JP6694961B2 - めっき性及び溶接性に優れたオーステナイト系溶融アルミニウムめっき鋼板及びその製造方法 - Google Patents
めっき性及び溶接性に優れたオーステナイト系溶融アルミニウムめっき鋼板及びその製造方法 Download PDFInfo
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- JP6694961B2 JP6694961B2 JP2018532609A JP2018532609A JP6694961B2 JP 6694961 B2 JP6694961 B2 JP 6694961B2 JP 2018532609 A JP2018532609 A JP 2018532609A JP 2018532609 A JP2018532609 A JP 2018532609A JP 6694961 B2 JP6694961 B2 JP 6694961B2
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- steel sheet
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- aluminum
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- austenitic
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- 238000004519 manufacturing process Methods 0.000 title claims description 13
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- 229910052718 tin Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Coating With Molten Metal (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Description
炭素は、オーステナイト組織の安定化に寄与する元素であり、その含量が増加するほど、オーステナイト組織の確保に有利になる。また、炭素は、鋼の積層欠陥エネルギーを増加させて引張強度及び伸びをともに増加させる役割を果たす。炭素の含量が0.3%未満である場合には、鋼板の高温加工において脱炭によってα’−マルテンサイト組織が形成され、遅れ破壊に脆弱になるという問題があり、また、目標とする引張強度及び伸びを確保することが困難であるという問題がある。これに対し、その含量が0.9%を超える場合には、電気比抵抗が増加して溶接性が劣化し得る。したがって、本発明では、炭素の含量を0.3〜0.9%に限定することが好ましい。
マンガンは、炭素とともにオーステナイト組織を安定化させる元素である。その含量が12%未満である場合には、変形中にα’−マルテンサイト組織が形成され、安定したオーステナイト組織を確保することが困難であり、これに対し、その含量が25%を超える場合には、強度向上の効果は飽和され、製造コストが上昇するという欠点がある。したがって、本発明では、マンガンの含量を12〜25%に限定することが好ましい。
シリコンは、通常、鋼の脱酸剤として用いられる元素であるが、本発明では、固溶強化によって鋼の降伏強度及び引張強度を向上させる役割を果たす。特に、本発明では、適切な含量のシリコンが炭窒化物形成元素であるチタン及びバナジウムと複合添加される場合、炭窒化物が微細化して、単純に炭窒化物形成元素のみが添加された場合に比べてさらに微細な結晶粒が得られることを確認している。本発明においてこのような効果を得るためには、シリコンの含量が0.5%以上であることが好ましい。但し、その含量が2.5%を超える場合には、熱間圧延において表面に多量のシリコン酸化物が形成されて酸洗性が低下し、電気比抵抗が増加して溶接性が劣化し得る。したがって、本発明では、シリコンの含量を0.5〜2.5%に限定することが好ましい。
アルミニウムは、通常、鋼の脱酸のために添加する元素であるが、本発明では、積層欠陥エネルギーを高めてε−マルテンサイトの生成を抑えることで、鋼の延性及び耐遅れ破壊特性を向上させる役割を果たす。アルミニウムの含量が0.3%未満である場合には、急激な加工硬化現象によって鋼の延性が低下し、耐遅れ破壊特性が劣化するという問題がある。これに対し、3.0%を超える場合には、鋼の引張強度が低下し、鋳造性が劣化し、熱間圧延における鋼の表面酸化が激しくなって表面品質が劣化するという問題がある。したがって、本発明では、アルミニウムの含量を0.3〜3.0%に限定することが好ましい。
チタンは、鋼中の窒素と反応して窒化物を形成することで鋼の成形性を向上させ、鋼中の炭素と反応して炭化物を形成することで鋼の強度を向上させる。本発明においてこのような効果を得るためには、チタンの含量が0.01%以上であることが好ましい。但し、その含量が0.5%を超える場合には、析出物が過度に形成されて鋼の疲労特性が劣化するという問題がある。したがって、本発明では、チタンの含量を0.01〜0.5%に限定することが好ましい。
バナジウムは、炭素及び/または窒素と反応して析出物を形成する元素であり、特に、本発明では、低温で微細析出物を形成させて鋼の降伏強度を増加させる重要な役割を果たす。本発明においてこのような効果を得るためには、バナジウムの含量が0.05%以上であることが好ましい。但し、その含量が0.5%を超える場合には、高温で粗大な炭窒化物が形成されて熱間加工性が劣化し、鋼の降伏強度が低下するという問題がある。したがって、本発明では、バナジウムの含量を0.05〜0.5%に限定することが好ましい。
モリブデンは、高温強度を向上させる役割を果たす元素であり、特に、本発明では、鋼の降伏強度を増加させる役割を果たす。このような効果を得るためには、鋼中に0.01%以上含まれることが好ましい。但し、その含量が0.5%を超える場合には、熱間加工性が劣化し得るだけでなく、製品のコスト競争力の点で不利になるという問題がある。したがって、本発明では、モリブデンの含量を0.01〜0.5%に限定することが好ましい。
一般に、本発明のように鋼中に多量のシリコン及びマンガンが含有される場合、焼鈍において、酸素親和力の高いシリコン及びマンガンが鋼板の表層に単独若しくは複合酸化物を形成することで、めっき性が劣化することがある。スズは、鋼中のマンガンの表面濃化を効果的に抑えてマンガン系酸化物の形成を抑えることで、めっき性を改善するのに重要な役割を果たす。本発明においてこのような効果を得るためには、スズの含量が0.01%以上であることが好ましい。但し、その含量が0.2%を超える場合には、その効果が飽和されるだけでなく、コスト競争力の点で経済性を確保することが困難である。したがって、本発明では、スズの含量を0.01〜0.2%に限定することが好ましい。
タングステンは粒界強化元素であり、鋼の強度を改善するために微量添加する。さらに、タングステンは、粒界炭化物を形成させ、焼鈍熱処理において粒界を介したマンガンの表面拡散を抑えることでめっき性を改善し、スポット溶接における溶融金属の母材浸透において粒界拡散を阻止することでLMEクラックの発生を抑える。本発明においてこのような効果を得るためには、タングステンの含量が0.001%以上であることが好ましい。但し、その含量が0.1%を超える場合には、その効果が飽和されるだけでなく、コスト競争力の点で経済性を確保することが困難である。したがって、本発明では、タングステンの含量を0.001〜0.1%に限定することが好ましい。
コバルトは、タングステンと複合添加される際に、化合物を形成して高温強度の改善に寄与する。尚、タングステンとともに、焼鈍熱処理において粒界を介したマンガンの表面拡散を抑えることでめっき性を改善し、スポット溶接における溶融金属の母材浸透において粒界拡散を阻止することでLMEクラックの発生を抑える。本発明においてこのような効果を得るためには、コバルトの含量が0.001%以上であることが好ましい。但し、その含量が0.1%を超える場合には、その効果が飽和されるだけでなく、コスト競争力の点で経済性を確保することが困難である。したがって、本発明では、コバルトの含量を0.001〜0.1%に限定することが好ましい。
クロムは、表層に緻密な酸化物皮膜を形成することで、内部への酸素の流入を抑えて脱炭を抑えることにより、オーステナイト組織を安定化させる役割を果たす。しかし、0.5%以上添加する場合、粒界に炭化物を形成することでクラック核を生成する役割をし、耐遅れ破壊性を劣化させるという問題があるため、0.5%以下で添加することが好ましい。
ニオブは、バナジウムと複合添加する際に、炭窒化物を形成することで結晶粒を微細化し、強度上昇の役割を果たす。しかし、0.05%以上添加する場合には、高温延性を減少させてスラブ品質を劣化させるため、0.05%以下で添加することが好ましい。
アンチモンは、焼鈍熱処理において鋼板表層直下に濃化する元素であり、Si、Mn、及びAl合金元素が粒界に沿って表面へ拡散することを抑え、溶融アルミニウムめっき性の確保を可能とする。しかし、冷延酸洗において表層部にスケールの残存を誘発して酸洗性を劣化させるため、0.1%以下に制御することが好ましい。
優れた加工性若しくは耐酸化性が要求される場合、適量のSiを添加することができる。但し、過多なSiの添加は、めっき浴の温度を過度に上昇させ、粗大なSi初晶が晶出して、却って耐食性及び加工性が劣化する恐れがある。これを考慮すると、Siの含量は7〜12%であることができ、8〜10%であることが好ましい。
優れた耐食性が要求される場合、適量のMgを添加することができる。また、Mgの添加は、めっき層の表層硬度を上昇させて摩擦系数を低減させ、加工性を向上させる。但し、その含量が過多である場合には、強い酸素親和力によってMg酸化物を形成させ、めっき浴にドロスの発生をもたらす。これを考慮すると、Mgの含量は3〜5%であってよい。
Claims (14)
- 重量%で、C:0.3〜0.9%、Mn:12〜25%、Si:0.5〜2.5%、Al:0.3〜3.0%、Ti:0.01〜0.5%、V:0.05〜0.5%、Mo:0.01〜0.5%、Sn:0.01〜0.2%、Co:0.001〜0.1%、W:0.001〜0.1%、残部Fe及び不可避不純物からなり、W及びCoの合計が0.01%以上でありMo及びVの合計が0.6%以上である、素地鋼板と、
前記素地鋼板の表面に形成された溶融アルミニウム系めっき層と、を含む、オーステナイト系溶融アルミニウムめっき鋼板。 - 前記素地鋼板は、重量%で、Cr:0.5%以下(0%を除く)、Nb:0.05%以下(0%を除く)、及びSb:0.1%以下(0%を除く)からなる群から選択される1種以上をさらに含む、請求項1に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 前記素地鋼板は、平均円相当径が100nm以下である炭窒化物を含む、請求項1に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 前記素地鋼板の降伏比(降伏強度/引張強度)が0.68以上である、請求項1に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 前記溶融アルミニウム系めっき層は、7〜12重量%のSiを含む、請求項1に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 前記溶融アルミニウム系めっき層は、3〜5重量%のMgをさらに含む、請求項5に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 前記素地鋼板と溶融アルミニウム系めっき層との界面に形成されたAl−Fe−Si−Mn系合金層をさらに含み、
前記Al−Fe−Si−Mn系合金層は、Fe及びMnを合計で23重量%以上含む、請求項1に記載のオーステナイト系溶融アルミニウムめっき鋼板。 - 前記Al−Fe−Si−Mn系合金層の厚さをxとし、前記溶融アルミニウム系めっき層の厚さをyとしたときに、y/xは1以上6以下である、請求項7に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 前記Al−Fe−Si−Mn系合金層と溶融アルミニウム系めっき層との界面には、厚さが1μm以下(0μmを除く)のAl−Si−Mg合金相が、素地鋼板に水平な方向に2μm以下(0μmを除く)の間隔で断続的に形成されている、請求項7に記載のオーステナイト系溶融アルミニウムめっき鋼板。
- 重量%で、C:0.3〜0.9%、Mn:12〜25%、Si:0.5〜2.5%、Al:0.3〜3.0%、Ti:0.01〜0.5%、V:0.05〜0.5%、Mo:0.01〜0.5%、Sn:0.01〜0.2%、Co:0.001〜0.1%、W:0.001〜0.1%、残部Fe及び不可避不純物からなり、W及びCoが合計で0.01%以上でありMo及びVが合計で0.6%以上である、素地鋼板を準備する段階と、
前記素地鋼板を−30℃以下の露点温度の還元雰囲気下で700〜850℃まで加熱した後、維持する段階と、
前記加熱及び維持された素地鋼板を冷却する段階と、
前記冷却された素地鋼板をアルミニウム系めっき浴に浸漬してめっきする段階と、を含む、オーステナイト系溶融アルミニウムめっき鋼板の製造方法。 - 前記冷却された素地鋼板の引込温度をTd(℃)とし、前記アルミニウム系めっき浴の温度をTp(℃)としたときに、前記Tdは、(Tp−80)℃以上(Tp−10)℃以下を満たす、請求項10に記載のオーステナイト系溶融アルミニウムめっき鋼板の製造方法。
- 前記還元雰囲気は、3〜20体積%の水素(H2)及び残部窒素(N2)ガス雰囲気である、請求項10に記載の溶融アルミニウムめっき鋼板の製造方法。
- 前記冷却された素地鋼板の引込温度(Td)が560〜660℃である、請求項10に記載のオーステナイト系溶融アルミニウムめっき鋼板の製造方法。
- 前記めっき後に、720〜840℃の温度で合金化熱処理する段階をさらに含む、請求項10に記載のオーステナイト系溶融アルミニウムめっき鋼板の製造方法。
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US20200262181A1 (en) | 2020-08-20 |
EP3395979A4 (en) | 2018-10-31 |
EP3395979B1 (en) | 2020-06-03 |
JP2019504205A (ja) | 2019-02-14 |
US11420419B2 (en) | 2022-08-23 |
EP3395979A1 (en) | 2018-10-31 |
CN108431269A (zh) | 2018-08-21 |
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