JP6436268B1 - めっき密着性に優れた高強度溶融亜鉛めっき鋼板の製造方法 - Google Patents
めっき密着性に優れた高強度溶融亜鉛めっき鋼板の製造方法 Download PDFInfo
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- JP6436268B1 JP6436268B1 JP2018524845A JP2018524845A JP6436268B1 JP 6436268 B1 JP6436268 B1 JP 6436268B1 JP 2018524845 A JP2018524845 A JP 2018524845A JP 2018524845 A JP2018524845 A JP 2018524845A JP 6436268 B1 JP6436268 B1 JP 6436268B1
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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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B32B15/013—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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- C—CHEMISTRY; METALLURGY
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C21D8/0273—Final recrystallisation annealing
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
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Abstract
成分組成として、質量%で、C:0.02%以上0.30%以下、Si:0.01%以上2.0%以下、Mn:0.2%以上3.0%以下、P:0.08%以下、S:0.02%以下、Al:0.001%以上0.40%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板上に、片面あたりのめっき付着量が30〜90g/m2のめっき層を有し、めっき層中には、剥離地鉄を0.3〜1.5g/m2含有する。
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2.0%以下、Mn:0.2%以上3.0%以下、P:0.08%以下、S:0.02%以下、Al:0.001%以上0.40%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板上に、片面あたりのめっき付着量が30〜90g/m2のめっき層を有し、該めっき層中には、剥離地鉄を0.3〜1.5g/m2含有することを特徴とするめっき密着性に優れた高強度溶融めっき鋼板。
[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、B:0.0003%以上0.01%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上記[1]に記載のめっき密着性に優れた高強度溶融めっき鋼板。
[3]上記[1]または[2]に記載の成分組成を有する鋼スラブを、熱間圧延し、圧下率1〜10%で圧延し、酸洗を行い、次いで、圧下率0.3〜5%で圧延し、溶融めっき処理を行うことを特徴とするめっき密着性に優れた高強度溶融めっき鋼板の製造方法。
[4]前記熱間圧延において、粗圧延後、仕上げ圧延温度820℃以上で圧延終了した後、巻取温度450〜650℃で巻き取ることを特徴とする上記[3]に記載のめっき密着性に優れた高強度溶融めっき鋼板の製造方法。
[5]圧下率0.3〜5%で前記圧延後前記溶融めっき処理前に、水素濃度2〜30vol%かつ露点−60〜−10℃の炉内雰囲気、鋼板到達温度600〜950℃で連続焼鈍を行うことを特徴とする上記[3]または[4]に記載のめっき密着性に優れた高強度溶融めっき鋼板の製造方法。
[6]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上記[3]〜[5]のいずれかに記載のめっき密着性に優れた高強度溶融めっき鋼板の製造方法。
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り、めっき外観やめっき密着性の低下を招く。以上より、Si含有量は0.01%以上2.0%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0.2%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に合金化の調整が困難となり、めっき外観やめっき密着性の低下を招く。以上より、Mn含有量は0.2%以上3.0%以下とする。好ましくは0.3%以上2.6%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%以下とする。
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。そのため、S含有量は0.02%以下とする。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、0.40%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0.40%以下とする。
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。一方、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%以下とする。
なお、Nb、V、Mo、WおよびB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含有量は0.001%以上0.200%以下、V含有量は0.001%以上0.500%以下、Mo含有量は0.01%以上0.50%以下、W含有量は0.001%以上0.200%以下、B含有量は0.0003%以上0.01%以下である。
めっき層は、片面あたりのめっき付着量が30〜90g/m2である。付着量が30g/m2未満では耐食性の確保が困難になる。一方、90g/m2を超えると耐めっき剥離性が劣化する。
熱間圧延開始温度(スラブ加熱温度)(好適条件)
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℃以下が好ましい。より好ましくは1100℃以上1200℃以下である。
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820℃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ことがある。よって、仕上げ圧延温度は820℃以上、より好ましくは820℃以上1000℃以下とする。より好ましくは850℃以上950℃以下である。
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650℃以下であることが好ましい。一方、巻取り温度が450℃未満の場合には、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450℃以上650℃以下が好ましい。より好ましくは450℃以上600℃以下である。
熱間圧延・熱延巻取り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、圧延を実施する。酸洗は特に限定せず、常法でよい。ここで、本発明では、酸洗の前段階で圧延を施す。酸洗の前段階で圧延を施すことは本発明において重要な要件である。酸洗の前段階で圧延を施すことで、スケール押付による鋼板表面への適度な凹凸付与が行われ、めっき層内への剥離地鉄取り込みが促進される。圧下率は1〜10%である。圧下率が1%未満の場合、鋼板表面への凹凸付与が十分に行われず、十分なめっき密着性改善効果が得られない。一方、圧下率が10%超えの場合、スケールが地鉄に噛み込み、脱スケール性が著しく低下する。
本発明では、酸洗後に圧下率0.3〜5%の圧延を施す。酸洗後に圧下率0.3〜5%の圧延を施すことは本発明において重要な要件である。圧下を加えることで表面形状の制御と母材表面に残留応力の導入を行う。圧下率を0.3%以上とすることで残留応力の導入が充分となり、鋼板表面のめっき反応性が改善される。圧下率が5%超えでは、歪導入によるめっき反応性の改善効果が飽和することに加え、鋼板表面が平滑化し、剥離地鉄をめっき層内に取り込ませることが困難となる。
圧下率0.3〜5%の圧延後溶融めっき処理前に焼鈍を行うことが好ましい。好適条件は、水素濃度2〜30vol%かつ露点−60〜−10℃の炉内雰囲気、鋼板到達温度600〜950℃である。焼鈍到達温度が600℃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、950℃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。より好ましくは、鋼鈑到達温度は650℃以上850℃以下である。
炉内雰囲気は水素濃度2〜30%かつ露点−60〜−10℃とすることが好ましい。炉内雰囲気は還元性であれば良く、露点−60〜−10℃、水素濃度2〜30%で残部が不活性ガスからなる雰囲気が好適である。露点が−10℃より高いと、鋼板表面に生成するSi酸化物の形態が膜状となり易い。より好ましくは、露点−20℃以下である。一方、−60℃より低い露点は工業的に実現が困難である。水素濃度が2%より低い場合は、還元性が弱い。30%以下であれば十分な還元能力が得られる。より好ましくは、水素濃度5%以上20%以下である。
溶融めっき処理は連続溶融めっきラインにて、好ましくは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0.01〜0.25%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0.25%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。
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。一方で、合金化処理温度480℃未満では十分に合金化がなされず、十分なめっき特性を得ることができない。そのため、合金化処理温度は480℃以上が望ましい。
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秒以下である。
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に示す成分組成を有するスラブを用い、通常の鋳造後、表2に示す条件で熱間圧延、圧延、酸洗、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。
亜鉛めっき層中の剥離地鉄量については、ICP発光分光分析法を使用し、以下の手順で測定した。まず、亜鉛めっき層を、インヒビターを添加した希塩酸で溶解することで、めっき鋼板中の亜鉛めっき層のみを剥離・溶解する。インヒビターとは、地鉄の過溶解防止のために使用する添加剤であり、市販のもので良い。本発明では、10〜100倍に希釈した塩酸に、0.6g/Lの濃度になるよう朝日化学工業株式会社製の塩酸酸洗用腐食抑制剤「イビットNo.700BK」を添加した。希塩酸でのめっき鋼板溶解後、未溶解の剥離地鉄を含んだ溶液を抽出し、2つの溶液に分ける。そのうち、片方の溶液については剥離地鉄未溶解のまま組成分析を行い、もう一方の溶液についてはインヒビター未添加の塩酸で再溶解後、組成分析を行う。こうして得られた結果の差分を、剥離地鉄量とした。
溶融亜鉛めっき鋼板(GI)もしくは合金化溶融亜鉛めっき鋼板(GA)より圧延方向に対して直角方向にJIS5号引張試験片(JIS Z2201)を採取し、歪速度が10-3/sとするJIS Z 2241の規定に準拠した引張試験を行い、TSを求めた。
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
3000未満 : ◎(良)
3000以上6000未満 : ○
6000以上 : ×(劣)
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2.0%以下、
Mn:0.2%以上3.0%以下、
P:0.08%以下、
S:0.02%以下、
Al:0.001%以上0.40%以下を含有し、残部がFeおよび不可避的不純物からなる成分組成を有する鋼スラブを、熱間圧延し、圧下率1〜10%で圧延し、酸洗を行い、次いで、圧下率0.3〜5%で圧延し、溶融亜鉛めっき処理を行うことを特徴とするめっき密着性に優れた高強度溶融亜鉛めっき鋼板の製造方法。 - 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、
B:0.0003%以上0.01%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に記載のめっき密着性に優れた高強度溶融亜鉛めっき鋼板の製造方法。 - 前記熱間圧延において、粗圧延後、仕上げ圧延温度820℃以上で圧延終了した後、巻取温度450〜650℃で巻き取ることを特徴とする請求項1または2に記載のめっき密着性に優れた高強度溶融亜鉛めっき鋼板の製造方法。
- 圧下率0.3〜5%で前記圧延後前記溶融めっき処理前に、水素濃度2〜30vol%かつ露点−60〜−10℃の炉内雰囲気、鋼板到達温度600〜950℃で連続焼鈍を行うことを特徴とする請求項1〜3のいずれかに記載のめっき密着性に優れた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1〜4のいずれか一項に記載のめっき密着性に優れた高強度溶融亜鉛めっき鋼板の製造方法。
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