JP7189306B2 - 水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板及びその製造方法 - Google Patents
水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板及びその製造方法 Download PDFInfo
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- JP7189306B2 JP7189306B2 JP2021180241A JP2021180241A JP7189306B2 JP 7189306 B2 JP7189306 B2 JP 7189306B2 JP 2021180241 A JP2021180241 A JP 2021180241A JP 2021180241 A JP2021180241 A JP 2021180241A JP 7189306 B2 JP7189306 B2 JP 7189306B2
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- Heat Treatment Of Sheet Steel (AREA)
- Heat Treatment Of Articles (AREA)
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Description
(但し、上記明度値は、KS A 0067で規定するCIE表色系(L*a*b*表色系)のうちL値を意味する。)
[化1]
2Al+3H2O=Al2O3+3H2
[化2]
H2=2[H]
上記Cは、熱処理部材の強度を向上させるための不可欠な元素であって、適正量で添加することができる。すなわち、熱処理部材の強度を十分に確保するために、上記Cは0.04%以上添加することができる。一実施例において、上記Cの含有量の下限は0.1%であることができる。但し、その含有量が高すぎると、冷延材を生産する場合、熱延材を冷間圧延する際に熱延材の強度が高すぎ、冷間圧延性が大きく劣化するだけでなく、点溶接性を大きく低下させるため、十分な冷間圧延性及び点溶接性を確保するために0.5%以下添加することができる。また、上記Cの含有量は、0.45%以下、または0.4%以下とその含有量を制限することもできる。
上記Siは、製鋼において脱酸剤として添加される必要があるだけでなく、熱間プレス成形部材の強度に最も大きく影響を与える炭化物の生成を抑制するとともに、熱間プレス成形におけるマルテンサイトの生成後に、マルテンサイトのラス(lath)粒界に炭素を濃化させて残留オーステナイトを確保する役割を果たす元素である。したがって、Siは0.01%以上の含有量で添加することができる。また、圧延後の鋼板にアルミニウムめっきを行う際に、十分なめっき性を確保するために、上記Siの含有量の上限を2%で決定することができる。本発明の一実施例では、上記Siの含有量を1.5%以下に制限することもできる。
上記Mnは、固溶強化の効果を確保することができるだけでなく、熱間プレス成形部材においてマルテンサイトを確保するための臨界冷却速度を下げるために、0.01%以上の含有量で添加することができる。また、鋼板の強度を適切に維持することにより、熱間プレス成形工程の作業性を確保するとともに、製造コストを削減し、点溶接性を向上させる点から、上記Mnの含有量は10%以下にすることができる。本発明の一実施例では、9%以下、または8%以下とすることができる。
上記Alは、Siとともに製鋼において脱酸作用を行って鋼の清浄度を高めることができるため、0.001%以上の含有量で添加することができる。また、Ac3温度が高すぎないようにして熱間プレス成形時に必要な加熱を適切な温度範囲で行うことができるようにするために、上記Alの含有量は1.0%以下とすることができる。
上記Pは、鋼内に不純物として存在し、できる限りその含有量が少ないほど有利である。したがって、本発明の一実施例において、Pは0.05%以下の含有量で含まれることができる。本発明の他の一実施例において、Pは0.03%以下に制限されることもできる。Pは少なければ少ないほど有利な不純物元素であるため、その含有量の上限を特に決定する必要はない。但し、Pの含有量を過度に下げるためには製造コストが上昇するおそれがあるため、これを考慮すると、その下限を0.001%とすることもできる。
上記Sは、鋼中不純物として部材の延性、衝撃特性、及び溶接性を阻害する元素であるため、最大含有量を0.02%とする(好ましくは0.01%以下)。また、その最小含有量が0.0001%未満では、製造コストが上昇する可能性があるため、本発明の一実施例において、その含有量の下限を0.0001%とすることができる。
上記Nは、鋼中に不純物として含まれる元素であって、スラブの連続鋳造時にクラック発生に対する敏感度を減少させ、衝撃特性を確保するためには、その含有量が低いほど有利であることから、0.02%以下含むことができる。ここで、下限を特に決定する必要があるが、製造コストの上昇などを考慮して、一実施例では、Nの含有量を0.001%以上で決定することができる。
上記Cr、Mo、及びWは、硬化能の向上と、析出強化の効果による強度及び結晶粒微細化を確保することができるため、これらのうち1種以上を含有量合計基準で0.01%以上添加することができる。また、部材の溶接性を確保するために、その含有量を4.0%以下に制限することもできる。尚、これら元素の含有量が4.0%を超えると、それ以上の効果上昇も弱くなるため、含有量を4.0%以下に制限する場合には、追加の元素添加によるコストの上昇を防止することもできる。
上記Ti、Nb、及びVは、微細析出物の形成によって熱処理部材の鋼板の向上と、結晶粒微細化によって残留オーステナイトの安定化、及び衝撃靭性の向上に効果があるため、これらのうち1種以上を含有量合計で0.001%以上添加することができる。但し、その添加量が0.4%を超えると、その効果が飽和するだけでなく、過度な合金鉄の添加が原因となってコストの上昇を招く可能性がある。
上記Cu及びNiは、微細析出物を形成して強度を向上させる元素である。上述した効果を得るために、これらのうち1つ以上の成分の合計を0.005%以上とすることができる。但し、その値が2.0%を超えると、過度なコスト増加となるため、その上限を2.0%とする。
上記Sb及びSnは、Al-Siめっきのための焼鈍熱処理時に、表面に濃化してSiまたはMn酸化物が表面に形成されることを抑制することで、めっき性を向上させることができる。このような効果を得るために、0.001%以上添加することができる。但し、その添加量が1.0%を超えると、過度な合金鉄のコストだけでなく、スラブの粒界に固溶し、熱間圧延時のコイルのエッジ(edge)クラックを誘発させる可能性があるため、その上限を1.0%とする。
上記Bは、少量の添加でも硬化能を向上させるだけでなく、旧オーステナイト結晶粒界に偏析されて、Pまたは/及びSの粒界偏析による熱間プレス成形部材の脆性を抑制することができる元素である。したがって、Bは0.001%以上添加することができる。但し、0.01%を超えると、その効果が飽和するだけでなく、熱間圧延において脆性をもたらすため、その上限を0.01%とすることができる。一実施例では、上記Bの含有量を0.005%以下とすることができる。
本発明の一実施例では、素地鋼板を用意し、上記素地鋼板の表面を適切な条件でアルミニウムめっきして巻取ることでアルミニウムめっき鋼板(コイル)を得る過程が行われる。
圧延された鋼板の表面にアルミニウムめっき処理を施すことができる。アルミニウムめっきは、通常、「type I」と命名されるAlSiめっき(80%以上のAlと5~20%のSiとを含み、必要によっては追加の元素も含むことが可能)、及び「type II」と命名されるAlを90%以上含み、必要によっては追加の元素を含むめっきをともに用いることができる。めっき層を形成するために溶融アルミニウムめっきを行うことができ、めっき前の鋼板に対して焼鈍処理を施すこともできる。めっき時における適切なめっき量は、片面当たりに30~200g/m2である。めっき量が多すぎる場合には、表面まで合金化するのに時間が過度にかかることがあり、逆にめっき量が少なすぎる場合には十分な耐食性を得ることが難しい。
めっき後の鋼板を巻取ってコイルを得るとき、コイルの巻取り張力を調節することができる。コイルの巻取り張力の調節に応じて、後で行われる焼鈍処理時のコイルの合金化挙動及び表面品質が異なり得る。本発明の一実施例において、上記巻取り張力は0.7~3kg/mm2とすることができる。
上述した過程によってアルミニウムめっきされた鋼板に対して、次のような条件で焼鈍処理を施してアルミニウム合金めっき鋼板を得る。
アルミニウムめっき鋼板(コイル)は、箱焼鈍炉(Batch annealing furnace)で加熱される。鋼板を加熱するとき、熱処理目標温度及び維持時間は、鋼板温度を基準に550~750℃の範囲内(本発明では、この温度範囲のうち素材が到達する最高温度を加熱温度と呼ぶ)で30分~50時間維持することが好ましい。ここで、維持時間とは、コイル温度が目標温度に達してから冷却開始するまでの時間を意味する。本発明の一実施例では、合金化が十分に行われない場合には、ロールレベリング時にめっき層が剥離する可能性があることから、十分な合金化のために加熱温度を550℃以上とすることができる。また、表層に酸化物が大量に生成されることを防止し、点溶接性を確保するために、上記加熱温度は750℃以下とすることができる。尚、めっき層を十分に確保するとともに、生産性の低下を防止するためには、上記維持時間は30分~50時間で決定することができる。本発明の一実施例において、鋼板の温度は、加熱温度に到達するまで冷却過程なしに温度が上昇し続ける形のパターンを有することができる。
上述した加熱温度で鋼板を加熱するとき、十分な生産性を確保するとともに、全鋼板(コイル)でめっき層を均一に合金化させるために、全温度区間(常温から加熱温度までの区間)に対する鋼板(コイル)温度を基準とする平均昇温速度を20~100℃/hとすることができる。また、全体的な平均昇温速度は、上記の数値範囲で制御することができるが、本発明の一実施例では、後述のように、特定の温度区間の昇温速度をともに制御して、本発明の課題を達成するようにした。
本発明の一実施例では、圧延時に混入した圧延油が気化する上記温度区間において圧延油が残存し、表面の汚れなどを引き起こすことを防止するとともに、十分な生産性を確保するために、昇温時の400~500℃の区間の平均昇温速度を1~15℃/hにして加熱することができる。本発明の一実施例では、上記昇温時の400~500℃の区間の平均昇温速度の下限を3℃/hrとすることができ、他の一実施例では、昇温時の400~500℃の区間の平均昇温速度の下限を4℃/hrとすることもできる。
本発明の一実施例では、めっき層の表面に酸化物を形成させるためにめっき層に含まれるアルミニウムと雰囲気ガス中の酸素とを反応させる方法を用いることができる。これは、めっき層内に存在するアルミニウムは、酸素親和力が非常に大きい元素であって、酸素と容易に酸化物を形成する元素であるためである。このために、酸素分圧は、10-70気圧以上に雰囲気を制御することができる。但し、酸素分圧が高すぎる場合には、酸化物の生成が多すぎるようになり、溶接性を低下させる可能性があるため、酸素分圧は10-20気圧以下に制御する。
一般の箱焼鈍炉の加熱は、鋼板(コイル)を直接加熱する方式よりは、焼鈍炉内の雰囲気温度の上昇を介して鋼板(コイル)を加熱する方式を取る。この場合、雰囲気温度とコイル温度の差は避けられないが、鋼板内の位置別材質とめっき品質の偏差を最小限に抑えるために、熱処理目標温度に達する時点を基準に雰囲気温度と鋼板温度の差を80℃以下とすることができる。温度差はできる限り小さくすることが理想的であるが、昇温速度を遅くして、全体の平均昇温速度の条件を満たすことは難しくなりうるため、これを考慮すると、5℃以上とすることができる。ここで、鋼板の温度とは、装入された鋼板(コイル)の底部(コイルのうち最も低い部分を意味する)の温度を測定したことを意味し、雰囲気温度とは、加熱炉の内部空間の中心で測定した温度を意味する。
<鋼板の製造>
発明例1
下記表1の組成を有する熱間プレス成形用冷間圧延鋼板を用意した。鋼板の表面にAl-9%Si-2.5%Feの組成を有する「type I」のめっき浴で鋼板を表面めっきした。めっき時におけるめっき量は片面当たりに75g/m2に調節し、めっき後の巻取り張力を1.44kg/mm2に調節してコイルを巻取った。
650℃までの全体の平均昇温速度:25℃/h
400~500℃の温度区間の平均昇温速度:12.5℃/h
加熱時の雰囲気:水素100vol%、酸素分圧10-30気圧
加熱温度における雰囲気と鋼板の間の温度差:30℃
上記表1の組成を有する鋼板の表面にAl-9%Si-2.5%Feの組成を有する「type I」のめっき浴で鋼板を表面めっきした。めっき時におけるめっき量は、片面当たりに90g/m2に調節し、めっき後の巻取り張力を1.9kg/mm2に調節してコイルを巻取った。
670℃までの全体の平均昇温速度:23℃/h
400~500℃の温度区間の平均昇温速度:11℃/h
加熱時の雰囲気:水素100vol%、酸素分圧10-34気圧
加熱温度における雰囲気と鋼板の間の温度差:20℃
上記発明例1と同一であるが、めっきだけを行い、加熱及び冷却は行っていないアルミニウムめっき鋼板を比較例1とした。
上記発明例2と同一であるが、めっきだけを行い、加熱及び冷却は行っていないアルミニウムめっき鋼板を比較例2とした。
上記発明例1と同一の鋼板の表面を発明例1と同一の条件でアルミニウムめっき及び巻取りしてアルミニウムめっき鋼板を得た後、上記アルミニウムめっき鋼板を箱焼鈍炉において次の条件で500℃まで加熱した。
500℃までの全体の平均昇温速度:50℃/h
400~500℃の温度区間の平均昇温速度:25℃/h
加熱時の雰囲気:水素100vol%、酸素分圧10-36気圧
加熱温度における雰囲気と鋼板の間の温度差:35℃
上記発明例1、2、及び比較例1、2、3の鋼板を950℃に加熱し、上記温度で5分間維持した後、プレスによって加圧しながら急冷する熱間プレス成形を行って熱間プレス成形部材を得た。
熱間プレス成形時における水素発生現象を確認するために水素発生挙動を模写する試験を行った。試験は、TGA(Thermo Gravimetric Analyzer)を用いており、図13の加熱パターン(黒線で示される)に示すように、各鋼板を加熱して加熱時の鋼板の重量増加を測定した。ここで、鋼板の重量が増加するとは、鋼板の表面に、化学式1のような形の酸化反応が起こり、その結果、水素が発生したことを意味する。
Claims (9)
- 素地鋼板、前記素地鋼板の表面に形成されたアルミニウム合金めっき層、及び前記めっき層の表面に形成された厚さ0.3μm以上の酸化物層を含む、水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板。
- 前記アルミニウム合金めっき層は35重量%以上のFeを含む、請求項1に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板。
- 前記アルミニウム合金めっき層は45重量%以上のFeを含む、請求項1に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板。
- 前記アルミニウム合金めっき層は50重量%以上のFeを含む、請求項1に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板。
- 前記素地鋼板は、重量%で、C:0.04~0.5%、Si:0.01~2%、Mn:0.01~10%、Al:0.001~1.0%、P:0.05%以下、S:0.02%以下、N:0.02%以下、残部Fe及びその他の不可避不純物を含む組成を有する、請求項1に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板。
- 前記素地鋼板の組成は、重量%で、Cr、Mo、及びWからなる群より選択された1種以上の合計:0.01~4.0%、Ti、Nb、Zr、及びVからなる群より選択された1種以上の合計:0.001~0.4%、Cu+Ni:0.005~2.0%、Sb+Sn:0.001~1.0%、及びB:0.0001~0.01%のうちから1つ以上をさらに含む、請求項5に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板。
- 素地鋼板の表面をアルミニウムめっきして巻取ることでアルミニウムめっき鋼板を得る段階と、
前記アルミニウムめっき鋼板を焼鈍してアルミニウム合金めっき鋼板を得る段階と、
前記アルミニウム合金めっき鋼板を冷却する段階と、を含む熱間プレス成形部材用鋼板の製造方法であって、
前記アルミニウムめっき量は鋼板の片面基準で30~200g/m2であり、
巻取り時の巻取り張力を0.5~5kg/mm2とし、
前記焼鈍は箱焼鈍炉において550~750℃の加熱温度範囲で30分~50時間行い、
前記焼鈍時に、常温で前記加熱温度まで加熱するとき、平均昇温速度を20~100℃/hとし、加熱温度-50℃~加熱温度区間の昇温速度を1~15℃/hとし、
熱処理時における箱焼鈍炉内の酸素分圧を10-70~10-20の気圧範囲とし、
前記箱焼鈍炉内の雰囲気温度と鋼板温度の差を5~80℃とする、
めっきの層の表面に厚さ0.3μm以上の酸化物層が形成された水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板の製造方法。 - 前記素地鋼板は、重量%で、C:0.04~0.5%、Si:0.01~2%、Mn:0.01~10%、Al:0.001~1.0%、P:0.05%以下、S:0.02%以下、N:0.02%以下、残部Fe及びその他の不可避不純物を含む組成を有する、請求項7に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板の製造方法。
- 前記素地鋼板の組成は、重量%で、Cr、Mo、及びWからなる群より選択された1種以上の合計:0.01~4.0%、Ti、Nb、Zr、及びVからなる群より選択された1種以上の合計:0.001~0.4%、Cu+Ni:0.005~2.0%、Sb+Sn:0.001~1.0%、及びB:0.0001~0.01%のうちから1つ以上をさらに含む、請求項8に記載の水素遅れ破壊抵抗性に優れた熱間プレス成形部材用鋼板の製造方法。
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WO2023176027A1 (ja) * | 2022-03-17 | 2023-09-21 | Jfeスチール株式会社 | 表面処理亜鉛めっき鋼板 |
KR20240098870A (ko) * | 2022-12-21 | 2024-06-28 | 주식회사 포스코 | 롤소착 저항성이 우수한 알루미늄 도금강판, 이를 이용한 열간 성형 부재 및 이들의 제조방법 |
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