JP6398967B2 - 表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板およびその製造方法 - Google Patents
表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板およびその製造方法 Download PDFInfo
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- JP6398967B2 JP6398967B2 JP2015252719A JP2015252719A JP6398967B2 JP 6398967 B2 JP6398967 B2 JP 6398967B2 JP 2015252719 A JP2015252719 A JP 2015252719A JP 2015252719 A JP2015252719 A JP 2015252719A JP 6398967 B2 JP6398967 B2 JP 6398967B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B32B15/043—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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- C—CHEMISTRY; METALLURGY
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Description
[1]成分組成として、質量%で、C:0.02%以上0.30%以下、Si:0.01%以上1.0%以下、Mn:0.3%以上2.5%以下、P:0.08%以下、S:0.02%以下、Al:0.001%以上0.20%以下を含有し、残部がFeおよび不可避的不純物からなる鋼を、熱間圧延、酸洗し、次いで、1〜10%の圧下率で圧延後、溶融めっき処理を行うことを特徴とする表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
[2]成分組成として、さらに、質量%で、Ti:0.01%以上0.40%以下、Nb:0.001%以上0.200%以下、V:0.001%以上0.500%以下、Mo:0.01%以上0.50%以下、W:0.001%以上0.200%以下のうち1種または2種以上を含有することを特徴とする前記[1]に記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
[3]前記圧延後、前記溶融めっき処理前に、炉内雰囲気を水素濃度2〜20vol%かつ露点−60〜−10℃とし、鋼板到達温度(T)が650〜750℃、T−50℃以上T℃以下の温度域で10〜500秒保持する焼鈍を行うことを特徴とする前記[1]または[2]に記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
[4]前記溶融めっき処理後、さらに、合金化処理を行うことを特徴とする前記[1]〜[3]のいずれかに記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
[5]成分組成は、質量%で、C:0.02%以上0.30%以下、Si:0.01%以上1.0%以下、Mn:0.3%以上2.5%以下、P:0.08%以下、S:0.02%以下、Al:0.001%以上0.20%以下を含有し、残部がFeおよび不可避的不純物からなり、鋼板表面の算術平均粗さRaが2.0μm以下であり、鋼板表面のα-Fe(211)面の平均残留応力σが−250MPa≦σ≦−30MPaを満たし、かつ、590MPa以上の引張強度を有することを特徴とする表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板。
[6]成分組成として、さらに、質量%で、Ti:0.01%以上0.40%以下、Nb:0.001%以上0.200%以下、V:0.001%以上0.500%以下、Mo:0.01%以上0.50%以下、W:0.001%以上0.200%以下のうち1種または2種以上を含有することを特徴とする前記[5]に記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板。
熱延鋼板を母材とし、溶融めっき処理を行うもの、溶融めっき処理後さらに合金化処理を行うもの、いずれも含むものである。また、めっきとしては、Znめっき、Zn−Alめっき、Alめっきなどのめっきを対象とする。
Si、Mnを含有する溶融めっき熱延鋼板を安定して製造することができる。かつ、Si、Mn含有量の制限が緩和されるので、Si 、Mnを大量に含有する母材を使用することが可能となり、鋼成分の設計が容易になるなど、工業的に大きな効果を得ることができる。
なお、以下の説明において、鋼成分組成の各元素の含有量の単位およびめっきの成分組成の各元素の含有量の単位はいずれも「質量%」であり、特に断らない限り単に「%」で示す。また、水素濃度の単位はいずれも「vol%」であり、特に断らない限り単に「%」で示す。
Cは少ないほど母材の成形性が良好となるが、Cを含有させることで鋼板の強度を安価に高めることができる。従って、C含有量は0.02%以上とする。好ましくは0.04%以上である。一方、Cを過剰に含有させると鋼板の靱性や溶接性が低下するので、C含有量は0.30%以下とする。好ましくは0.20%以下である。
Si は固溶強化元素として有効であり、鋼板の強度を高めるためにも0.01%以上が必要である。しかしながら、Si を過度に含有させると溶融めっき時の濡れ性を損ない、合金化反応性を損なうために、合金化の調整が困難となってめっき外観やめっき密着性、耐パウダリング性の低下を招く。以上より、Si含有量は0.01%以上1.0%以下とする。
Mn は鋼の強度を高めるのに有用な元素である。この効果を得るには、Mn を0.3%以上含有させる必要がある。しかしながら、Mnを過度に含有させると溶融めっき時の濡れ性を損ない、合金化反応性を損なうため、合金化の調整が困難となってめっき外観やめっき密着性、耐パウダリング性の低下を招く。以上より、Mn含有量は0.3%以上2.5%以下とする。好ましくは0.3%以上2.0%以下である。
Pが0.08%を超えて含有すると溶接性が劣化すると共に、表面品質が劣化する。また、合金化処理時には合金化処理温度をより高くしないと所望の合金化度とすることができないが、合金化処理温度を上昇させると母材鋼板の延性が劣化すると同時に合金化溶融めっき層の密着性が劣化する。そのため、P含有量は0.08%以下である。
Sは粒界に偏析またはMnSが多量に生成した場合、靭性を低下させるため、含有量を0.02%以下とする必要がある。S含有量の下限は特に限定されず、不純物程度であってもよい。
Alは溶鋼の脱酸を目的に添加されるが、その含有量が0.001%未満の場合、その目的が達成されない。一方、0.20%を超えて含有すると、介在物が多量に発生し、鋼板の疵の原因となる。そのため、Al含有量は0.001%以上0.20%以下である。
これらの元素のなかで、特にTiは析出強化能が高く、コストの観点からも有効な元素である。しかしながら、添加量が0.01%未満では合金化溶融めっき層中に析出物(特に、炭化物)を含有させるために必要な母材鋼板中の析出物量が不十分な場合がある。0.40%を超えるとその効果は飽和し、コストアップとなる。そのため、Tiを含有する場合は、Ti含有量は、0.01%以上0.40%以下である。
なお、Nb、V、Mo、Wについても上記Tiの含有範囲の上限および下限に関する同様の理由から、含有する場合は、Nb量は0.001〜0.200%、V量は0.001〜0.500%、Mo量は0.01〜0.50%、W量は0.001〜0.200%である。
本発明では、鋼板の表面粗さを制御することで、鋼板表面のFe−Al及びFe−Zn反応を均一化し、めっき付着量ムラを軽減させる。鋼板表面粗さとして算術平均粗さ(Ra)を使用し、めっき特性の改善効果を得るためにRaを2.0μm以下とする。特にSi 、Mnを大量に含有する母材を使用した場合には、赤スケールを代表としたスケール疵に起因して表面粗さが増大することに加え、焼鈍時に形成されるSi 、Mn酸化物によって合金化速度が遅延し、合金化ムラが顕在化しやすくなる。これに対して、Raが2.0μm以下であれば、鋼板表面でのFe−Al及びFe−Zn反応を均一化させ、曲げ加工時の応力集中を防ぎ、表面外観、めっき密着性および耐パウダリング性が劣化することがない。なお、算術平均粗さRaは後述する実施例に記載の方法にて測定することができる。また、酸洗後の圧延の圧下率を1〜10%とすることで、Si 、Mnを大量に含有する母材を使用した場合でも鋼板表面の算術平均粗さRaを2.0μm以下とすることができる。
本発明では、母材表面に圧縮残留応力を導入することで、Fe−Al反応性、Fe−Zn合金化反応性を向上させる。また、酸洗後に形成される酸化被膜の還元を促進する。このようなめっき特性の改善効果を得るために、上記残留応力を−250MPa≦σ≦−30MPaとする。−30MPa超えの場合は、圧縮残留応力の導入が不十分となり、めっき特性の改善効果が発現しにくい。−250MPa未満の場合はめっき性特性の改善効果が飽和することに加え、鋼板表層に多量の転位が導入されることでめっき処理前の焼鈍中に表層組織が粗大化し、強度の低下につながる。よって、鋼板表面のα-Fe(211)面の平均残留応力σは、−250MPa≦σ≦−30MPaとする。なお、平均残留応力σは、酸洗後の圧延の圧下率を1〜10%とすることで−250MPa≦σ≦−30MPaとすることができる。
R=ΔS/(sin2ψ) (1)
σ=R×E (2)
次に、表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法について、説明する。
熱間圧延開始温度(スラブ加熱温度)
TiやNb等の微細析出の分散を行うためには、熱間圧延を行う前にTiやNb等を一旦鋼板中に溶解させる必要がある。そのため、熱間圧延する前の加熱温度(スラブ加熱温度)は1100℃以上が好ましい。一方で、1300℃を超えて加熱した場合には、鋼表層での内部酸化が促進され、表面性状が劣化する恐れがある。よって、熱間圧延前のスラブ加熱温度は1100℃以上1300℃以下が望ましい。
仕上げ圧延温度
熱間圧延時の変形抵抗を小さくし、操業を容易にするために、仕上げ圧延温度を800℃以上とすることが好ましい。一方、1000℃を超えて仕上げ圧延した場合には、スケール疵が発生しやすくなり、表面性状が劣化する。よって、仕上げ圧延温度は800℃以上1000℃以下とすることが好ましい。
熱延巻取り温度
本発明にかかる鋼板は、SiやMn、Tiを初めとした易酸化性元素を含有する。そのため、鋼板の過度な酸化を抑制し、良好な表面性状を確保するためには、巻取り温度は600℃以下であることが好ましい。一方、巻取り温度が400℃以下の場合には、冷却ムラに起因したコイル性状不良が生じやすくなるために、生産性を損なう恐れがある。よって、熱延巻取り温度は400℃以上600℃以下が好ましい。
前記熱間圧延工程によって得られた熱延鋼板は、酸洗によって脱スケールを施し、その後に圧延を実施する。酸洗は特に限定せず、常法でよい。この時、酸洗工程の前段階でも5%以下の圧延を施しても良く、この軽度の圧延によって脱スケール性が向上し、表面性状の改善に繋がる。
鋼板表面のめっき性を改善するために、熱延、酸洗後に圧延を実施する。圧延の際の圧下率は、1%以上10%以下とする。圧下を加えることで表面粗さの制御と母材表面に残留応力の導入を行う。圧下率を1%以上とすることで残留応力の導入が充分となり、鋼板表面のめっき性が改善される。圧下率が10%超えでは、めっき性特性の改善効果が飽和することに加え、鋼板表層に多量の転位が導入されることでめっき処理前の焼鈍中に表層組織が粗大化し、強度の低下につながる。
めっき処理前に焼鈍を行うことができる。条件は特に限定しないが、鋼板到達温度(T)が650〜750℃、T−50℃以上T℃以下の温度域で10〜500秒保持することが好ましい。鋼板到達温度が650℃より低い温度の場合、酸洗後の酸化皮膜が完全には還元されず、所望するめっき特性を得ることができない場合がある。また、750℃より高い温度では、Si、Mnなどが表面濃化してめっき性が劣化する恐れがある。また、T−50℃以上T℃以下の温度域での保持時間が10秒より短い場合、酸洗後の酸化皮膜が完全には還元されず、溶融めっき外観とめっき特性が低下する場合がある。一方、T−50℃以上T℃以下の温度域で保持時間が500秒より長くなると、溶融めっき鋼板の生産性に支障をきたす場合がある。
溶融めっき処理は連続溶融めっきラインにて、前記鋼板を還元焼鈍したのち、溶融めっき浴を用いて実施する。
溶融めっき浴の組成は、例えば、溶融亜鉛めっき処理の場合は、Al濃度0.01〜1.0%の範囲とし、残部をZnおよび不可避的不純物とする。Al濃度が0.01%未満の場合、めっき処理時にZn−Fe合金化反応が起こり、めっきと鋼板(母材)の界面に脆い合金層が発達し、めっき密着性が劣化する。Al濃度が0.2%を超えるとFe−Al合金層の成長が顕著となり、めっき密着性を阻害する。めっき浴温度は特に限定する必要はなく、通常の操業範囲である440℃以上、480℃以下でよい。また、めっき目付量については特に制約はないが、耐食性の観点30g/m2以上、加工性の観点150g/m2以下であることが好ましい。
合金化処理温度が550℃を超えると、合金化処理時に、鋼板(母材)とめっき皮膜の界面に硬質で脆いΓ相の生成が著しく、表面粗さが大きくなると共に耐パウダリング性が劣化するため、合金化処理温度は550℃以下が好ましい。さらに好ましくは530℃以下である。
合金化処理時間は、コストや制御上の問題点から、10秒以上60秒以下とするのが好ましい。より好ましくは40秒以内である。
合金化処理における加熱方法は特に限定する必要がなく、輻射加熱、通電加熱、高周波誘導加熱など、公知のいずれの方法でもよい。合金化処理を施した後は常温まで冷却する。めっき後の後処理は特に限定する必要はなく、調質圧延による材質の調整やレベリング等による平坦形状の調整、さらには必要に応じてクロメート処理等通常行われる後処理を施しても構わない。
表1に示す成分を有するスラブを用い、通常の鋳造、熱延酸洗後に、表2に示すような条件で圧延、焼鈍、溶融亜鉛めっき処理、さらに一部については合金化処理を行った。
熱延酸洗後の鋼板表面の残留応力(σ)は、X線回折装置を用いて、任意の場所・方向からの分析結果10点の平均により導出した。
鋼板表面の算術平均粗さRaは、圧延方向及び圧延方向と直行する方向について算術平均粗さを測定し、それぞれの方向に対して3回測定を行い、得られた結果の平均値とした。
引張試験は、引張方向が鋼板の圧延方向と直角方向となるようにサンプルを採取したJIS5号試験片、および、引張方向が鋼板の圧延方向と平行となるようにサンプルを採取したJIS5号試験片を用いて、JIS Z 2241(2011年)に準拠して行い、TS(引張強度)を測定した。引張方向が鋼板の圧延方向と直角方向となるように採取したサンプルと引張方向が鋼板の圧延方向と平行となるように採取したサンプル、それぞれで各5本引張試験を行い、平均値を引張強度(TS)とし、引張特性(TS)が590MPa以上を良好と判断した。
溶融めっき後及び合金化処理後の外観を目視観察し、不めっき、合金ムラがないものを○、不めっきや合金ムラがあるものは×とした。
溶融亜鉛めっき熱延鋼板のめっき密着性は、ボールインパクト試験で評価した。ボール重量2.8kg、落下高さ1mの条件で、ボールインパクト試験を行い、加工部をテープ剥離し、めっき層の剥離有無を目視判定した。
○ めっき層の剥離なし
× めっき層が剥離
耐パウダリング性
(合金化)溶融亜鉛めっき熱延鋼板のめっき密着性は、耐パウダリング性を試験することで評価した。合金化溶融めっき鋼板にセロハンテープを貼り、テープ面に90度曲げ、曲げ戻しを施し、テープを剥がす。剥がしたテープに付着した鋼板から、曲げ戻し部10mm×40mm当たりの剥離しためっきの量を、蛍光X線によるZnカウント数として測定し、下記基準に照らして評価した。
蛍光X線カウント数 ランク
1500未満 : ◎(良)
1500以上3000未満 : ○
3000以上5000未満 : △
5000以上 : ×(劣)
以上により得られた結果を製造条件と併せて表2に示す。
Claims (5)
- 成分組成として、質量%で、C:0.02%以上0.30%以下、Si:0.01%以上1.0%以下、Mn:0.3%以上2.5%以下、P:0.08%以下、S:0.02%以下、Al:0.001%以上0.20%以下を含有し、残部がFeおよび不可避的不純物からなる鋼を、熱間圧延、酸洗し、次いで、1〜10%の圧下率で圧延後、炉内雰囲気を水素濃度2〜20vol%かつ露点−60〜−10℃とし、鋼板到達温度(T)が650〜750℃、T−50℃以上T℃以下の温度域で10〜500秒保持する焼鈍を行い、次いで溶融めっき処理を行い、圧延を行うことなく鋼板を得ることを特徴とする、めっき前の鋼板表面の算術平均粗さRaが2.0μm以下であり、めっき前の鋼板表面のα-Fe(211)面の平均残留応力σが−250MPa≦σ≦−30MPaを満たす表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
- 成分組成として、さらに、質量%で、Ti:0.01%以上0.40%以下、Nb:0.001%以上0.200%以下、V:0.001%以上0.500%以下、Mo:0.01%以上0.50%以下、W:0.001%以上0.200%以下のうち1種または2種以上を含有することを特徴とする請求項1に記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
- 前記溶融めっき処理後、さらに、合金化処理を行うことを特徴とする請求項1または2に記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板の製造方法。
- 成分組成は、質量%で、C:0.02%以上0.30%以下、Si:0.01%以上1.0%以下、Mn:0.3%以上2.5%以下、P:0.08%以下、S:0.02%以下、Al:0.001%以上0.20%以下を含有し、残部がFeおよび不可避的不純物からなり、
めっき前の鋼板表面の算術平均粗さRaが2.0μm以下であり、めっき前の鋼板表面のα-Fe(211)面の平均残留応力σが−250MPa≦σ≦−30MPaを満たし、かつ、590MPa以上の引張強度を有することを特徴とする表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板。 - 成分組成として、さらに、質量%で、Ti:0.01%以上0.40%以下、Nb:0.001%以上0.200%以下、V:0.001%以上0.500%以下、Mo:0.01%以上0.50%以下、W:0.001%以上0.200%以下のうち1種または2種以上を含有することを特徴とする請求項4に記載の表面外観及びめっき密着性に優れた高強度溶融めっき熱延鋼板。
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