JP2023505445A - 電気抵抗スポット溶接部の疲労強度に優れた亜鉛めっき鋼板、及びその製造方法 - Google Patents
電気抵抗スポット溶接部の疲労強度に優れた亜鉛めっき鋼板、及びその製造方法 Download PDFInfo
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- JP2023505445A JP2023505445A JP2022532726A JP2022532726A JP2023505445A JP 2023505445 A JP2023505445 A JP 2023505445A JP 2022532726 A JP2022532726 A JP 2022532726A JP 2022532726 A JP2022532726 A JP 2022532726A JP 2023505445 A JP2023505445 A JP 2023505445A
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- steel sheet
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 36
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 117
- 239000010959 steel Substances 0.000 claims abstract description 117
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011572 manganese Substances 0.000 claims abstract description 51
- 239000001301 oxygen Substances 0.000 claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 44
- 239000010703 silicon Substances 0.000 claims abstract description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- 239000012298 atmosphere Substances 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000005261 decarburization Methods 0.000 description 9
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
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- 229910000794 TRIP steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910052595 hematite Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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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
- 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
- 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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- C21D6/002—Heat treatment of ferrous alloys containing Cr
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Abstract
Description
固溶元素を十分に溶体化し、圧延抵抗を減らすためにスラブを950℃以上の温度で加熱する必要がある。本発明の場合には、合金元素が多量含まれることがあるため、上記スラブ加熱温度は1000℃以上であり、好ましくは1100℃以上、さらに好ましくは1150℃以上である。但し、スラブ加熱温度が高すぎる場合には、固溶元素の酸化などの問題が発生することがあり、オーステナイト結晶粒の大きさが粗大になることがあり、エネルギー面でも有利でない。そのため、上記加熱温度の上限は1,350℃、好ましくは1,300℃、より好ましくは1,280℃以下とすることができる。
熱間圧延された鋼板は、この後にコイル状に巻き取られて保管されるが、巻き取られた鋼板は、徐冷過程を経るようになる。このような過程によって鋼板表層部に含まれた酸化性元素が除去されるようになるが、熱延鋼板の巻取り温度が低すぎる場合には、これらの元素の酸化除去に必要な温度より低い温度でコイルが徐冷するため、十分な効果を得ることが難しい。
上述した過程を経た熱延鋼板に対して熱延スケールを除去するために、塩酸浴に投入して酸洗処理を行う。酸洗時の塩酸浴の塩酸濃度は10~30体積%の範囲で行い、酸洗の通板速度は180~250mpmで行う。酸洗速度が250mpmを超過する場合には、熱延鋼板表面スケール(scale)が完全に除去されない場合があり、酸洗速度が180mpmより低い場合、素地鉄の表層部が塩酸によって腐食する可能性があるため、180mpm以上で行う。
酸洗を行った後に冷間圧延を行う。冷間圧延時の冷間圧下率は35~60%の範囲で行う。冷間圧下率が35%未満であると、特別な問題はないが焼鈍時の再結晶駆動力が不足して、十分に微細組織を制御し難い点が発生することがある。冷間圧下率が60%を超えると、熱延時に確保した内部酸化層の厚さが薄くなって、焼鈍後に十分な内部酸化の深さ及び酸素濃度の極大値を有することが難しい。
十分な生産性を確保するために、上記冷延鋼板の通板速度は40mpm以上である必要がある。但し、通板速度が過度に速い場合には、材質確保の側面から不利であるため、本発明の一実施形態では、上記通板速度の上限を130mpmに定めることができる。
適切な範囲の表層部の脱炭率値を得るために、焼鈍炉内の露点を制御することが有利である。露点が低すぎる場合には、内部酸化ではなく表面酸化が発生して表面にSiやMnなどの酸化物が形成されるおそれがある。これらの酸化物は、めっきに悪影響を及ぼす。したがって、露点は-10℃以上に制御する必要がある。一方、露点が高すぎる場合には、Feの酸化が発生するおそれがあるため、露点は30℃以下に制御される必要がある。このように露点制御のための温度は、十分な内部酸化効果が奏される温度である650℃以上であってよい。本発明の一実施形態において、上述した焼鈍炉内の温度及び露点は、均熱帯の温度及び露点を基準に定めることができる。但し、温度が高すぎる場合には、Siなどの表面酸化物が形成されて酸素が内部に拡散することを妨げるだけでなく、均熱帯の加熱中にオーステナイトが過度に発生して炭素拡散速度が低下し、それにより内部酸化レベルが減少することがあり、均熱帯のオーステナイトの大きさが過度に成長して材質軟化を発生させる。また、焼鈍炉への負荷が生じて設備の寿命を短縮し、工程費用を増加させるという問題を引き起こす可能性があるため、上記露点を制御する温度は900℃以下であってよい。
めっき浴内の鋼板の引き込み温度が低いと、鋼板と液相亜鉛との接触界面内の濡れ性が十分に確保できないため、420度以上の温度を維持する必要がある。温度が過度に高い場合、鋼板と液相亜鉛との反応が起こりすぎて、界面にFe-Zn合金相であるゼータ(Zetta)相が発生し、めっき層の密着性が低下し、めっき浴内の鋼板のFe元素の溶出量が過度になって、めっき浴内でドロスが発生するという問題がある。
めっき浴内のAl濃度は、めっき層の濡れ性及びめっき浴の流動性の確保のために、適正濃度を維持する必要がある。このために、本発明では、めっき浴内のAl濃度を0.10~0.25%の範囲に制御する。また、合金化処理の有無によってGA(合金化溶融亜鉛めっき、Galvannealed)鋼板と、GI(溶融亜鉛めっき、Galvanized)鋼板に分けられるが、本発明の一実施形態では、めっき浴内のドロス(dross)形成を適正水準に維持し、めっき表面品質及び性能を確保するために、GA鋼板の場合は、Al含有量を0.10~0.15%とすることができ、GI鋼板の場合は、Al含有量を0.2~0.25%に制御することができる。
480℃未満ではFe拡散量が少なく、合金化度が十分でないため、めっき物性が良くないことがあり、560℃を超える場合、過度な合金化によるパウダリング(powdering)問題が発生し、残留オーステナイトのフェライト変態によって材質が劣化することがあるため、合金化温度を上述の範囲に定める。
本発明の一実施形態では、エッジ部のGDOESの酸素の深さプロファイルにおいて極小値と極大値との差値をさらに大きくするために、熱延コイルのエッジ部を加熱することもできる。熱延コイルのエッジ部の加熱とは、巻き取られたコイルの幅方向の両端部、すなわち、エッジ部を加熱することを意味しており、エッジ部の加熱によってエッジ部が酸化に適した温度で先に加熱される。すなわち、巻き取られたコイルの内部は高温で維持されるが、エッジ部は比較的迅速に冷却され、これによりエッジ部は内部酸化に適した温度で維持される時間がより短くなる。したがって、幅方向の中心部に比べてエッジ部では酸化性元素の除去が活発に行われない。エッジ部の加熱は、エッジ部の酸化性元素を除去するための一方法として用いることができる。
下記表1に記載された組成を有する鋼スラブ(表に記載されていない残りの成分は、Fe及び不可避不純物である。なお、表中のB及びNは、ppm単位で表し、残りの成分は重量%単位で表し、表に示されていない成分の含有量は0重量%であることを意味する。)を1,230℃で加熱して熱間圧延した後、熱延コイルに対してエッジ部の加熱を行い、その後、長さ100mmの酸洗ラインにおいて210mpmの通板速度で鋼板を19.2体積%の塩酸溶液で酸洗してから冷間圧延し、得られた冷延鋼板を焼鈍炉で焼鈍した後、直ちにGAはAlが0.13%であるめっき浴に、GIはAlを0.24重量%含む456℃の亜鉛系めっき浴に浸漬して溶融亜鉛めっきを行った。得られた溶融亜鉛めっき鋼板に必要に応じて合金化(GA)熱処理を行い、最終的に合金化溶融亜鉛めっき鋼板を得た。
Claims (13)
- 素地鋼板、及び
前記素地鋼板の表面に形成された亜鉛系めっき層
を含む亜鉛めっき鋼板であって、
前記素地鋼板の表面から深さ方向に測定された酸素とシリコン及びマンガンのうち1つまたは2つの濃度プロファイルが、表面から深さ方向に極大点が現れる形態を有し、
前記酸素の濃度プロファイルの極大点が形成される深さと前記シリコン及びマンガンのうち1つの濃度プロファイルの極大点が形成される深さの差が絶対値で0.5μm以下である、亜鉛めっき鋼板。 - 前記酸素の濃度プロファイルの極大点が形成される深さが4~15μmである、請求項1に記載の亜鉛めっき鋼板。
- 前記極大点での酸素濃度が0.3重量%以上である、請求項2に記載の亜鉛めっき鋼板。
- 前記酸素の濃度プロファイルの極大点が形成される深さが、前記シリコン及びマンガンのうち1つまたは2つの全ての濃度プロファイルの極大点が形成される深さよりも小さい、請求項1に記載の亜鉛めっき鋼板。
- 前記濃度プロファイルがGDOESで測定したものである、請求項1に記載の亜鉛めっき鋼板。
- 前記亜鉛系めっき層のめっき付着量が30~70g/m2である、請求項1に記載の亜鉛めっき鋼板。
- 前記鋼板が、C:0.05~1.5%、Si:2.0%以下、Mn:1.0~30%、S-Al(酸可溶性アルミニウム):3%以下、Cr:2.5%以下、Mo:1%以下、B:0.005%以下、Nb:0.2%以下、Ti:0.2%以下、V:0.2%以下、Sb+Sn+Bi:0.1%以下、N:0.01%以下を含む組成を有する、請求項1~6のいずれか1項に記載の亜鉛めっき鋼板。
- 鋼スラブを950~1350℃の温度で加熱する段階、
前記鋼スラブを熱間圧延して熱延鋼板を得る段階、
前記熱延鋼板を590~750℃の温度で巻き取って熱延鋼板を得る段階、
前記熱延鋼板を180~250mpmの通板速度で酸洗する段階、
前記熱延鋼板を35~60%の圧下率で冷間圧延して冷延鋼板を得る段階、
650~900℃から-10~30℃の露点の雰囲気で前記冷延鋼板を再結晶焼鈍する段階、及び
前記焼鈍した冷延鋼板を溶融亜鉛めっきする段階
を含む、亜鉛めっき鋼板の製造方法。 - 前記再結晶焼鈍する段階が、水素(H2)を5~10体積%含む湿窒素ガス雰囲気で行われる、請求項8に記載の亜鉛めっき鋼板の製造方法。
- 前記再結晶焼鈍時の通板速度が40~130mpmである、請求項9に記載の亜鉛めっき鋼板の製造方法。
- 前記溶融亜鉛めっきが、420~500℃の鋼板引き込み温度でAl濃度が0.1~0.25重量%である溶融めっき浴に浸漬して行われる、請求項8に記載の亜鉛めっき鋼板の製造方法。
- 溶融亜鉛めっき後に480~560℃の温度で合金化する段階をさらに含む、請求項11に記載の亜鉛めっき鋼板の製造方法。
- 前記鋼スラブが、C:0.05~1.5%、Si:2.0%以下、Mn:1.0~30%、S-Al(酸可溶性アルミニウム):3%以下、Cr:2.5%以下、Mo:1%以下、B:0.005%以下、Nb:0.2%以下、Ti:0.2%以下、V:0.2%以下、Sb+Sn+Bi:0.1%以下、N:0.01%以下を含む組成を有する、請求項8~12のいずれか1項に記載の亜鉛めっき鋼板の製造方法。
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KR102604165B1 (ko) | 2023-11-20 |
CN114746571A (zh) | 2022-07-12 |
KR20210069758A (ko) | 2021-06-14 |
CN118326303A (zh) | 2024-07-12 |
EP4071263A4 (en) | 2022-12-21 |
US11981973B2 (en) | 2024-05-14 |
US20230002845A1 (en) | 2023-01-05 |
EP4071263A1 (en) | 2022-10-12 |
KR20210145699A (ko) | 2021-12-02 |
WO2021112581A1 (ko) | 2021-06-10 |
KR102330604B1 (ko) | 2021-11-24 |
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