JP6696047B2 - リン酸塩処理性と成形性が優れた冷間圧延高強度鋼板及びその製造方法 - Google Patents
リン酸塩処理性と成形性が優れた冷間圧延高強度鋼板及びその製造方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims description 187
- 239000010959 steel Substances 0.000 title claims description 187
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 238000000137 annealing Methods 0.000 claims description 44
- 229910001566 austenite Inorganic materials 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 32
- 239000011572 manganese Substances 0.000 claims description 31
- 229910019142 PO4 Inorganic materials 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 28
- 239000010452 phosphate Substances 0.000 claims description 28
- 230000000717 retained effect Effects 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000002344 surface layer Substances 0.000 claims description 15
- 238000005097 cold rolling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910000734 martensite Inorganic materials 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 14
- 238000003303 reheating Methods 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 12
- 238000005098 hot rolling Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 claims description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 17
- 239000013078 crystal Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 238000013461 design Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- 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
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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
- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- 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
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- C21D8/0226—Hot rolling
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
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- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Heat Treatment Of Sheet Steel (AREA)
- Chemical Treatment Of Metals (AREA)
Description
リン酸塩処理性と成形性が優れた冷間圧延高強度鋼板であって、前記鋼板の化学成分が、重量百分率で、C 0.15〜0.25%、Si 1.50〜2.50%、Mn 2.00〜3.00%、P≦0.02%、S≦0.01%、Al 0.03〜0.06%、N≦0.01%を含み、残部がFe及び不可避不純物元素であり、前記鋼板の表層に厚さ1〜5μmの内部酸化層が存在し、前記内部酸化層は鉄をマトリックスとし、当該マトリックスは酸化物粒子を含有し、前記酸化物粒子はSi酸化物、SiとMnとの複合酸化物のうちの少なくとも1種であり、鋼板の表面にSi、Mn元素が富化されていない。
Cは、鋼において、強度を確保するために必要な固溶強化元素であり、オーステナイト安定化元素である。C含有量が少なすぎると残留オーステナイトの含有量が不足し、かつ材料強度が低くなり、C含有量が多すぎると鋼材の溶接性が著しく悪化する。よって、本発明では、C含有量を0.15〜0.25%に制御する。
上記化学成分になるように製錬し、鋳造して、スラブを製造する。
スラブを1170〜1300℃に加熱し、0.5〜4h保温し、圧延し、仕上げ圧延温度を850℃以上に制御し;巻き取りにおいて、巻き取り温度を400〜700℃として、熱間圧延コイルを得る。
熱間圧延コイルを巻き出し、酸洗い及び冷間圧延を行い、酸洗い速度を150m/min以下とし、冷間圧延の圧下率を40〜80%として、圧延硬質帯鋼を得る。
得られた圧延硬質帯鋼を巻き出し、洗浄して、温度790〜920℃まで均一に加熱し、30〜200s保温し、そのうち、加熱速率を1〜20℃/sとし、加熱ゾーン及び保温ゾーンの雰囲気としてN2−H2混合ガスを使用し、そのうち、H2含有量が0.5〜20%であり;焼鈍の雰囲気の露点が−25〜10℃であり;
その後、200〜300℃に急冷し、冷却速度が30℃/s以上であり;
その後、さらに350〜450℃に加熱し、60〜250s保温して、優れたリン酸塩処理性と成形性を有する冷間圧延高強度鋼板を得る。
さらに、工程4)では、焼鈍雰囲気の露点を−10〜5℃とする。
本発明では、熱間圧延の時に、スラブに対する再加熱の温度が1170〜1300℃、好ましくは1210〜1270℃である。加熱温度が高すぎると、スラブが過焼成され、スラブ内の結晶粒組織が粗大化して熱間加工性が低下してしまい、また、超高温はスラブ表面の激しい脱炭を引き起こす。加熱温度が低すぎると、スラブは高圧水によってスケール除去及び初期圧延を経て、仕上げ温度が低すぎるため、ブランクの変形抵抗力が大きくなってしまう。熱間圧延の時に、保温時間が0.5〜4hである。保温時間が4hを超えると、スラブ内の結晶粒組織が粗大になると共に、スラブ表面が著しく脱炭する。保温時間が0.5h未満であると、スラブの内部温度はまだ均一とならない。
1) 本発明の冷間圧延高強度鋼板の表面層は、鉄をマトリックスとし、厚さ1〜5μm、酸化物粒子を含む内部酸化層を有し、当該内部酸化層はSi、Mnなどの元素が鋼板の表面に富化するのを阻止することで、上記元素の酸化反応が鋼板表面で発生しないようにさせ、外部酸化から内部酸化へと変化し、当該鋼板の表面にSi、Mn元素の富化がないため、鋼板のリン酸塩処理性を向上し、高Si含有量の冷間圧延高強度鋼板の優れたリン酸塩処理性を確保できる。
本発明の実施例1〜16のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板、及び比較例1〜5の鋼板は、以下の工程を採用した。
Claims (9)
- 化学成分が、重量百分率で、C 0.15〜0.25%、Si 1.50〜2.50%、Mn 2.00〜3.00%、P≦0.02%、S≦0.01%、Al 0.03〜0.06%、N≦0.01%を含み、残部がFe及び不可避不純物元素であるリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板であって、前記鋼板の表層に厚さ1〜5μmの内部酸化層が存在し、前記内部酸化層は鉄をマトリックスとし、当該マトリックスは酸化物粒子を含有し、前記酸化物粒子はSi酸化物、SiとMnとの複合酸化物のうちの少なくとも1種であり、鋼板の表面にSi、Mn元素が富化されていなく;
前記酸化物粒子の平均直径は50〜200nmであり、酸化物粒子間の平均間隔λは、以下の関係を満足しており、
- 前記鋼板は、さらにCr 0.01〜1.0%、Mo 0.01〜0.5%及びNi 0.01〜2.0%のうちの少なくとも1種を含むことを特徴とする請求項1に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板。
- 前記鋼板は、さらにTi 0.005〜0.05%、Nb 0.005〜0.1%及びV 0.005〜0.1%のうちの少なくとも1種を含むことを特徴とする請求項1に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板。
- 前記酸化物粒子は、酸化ケイ素、ケイ酸マンガン、ケイ酸鉄、及びケイ酸フェロマンガンのうちの少なくとも1種であることを特徴とする請求項1〜3のいずれか1項に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板。
- 前記リン酸塩処理性と成形性が優れた冷間圧延高強度鋼板の室温組織はフェライト、マルテンサイト及び残留オーステナイトを含む複合組織であり、そのうち、残留オーステナイト含有量が5%以上であることを特徴とする請求項1に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板。
- 前記冷間圧延高強度鋼板の引張強度が1180MPa以上、伸び率が14%以上であることを特徴とする請求項1に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板。
- 以下の工程:
1) 製錬、鋳造
前記化学成分になるように製錬し、鋳造して、スラブを製造し;
2) 熱間圧延、巻き取り
スラブを1170〜1300℃に加熱し、0.5〜4h保温し、圧延し、仕上げ圧延温度を850℃以上に制御し;巻き取りにおいて、巻き取り温度を400〜700℃として、熱間圧延コイルを得り;
3) 酸洗い、冷間圧延
熱間圧延コイルを巻き出し、酸洗い及び冷間圧延を行い、酸洗い速度を150m/min以下とし、冷間圧延の圧下率を40〜80%として、圧延硬質帯鋼を得り;
4) 連続焼鈍
得られた圧延硬質帯鋼を巻き出し、洗浄して、温度790〜920℃まで均一に加熱し、30〜200s保温し、そのうち、加熱速率を1〜20℃/sとし、加熱ゾーン及び保温ゾーンの雰囲気として、N2−H2混合ガスを使用し、そのうち、H2含有量が0.5〜20%であり;焼鈍の雰囲気の露点が−25〜10℃であり;
その後、200〜300℃に急冷し、冷却速度が30℃/s以上であり;
その後、さらに350〜450℃に加熱し、60〜250s保温して、優れたリン酸塩処理性と成形性を有する冷間圧延高強度鋼板を得る、
を含む請求項1〜6のいずれか1項に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板の製造方法。 - 工程2)で熱間圧延を行う際に、スラブに対する再加熱の温度を1210〜1270℃とし、巻き取り温度を450〜550℃とすることを特徴とする請求項7に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板の製造方法。
- 工程4)において、均熱温度を810〜870℃とし、焼鈍雰囲気の露点を−10〜5℃とすることを特徴とする請求項7又は8に記載のリン酸塩処理性と成形性が優れた冷間圧延高強度鋼板の製造方法。
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