炭化水素ガスの合計濃度60vol%以下を含み残部H2、N2及び不可避的不純物である可燃性ガスと、O2濃度20〜50vol%を含み残部N2及び不可避的不純物である支燃性ガスとを燃焼させて、鋼板表面の到達温度を600〜800℃の範囲に加熱する熱処理を行った後、
水素濃度3〜25vol%および水蒸気濃度0.070vol%以下を含み残部N2及び不可避的不純物である雰囲気において均熱温度630〜850℃で鋼板を加熱した後、
溶融亜鉛めっき処理を施すことを特徴とする外観性とめっき密着性に優れる溶融亜鉛めっき鋼板の製造方法。 - 溶融亜鉛めっき処理後、亜鉛めっきを合金化処理することを特徴とする請求項5に記載の外観性とめっき密着性に優れる合金化溶融亜鉛めっき鋼板の製造方法。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015146692A1 (ja) * | 2014-03-28 | 2015-10-01 | 株式会社神戸製鋼所 | 加工性、および耐遅れ破壊特性に優れた高強度合金化溶融亜鉛めっき鋼板、並びにその製造方法 |
CN106636921A (zh) * | 2016-12-19 | 2017-05-10 | 武汉钢铁股份有限公司 | 一种屈服强度为420MPa级的铁‑锌镀层钢板及生产方法 |
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CN108699664A (zh) * | 2016-02-25 | 2018-10-23 | 新日铁住金株式会社 | 耐冲击剥离性及加工部耐腐蚀性优异的高强度热浸镀锌钢板 |
WO2018207560A1 (ja) * | 2017-05-11 | 2018-11-15 | Jfeスチール株式会社 | 溶融亜鉛めっき鋼板の製造方法 |
JP2019031721A (ja) * | 2017-08-09 | 2019-02-28 | Jfeスチール株式会社 | 高強度溶融亜鉛めっき鋼板の製造方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011117063A (ja) * | 2009-11-02 | 2011-06-16 | Kobe Steel Ltd | 溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板の製造方法 |
JP2011214042A (ja) * | 2010-03-31 | 2011-10-27 | Kobe Steel Ltd | 合金化溶融亜鉛めっき鋼板の製造方法 |
JP2013014834A (ja) * | 2011-06-07 | 2013-01-24 | Jfe Steel Corp | めっき密着性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 |
WO2013047739A1 (ja) * | 2011-09-30 | 2013-04-04 | 新日鐵住金株式会社 | 機械切断特性に優れた高強度溶融亜鉛めっき鋼板、高強度合金化溶融亜鉛めっき鋼板、並びにそれらの製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2587724B2 (ja) | 1990-11-30 | 1997-03-05 | 新日本製鐵株式会社 | めっき密着性の良好な高Si含有高張力溶融亜鉛めっき鋼板の製造方法 |
JP3415191B2 (ja) | 1993-04-26 | 2003-06-09 | Jfeスチール株式会社 | 高張力溶融亜鉛めっき鋼板の製造方法 |
JP4552310B2 (ja) | 1999-11-08 | 2010-09-29 | Jfeスチール株式会社 | 強度−延性バランスとめっき密着性に優れた溶融亜鉛めっき鋼板およびその製造方法 |
PL1980638T3 (pl) * | 2006-01-30 | 2014-03-31 | Nippon Steel & Sumitomo Metal Corp | Wysokowytrzymała blacha cynkowana ogniowo o doskonałej podatności na formowanie i nadająca się do platerowania, wysokowytrzymała stopowa blacha cynkowana ogniowo oraz procesy i urządzenie do ich wytwarzania |
JP4972775B2 (ja) | 2006-02-28 | 2012-07-11 | Jfeスチール株式会社 | 外観性とめっき密着性に優れる高強度溶融亜鉛めっき鋼板の製造方法 |
JP2010116590A (ja) | 2008-11-12 | 2010-05-27 | Sumitomo Metal Ind Ltd | 溶融亜鉛系めっき鋼板およびその製造方法 |
CA2751593C (en) * | 2009-03-31 | 2013-08-27 | Jfe Steel Corporation | High-strength galvanized steel sheet and method for manufacturing the same |
PL2762601T3 (pl) | 2011-09-30 | 2018-11-30 | Nippon Steel & Sumitomo Metal Corporation | Blacha stalowa cienka mająca warstwę cynkowaną ogniowo i wykazująca doskonalą zwilżalność powłoki galwanicznej i przyczepność powłoki galwanicznej oraz sposób jej wytwarzania |
-
2013
- 2013-09-12 JP JP2013188920A patent/JP5799997B2/ja active Active
-
2014
- 2014-09-11 US US15/021,518 patent/US9932659B2/en active Active
- 2014-09-11 CN CN201480049859.XA patent/CN105531389B/zh active Active
- 2014-09-11 WO PCT/JP2014/004700 patent/WO2015037241A1/ja active Application Filing
- 2014-09-11 MX MX2016003144A patent/MX355496B/es active IP Right Grant
- 2014-09-11 KR KR1020167009597A patent/KR101831173B1/ko active IP Right Grant
- 2014-09-11 EP EP14843639.7A patent/EP3045558A4/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011117063A (ja) * | 2009-11-02 | 2011-06-16 | Kobe Steel Ltd | 溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板の製造方法 |
JP2011214042A (ja) * | 2010-03-31 | 2011-10-27 | Kobe Steel Ltd | 合金化溶融亜鉛めっき鋼板の製造方法 |
JP2013014834A (ja) * | 2011-06-07 | 2013-01-24 | Jfe Steel Corp | めっき密着性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 |
WO2013047739A1 (ja) * | 2011-09-30 | 2013-04-04 | 新日鐵住金株式会社 | 機械切断特性に優れた高強度溶融亜鉛めっき鋼板、高強度合金化溶融亜鉛めっき鋼板、並びにそれらの製造方法 |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015193907A (ja) * | 2014-03-28 | 2015-11-05 | 株式会社神戸製鋼所 | 加工性、および耐遅れ破壊特性に優れた高強度合金化溶融亜鉛めっき鋼板、並びにその製造方法 |
WO2015146692A1 (ja) * | 2014-03-28 | 2015-10-01 | 株式会社神戸製鋼所 | 加工性、および耐遅れ破壊特性に優れた高強度合金化溶融亜鉛めっき鋼板、並びにその製造方法 |
CN108699664A (zh) * | 2016-02-25 | 2018-10-23 | 新日铁住金株式会社 | 耐冲击剥离性及加工部耐腐蚀性优异的高强度热浸镀锌钢板 |
JP2019522116A (ja) * | 2016-06-28 | 2019-08-08 | 宝山鋼鉄股▲ふん▼有限公司Baoshan Iron & Steel Co.,Ltd. | 優れたリン酸塩処理性を有する低密度冷間圧延鋼板及びその製造方法 |
US11371112B2 (en) | 2016-06-28 | 2022-06-28 | Baoshan Iron & Steel Co., Ltd. | Cold-rolled low-density steel sheet having excellent phosphorability, and manufacturing method therefor |
CN106636921A (zh) * | 2016-12-19 | 2017-05-10 | 武汉钢铁股份有限公司 | 一种屈服强度为420MPa级的铁‑锌镀层钢板及生产方法 |
CN106636902A (zh) * | 2016-12-19 | 2017-05-10 | 武汉钢铁股份有限公司 | 一种屈服强度为380MPa级的铁‑锌镀层钢板及生产方法 |
JP2018188717A (ja) * | 2017-05-11 | 2018-11-29 | Jfeスチール株式会社 | 溶融亜鉛めっき鋼板の製造方法 |
CN110612359A (zh) * | 2017-05-11 | 2019-12-24 | 杰富意钢铁株式会社 | 热浸镀锌钢板的制造方法 |
WO2018207560A1 (ja) * | 2017-05-11 | 2018-11-15 | Jfeスチール株式会社 | 溶融亜鉛めっき鋼板の製造方法 |
US11421312B2 (en) | 2017-05-11 | 2022-08-23 | Jfe Steel Corporation | Method for manufacturing hot-dip galvanized steel sheet |
JP2019031721A (ja) * | 2017-08-09 | 2019-02-28 | Jfeスチール株式会社 | 高強度溶融亜鉛めっき鋼板の製造方法 |
JP2022514847A (ja) * | 2018-12-19 | 2022-02-16 | ポスコ | 電気抵抗スポット溶接性に優れた高強度亜鉛めっき鋼板及びその製造方法 |
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