WO2018193787A1 - 高強度溶融亜鉛めっき鋼板およびその製造方法 - Google Patents
高強度溶融亜鉛めっき鋼板およびその製造方法 Download PDFInfo
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- WO2018193787A1 WO2018193787A1 PCT/JP2018/011504 JP2018011504W WO2018193787A1 WO 2018193787 A1 WO2018193787 A1 WO 2018193787A1 JP 2018011504 W JP2018011504 W JP 2018011504W WO 2018193787 A1 WO2018193787 A1 WO 2018193787A1
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- WIPO (PCT)
- Prior art keywords
- less
- steel sheet
- martensite
- temperature
- dip galvanized
- Prior art date
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 19
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 90
- 239000010959 steel Substances 0.000 claims abstract description 90
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 70
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 38
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 30
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 30
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000005096 rolling process Methods 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 230000009466 transformation Effects 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005246 galvanizing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000005275 alloying Methods 0.000 claims description 13
- 238000007747 plating Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 238000005097 cold rolling Methods 0.000 claims description 8
- 238000005098 hot rolling Methods 0.000 claims description 7
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 235000019362 perlite Nutrition 0.000 claims description 2
- 239000010451 perlite Substances 0.000 claims description 2
- 229910001562 pearlite Inorganic materials 0.000 abstract description 9
- 230000000717 retained effect Effects 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 235000019589 hardness Nutrition 0.000 description 23
- 239000013078 crystal Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000002955 isolation Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000005496 tempering Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001887 electron backscatter diffraction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 235000019587 texture Nutrition 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003954 pattern orientation Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229910002066 substitutional alloy Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- 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
- 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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- 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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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
- 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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- 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
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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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
- 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
- C21D8/0236—Cold rolling
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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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- 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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C—CHEMISTRY; METALLURGY
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- 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
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- 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
- C23C2/0224—Two or more thermal pretreatments
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- 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
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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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- 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
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- C21D2211/00—Microstructure comprising significant phases
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- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
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- Y10T428/12958—Next to Fe-base component
Definitions
- the present invention relates to a high-strength hot-dip galvanized steel sheet and a method for producing the same.
- the steel plate to be used is required to have stretchability and hole expansibility.
- the strength of the steel plate is increased, the elongation and hole expansion properties deteriorate.
- Patent Document 1 both the strength and the elongation are increased by making the metal structure of the steel sheet a composite structure including ferrite as a soft structure and martensite as a hard structure.
- the composite structure disclosed in Patent Document 1 is a combination of a soft tissue and a hard tissue.
- a composite structure composed of structures having a large difference in hardness is inferior in hole expansibility.
- the hardness of the steel sheet is reduced by reducing the hardness difference between the structures by making the metal structure of the steel sheet a single structure of upper bainite or lower bainite having intermediate hardness between ferrite and martensite. Improves sex.
- the upper bainite and the lower bainite are inferior in elongation because they are composed of bainitic ferrite containing a large amount of dislocations and hard cementite.
- Patent Documents 3 to 5 disclose techniques relating to high-strength steel sheets in which elongation and hole expansion rate are improved by utilizing processing-induced transformation (TRIP) of retained austenite.
- TRIP processing-induced transformation
- the amount of carbon in the steel must be increased, so that the weldability deteriorates.
- the present invention has been made in view of the above situation, and an object of the present invention is a high-strength hot-dip galvanized steel sheet having an excellent balance of elongation, hole expansibility and bendability, and a tensile strength of 980 MPa or more. And a method of manufacturing the same.
- the gist of the present invention is as follows. (1) In mass%, C: 0.050% to 0.130% Si: 0.010% to 2.00% Mn: 1.50% to 3.50% P: 0.10% or less S: 0.010% or less N: 0.010% or less O: 0.010% or less sol.
- the balance has a chemical composition consisting of Fe and inevitable impurities, Steel structure in the range of 1/8 thickness to 3/8 thickness centered on 1/4 thickness from the surface is area%, Ferrite: 1-50% Martensite: 20-70% Residual austenite: 0-5% Perlite: 0-5% Total of MA and cementite with a particle size of 0.2 ⁇ m or more: 0-5% Bainite: The number density of MA or cementite having a particle size of 0.2 ⁇ m or more that is the remainder and is isolated in the ferrite or bainite grains is 100 pieces / 1000 ⁇ m 2 or less, and the average hardness of martensite A high-strength hot-dip galvanized steel sheet having a thickness of 330 Hv to 500 Hv.
- the chemical composition is replaced with a part of Fe, V: 0.001% to 1.00% Nb: 0.001% to 0.200%
- the high-strength hot-dip galvanized steel sheet according to the present invention characterized by containing one or more of them.
- the chemical composition is replaced with a part of Fe, Ni: 0.001% to 1.00% Cu: 0.001% to 1.00% Co: 0.001% to 1.00% W: 0.001% to 1.00% Sn: 0.001% to 1.00% Sb: 0.001% to 0.50%
- the high-strength hot-dip galvanized steel sheet according to the present invention characterized by containing one or more of them.
- the chemical composition is replaced with a part of Fe, Ca: 0.0001% to 0.0100% Mg: 0.0001% to 0.0100% Ce: 0.0001% to 0.0100% Zr: 0.0001% to 0.0100% La: 0.0001% to 0.0100% Hf: 0.0001% to 0.0100% Bi: 0.0001% to 0.0100% Misch metal: 0.0001% to 0.0100%
- the high-strength hot-dip galvanized steel sheet according to the present invention characterized by containing one or more of them.
- the method for producing a high-strength hot-dip galvanized steel sheet according to the present invention which satisfies the following steps (A) to (C) in order.
- Hot rolling step comprising the following (A1) to (A5) (A1) Slab heating temperature: 1150 ° C. or higher (A2) Total rolling reduction at 1150 to 1050 ° C .: 50% or higher (A3) Less than 1050 ° C.
- Hot dip galvanizing step including the following steps (C-1) Maximum heating temperature: Ac3-50 ° C to Ac3 + 50 ° C, holding time in the temperature range: 1 second to 500 seconds (C-2) Cooling rate between 600 ° C to 720 ° C: 5 ° C / second (C-3) Residence time at 480 ° C. to 600 ° C .: 5 to 500 seconds (C-4) Residence time at 440 ° C.
- cooling is performed so that the following formula (1) exceeds 30000 and less than 150,000 in the temperature range of Ms to 150 ° C.
- a high-strength hot-dip galvanized steel sheet having a tensile strength of 980 MPa or more and excellent in balance of elongation, hole expansibility and bendability, which is suitable for applications such as automobile steel sheets.
- the present invention is a steel plate provided with a hot-dip galvanized layer on one side or both sides, and is not a steel plate for galvanization that is a steel plate before the galvanized layer is provided.
- a steel sheet Each configuration of the present invention will be described below.
- “Chemical composition” First, the reason why the chemical composition of the high-strength steel sheet according to the present invention (hereinafter also simply referred to as a steel sheet) is defined as described above will be described. In this specification, “%” which defines the chemical composition. Unless otherwise specified, all are “% by mass”.
- C 0.050% to 0.130%
- C (carbon) is an essential element for increasing the strength of the steel sheet, so 0.050% or more is added.
- the C content is 0.050% to 0.130%. It is preferably 0.060% to 0.100%, more preferably 0.065 to 0.090%.
- Si silicon
- Si is a solid solution strengthening element and is an element effective for increasing the strength of a steel sheet
- 0.010% or more is added.
- excessive addition of Si exceeding 2.00% deteriorates wettability with hot dip galvanizing.
- excessive addition exceeding 2.00% of Si raises the temper softening resistance of a martensite, it raises the hardness of a martensite. Therefore, the Si content is set to 0.010% to 2.00%.
- the content is preferably 0.10 to 1.00%, more preferably 0.30 to 0.70%.
- Mn 1.50% to 3.50%
- Mn manganese
- Mn is a strong austenite stabilizing element and is an element effective for increasing the strength of the steel sheet, so 1.50% or more is added.
- excessive addition exceeding 3.50% of Mn increases the sum of cementite having a particle size of 0.2 ⁇ m or more and the MA fraction, and the hole expandability is lowered. Therefore, the Mn content is 1.50 to 3.50%.
- it is 2.00 to 3.00%, more preferably 2.20 to 2.80%.
- P 0.10% or less
- P (phosphorus) is a solid solution strengthening element contained as an inevitable impurity in steel and is an element effective for increasing the strength of a steel sheet, but excessive addition deteriorates weldability and toughness. Therefore, the P content is limited to 0.10% or less. Preferably it is 0.05% or less, More preferably, it is 0.02% or less. However, in order to extremely reduce the P content, since the de-P cost increases, the lower limit is preferably made 0.001% from the viewpoint of economy.
- S sulfur
- S (sulfur) is an element contained as an inevitable impurity in steel, and forms MnS in the steel to deteriorate toughness and hole expansibility. Therefore, the S content is limited to 0.010% or less as a range in which deterioration of toughness and hole expansibility is not remarkable. Preferably it is 0.006% or less, More preferably, it is 0.003% or less. However, in order to extremely reduce the S content, the desulfurization cost increases, and therefore the lower limit is preferably made 0.0005% from the viewpoint of economy.
- N nitrogen
- nitrogen is an element contained as an unavoidable impurity in steel, and when its content exceeds 0.010%, coarse nitrides are formed in the steel and the bendability and hole expandability deteriorate. . Therefore, the N content is limited to 0.010% or less. Preferably it is 0.006% or less, More preferably, it is 0.003% or less. However, in order to extremely reduce the N content, since the N removal cost increases, the lower limit is preferably made 0.0005% from the viewpoint of economy.
- O oxygen
- oxygen is an element contained in the steel as an inevitable impurity.
- the content exceeds 0.010%, a coarse oxide is formed in the steel to cause bendability and hole expansion. Therefore, the O content is limited to 0.010% or less. Preferably it is 0.006% or less, More preferably, it is 0.003% or less. However, the lower limit is preferably set to 0.0001% from the viewpoint of manufacturing cost.
- Al (aluminum) is at least sol.
- Add 0.001% with Al Preferably it is 0.005% or more.
- the upper limit of the Al content is 1.0%.
- sol. Al does not include the amount of Al precipitated and dispersed in the steel in the form of an aluminum compound such as aluminum nitride, but indicates the amount of Al dissolved as an alloy component in the steel.
- Ti titanium
- Ti suppresses the formation of BN which becomes a hardenability lowering factor by fixing N as TiN in steel.
- at least 0.005% of Ti is added.
- the upper limit of Ti content is 0.20%.
- it is 0.050% or less.
- B (boron) segregates at the austenite grain boundary or ferrite / austenite grain boundary during heating of the steel sheet, and stabilizes the grain boundary to improve the hardenability of the steel and to secure the martensite amount by quenching.
- B it is an essential element.
- B needs to be added in an amount of 0.0005% or more.
- it is 0.0010% or more.
- the upper limit of the B content is 0.010%.
- it is 0.0060% or less, More preferably, it is 0.0040% or less.
- Cr + 2 ⁇ Mo 0.10 to 1.50%
- Both Cr and Mo are elements that suppress the bainite transformation, and in the present invention, Cr + 2 ⁇ Mo is added so as to be 0.10% or more.
- Cr + 2 ⁇ Mo is less than 0.10%, the bainite transformation proceeds excessively and the amount of tempered martensite decreases.
- the number density of MA or cementite which is a mixed structure of martensite and austenite of 0.2 ⁇ m or more present in isolation in bainite, increases.
- Cr + 2 ⁇ Mo is larger than necessary, deterioration of weldability and cold rollability are caused, so 1.50% is made the upper limit.
- the range of Cr + 2 ⁇ Mo is preferably 0.20 to 1.0%, more preferably 0.30 to 0.70%.
- Cr + 2 ⁇ Mo is within the above range
- the range of addition of Cr and Mo takes into consideration the effect of increasing the strength of steel plates of Cr and Mo, the cost, etc., Cr: 0 It is preferable to appropriately select from 0.001% to 1.00% and Mo: 0.001% to 1.00%.
- the high-strength cold-rolled steel sheet according to the present invention has the above-described chemical component composition, and the balance is composed of Fe and inevitable impurities, and further contains the following elements as needed instead of a part of the Fe. May be.
- V 0.001% to 1.00%
- Nb one or more of 0.001% to 0.200%
- V (vanadium) and Nb (niobium) are carbide forming elements and may be added as necessary because they are effective elements for increasing the strength of the steel sheet. However, even if added excessively, the effect is saturated and the cost is increased. Therefore, the contents are respectively V: 0.001% to 1.00% and Nb: 0.001% to 0.200%. A more preferable V content is V: 0.01% to 0.200%, and a more preferable Nb content is Nb: 0.005% to 0.10. 0%.
- Ni 0.001% to 1.0%, Cu: 0.001% to 1.0%, Co: 0.001% to 1.0%, W: 0.001% to 1.0%, Sn : 0.001% to 1.0%, Sb: one or more of 0.001% to 0.50%]
- Ni (nickel), Cu (copper), Co (cobalt), W (tungsten), Sn (tin), and Sb (antimony) are all effective elements for increasing the strength of steel sheets, so add as needed. May be. However, if these elements are added excessively, the effect is saturated and the cost is increased. Accordingly, the contents are Ni: 0.001% to 1.0%, Cu: 0.001% to 1.0%, Co: 0.001% to 1.0%, W: 0.001% to 1%.
- Sn 0.001% to 1.0%
- Sb 0.001 to 0.50%. More preferably, Ni: 0.1% to 0.8%, Cu: 0.1% to 0.5%, Co: 0.1% to 0.5%, W: 0.1% to 0.3% %, Sn: 0.05% to 0.2%, and Sb: 0.01 to 0.10%.
- Ca 0.0001% to 0.0100%
- Mg 0.0001% to 0.0100%
- Ce 0.0001% to 0.0100%
- Zr 0.0001% to 0.0100%
- La 0.0001% to 0.0100%
- Hf 0.0001% to 0.0100%
- Bi 0.0001% to 0.0100%
- Misch metal 0.0001% to 0.0100%
- Ca (calcium), Mg (magnesium), Ce (cerium), Zr (zirconium), La (lanthanum), Hf (hafnium), and misch metal are elements that contribute to the fine dispersion of inclusions in steel.
- Bismuth is an element that reduces microsegregation of substitutional alloy elements such as Mn and Si in the steel and contributes to improving the workability of the steel sheet. Therefore, it is preferably added as necessary. In order to obtain the effect, 0.0001% or more of each addition is required. On the other hand, excessive addition causes deterioration of ductility. Therefore, the upper limit of the content is 0.0100%.
- Misch metal is a mixed alloy of mixed rare earth metals whose main component is a lanthanoid metal.
- the high-strength cold-rolled steel sheet of the present invention is composed of Fe and unavoidable impurities other than the elements described above, but can be contained within the range not impairing the effects of the present invention in addition to the elements described above. .
- the target steel structure is a steel structure in the range of 1/8 thickness to 3/8 thickness centered on 1/4 thickness from the surface of the steel sheet, and “%” defining the steel structure in this specification is particularly “ Unless otherwise noted, all are “area%”.
- ferrite 1-50% Since ferrite is a structure with excellent ductility, it improves the elongation of the steel sheet. On the other hand, since it is soft, when it contains excessively, ensuring of intensity
- the steel sheet according to the present invention contains 20% to 70% martensite. If the martensite content is 20% or less, the strength of the steel sheet cannot be ensured. On the other hand, if it exceeds 70%, the elongation of the steel sheet deteriorates. A more preferred martensite content is 30% to 60%.
- “martensite” includes both fresh martensite, which is martensite that has not been tempered, and tempered martensite. However, in the present invention, as will be described later, self-tempering of martensite occurs after the plating alloying treatment. Therefore, most of the martensite in the present invention is martensite that has been tempered to some extent in practice. However, martensite in MA (Martensite-Austenite Constituent), which is a mixed structure of martensite and austenite present in isolation in the ferrite or bainite grains described later, is excluded from “martensite”.
- Residual austenite 0 to 5%
- Residual austenite is transformed into hard martensite by deformation-induced transformation during deformation of the steel sheet, thereby deteriorating the hole expanding property of the steel sheet. Therefore, the content is made 0 to 5%. Preferably, it is 0 to 3%.
- pearlite is a metal structure containing hard and coarse cementite, it becomes a starting point of voids when expanding holes, and deteriorates the hole expandability of the steel sheet. Therefore, the content is made 0 to 3%.
- cementite and MA are extremely hard structures, serve as starting points for fracture when steel sheets are processed, and act as deterioration factors of hole expansibility, so the content is preferably as small as possible. Moreover, the larger the particle size, the easier it is to work as a starting point of fracture when the steel sheet is processed. If the particle size is small, specifically less than 0.2 ⁇ m, the effect is minor. Therefore, in the present invention, the total of MA having a particle size of 0.2 ⁇ m or more and cementite is 0 to 5%. Preferably, it is 0 to 3%. On the other hand, the lower limit is not particularly limited, but is preferably 1% or more in order to improve the strength.
- the remainder of the organization other than the above is bainite.
- the remaining bainite may be either an upper bainite or a lower bainite, or a mixed structure thereof.
- the number density of MA or cementite having a particle size of 0.2 ⁇ m or more present in isolation in ferrite or bainite grains is set to 100/1000 ⁇ m 2 or less. Preferably it is 50 pieces / 1000 ⁇ m 2 or less, more preferably 20 pieces / 1000 ⁇ m 2 or less.
- “existing in the ferrite or bainite grains” refers to MA or cementite that is not in contact with a crystal grain boundary having an orientation difference of 15 ° or more. Accordingly, MA or cementite that is in contact only with a grain boundary with an orientation difference of less than 15 ° (for example, a lower structure boundary such as lath forming bainite) and not with a crystal grain boundary with an orientation difference of 15 ° or more is It is supposed to exist in isolation.
- the average hardness of the martensite according to the present invention is 500 Hv or less. Preferably it is 450 Hv or less.
- the hardness of martensite is set to 330 Hv or more.
- the average hardness of martensite (average hardness of martensite) is determined by measuring the hardness of martensite having a thickness of 1/4 part using a Vickers hardness tester. The load is determined so that the indentation formed in the Vickers hardness measurement is included in the martensite crystal grains to be measured. The hardness of 50 martensite grains is measured, and the average value of these hardnesses is defined as the average hardness of martensite.
- the method for calculating the area percentage of the steel structure in the present invention is as follows. For ferrite, martensite, pearlite, MA and cementite area percentages of 0.2 ⁇ m or larger, cut the steel sheet in the rolling direction, and after mirror polishing, reveal the steel structure with nital solution and use a scanning electron microscope Take a secondary electron image. A region having a substructure in a grain and in which carbides are precipitated with a plurality of variants is determined as martensite. In addition, a region where cementite is deposited in a lamellar shape is determined as pearlite. The region where the luminance is low and the substructure is not recognized is determined as ferrite.
- a region where the luminance is high and the underlying structure is not revealed by etching is determined to be MA or cementite.
- the area% of each by the point counting method the area% of martensite and pearlite is obtained.
- the total number of grid points to be measured by the point counting method is preferably 1000 points or more per 1000 ⁇ m 2 visual field area.
- the area% of retained austenite is measured by the X-ray diffraction method. In the range from 1/8 thickness to 3/8 thickness centered on 1/4 thickness from the surface of the plate thickness, the surface parallel to the plate surface is finished as a mirror surface, and the area ratio of FCC iron is measured by X-ray diffraction method Then, it is defined as area% of retained austenite.
- the number density of MA or cementite having a crystal grain size of 0.2 ⁇ m or more present in isolation in ferrite or bainite grains is measured by the following method. First, a cross section in the rolling direction of a steel sheet is cut out, and a grain boundary having a crystal orientation difference of 15 ° or more is drawn by an EBSP-OIM (Electron Back Scattering Pattern-Orientation Image Microscopy) method for a sample subjected to mechanical polishing and electrolytic polishing. . Next, the same sample is corroded with the nital solution, and a secondary electron image is taken using a scanning electron microscope in the same region as the region where EBSD observation was performed.
- EBSP-OIM Electro Back Scattering Pattern-Orientation Image Microscopy
- an area where the luminance is high and the substructure is not revealed by etching is determined to be MA or cementite.
- the secondary electron image and EBSD grain boundary map are superimposed, and the number of MA and cementite particles that are not in contact with the grain boundary and have a grain size of 0.2 ⁇ m or more is counted and divided by the area of the measurement field. Density.
- the effective crystal grain size is preferably 5 ⁇ m or less.
- the effective crystal grain size means a crystal grain size in a region surrounded by a grain boundary having a crystal orientation difference of 15 ° or more, which will be described later.
- the average effective crystal grain size is measured by the EBSP-OIM method.
- the grain boundary of steel is 15 °, which is a threshold of a large-angle grain boundary that is generally recognized as a grain boundary, and by visualizing the grain from an image mapping grain boundaries with an orientation difference of 15 ° or more The average crystal grain size is measured.
- the slab heating temperature is specified as described above.
- the steel slab to be used is preferably cast by a continuous casting method from the viewpoint of manufacturability, but may be an ingot-making method or a thin slab casting method.
- the cast slab may be once cooled to room temperature, or directly sent to the heating furnace without being cooled to room temperature.
- the above conditions are preferable for the rolling reduction and the rolling temperature in the hot rolling process including the rough rolling process and the finish rolling process.
- the total rolling reduction at 1050 ° C. or higher and 1150 ° C. or lower is less than 50%, recrystallization during hot rolling tends to be insufficient, and thus the hot-rolled steel sheet structure tends to be heterogeneous.
- the Mn segregation zone becomes heterogeneous and the MA fraction of the final structure tends to increase.
- the total rolling reduction from the time when the temperature is less than 1050 ° C.
- the total rolling reduction at 1150 to 1050 ° C. may be 50% or more only in the rough rolling process, or the total rolling reduction at 1150 to 1050 ° C. is 50% over both the rough rolling process and the finishing rolling process. That is all you need. More preferably, it is 60% or more.
- the total rolling reduction from the time when the temperature is less than 1050 ° C. to the time before the final pass of the finish rolling is the finish rolling process when the temperature is less than 1050 ° C., it may be 66 to 95% only in the finish rolling process. If the temperature is less than °C, the rough rolling process, the total rolling reduction from the time when the temperature is less than 1050 °C to before the final pass of the final rolling is 66-95% even across the rough rolling process and the finishing rolling process. I just need it. More preferably, it is 70% or more.
- the rolling reduction of the final finishing pass is 10% to 30%, and the rising temperature of the finishing final pass is 850 ° C to 1000 ° C
- the above conditions are preferable for the rolling distribution and the rolling temperature in the finish rolling process.
- the rolling reduction of the finishing final pass exceeds 30%, or the rising temperature (rolling completion temperature) of the finishing final pass is lower than 850 ° C.
- the texture of the hot-rolled steel sheet develops. Is easily manifested.
- the rolling reduction of the final finishing pass is less than 10%, or the rising temperature of the finishing final pass is higher than 1000 ° C., the hot rolled steel sheet structure becomes coarse, and the final product board structure becomes coarse and eventually deteriorates in workability. It is easy to be connected to.
- Winding temperature 450-700 ° C
- the winding temperature is 450 to 700 ° C.
- the coiling temperature is lower than 450 ° C.
- the strength of the hot-rolled steel sheet becomes excessive and the cold rolling property is impaired.
- the coiling temperature exceeds 700 ° C.
- the amount of martensite in the final product is less than a predetermined amount, and it becomes difficult to obtain product plate strength. What is necessary is just to follow the pickling method of a hot-rolled coil in a conventional method. Further, skin pass rolling may be performed to correct the shape of the hot-rolled coil and improve the pickling property.
- the cold rolling rate is preferably 20% or more.
- the upper limit is made 80%. More preferably, it is 30% to 70%.
- hot dip galvanizing is performed on the steel sheet surface by a continuous hot dip galvanizing line process.
- "Manufacturing conditions in the continuous galvanizing line process” [Heating rate from 600 ° C to maximum heating temperature: 0.2 to 10 ° C / sec] The heating rate is preferably the above conditions.
- the heating rate exceeds 10 ° C./second, the recrystallization of ferrite does not proceed sufficiently, and the elongation of the steel sheet tends to deteriorate.
- austenite is coarsened in this heating stage, so that the steel structure finally obtained tends to be coarse. More preferably, it is 0.5 ° C./second or more.
- Maximum heating temperature Ac3-50 ° C to Ac3 + 50 ° C, hold for 1 second to 500 seconds in this temperature range
- the maximum heating temperature is set to at least Ac3-50 ° C.
- the heating temperature is raised excessively, it is difficult to ensure the ferrite fraction. Further, not only does the toughness and chemical conversion deteriorate due to the coarsening of the austenite grain size, but it also leads to damage to the annealing equipment. Therefore, the upper limit of the heating temperature is Ac3 + 50 ° C. Ac3-30 ° C to Ac3 is preferred.
- the heating time is short, austenitization does not proceed sufficiently to the extent necessary, so it is at least 1 second. More preferably, it is 30 seconds or more. On the other hand, if the heating time is too long, productivity is hindered, so the upper limit is set to 500 seconds.
- the number density of MA or cementite having a particle size of 0.2 ⁇ m or more present in isolation in ferrite or bainite grains is finally 100/1000 ⁇ m 2 or more.
- the residence time is preferably 10 seconds or more, and more preferably 30 seconds or more. On the other hand, if the residence time is too long, pearlite transformation occurs. Preferably it is 300 seconds or less.
- the residence may be maintained at a constant temperature as long as the specified conditions are satisfied, or may vary, for example, when slowly cooling between 480 ° C. and 600 ° C.
- hot dip galvanization may be performed according to a conventional method.
- the plating bath temperature may be 440 to 480 ° C.
- the immersion time may be 5 seconds or less.
- the plating bath is preferably a plating bath containing 0.08 to 0.2% Al, but may contain other inevitable impurities such as Fe, Si, Mg, Mn, Cr, Ti, and Pb.
- the basis weight is preferably 25 to 75 g / m 2 per side.
- An alloying treatment may be performed on the high-strength hot-dip galvanized steel sheet on which the hot-dip galvanized layer is formed, if necessary.
- the alloying treatment temperature may be 460 ° C. or more. preferable.
- the alloying treatment temperature is preferably 600 ° C. or less. More preferably, it is 580 degrees C or less.
- Equation (1) is a parameter representing the degree of progression of self-tempering of martensite.
- the cooling pattern from Ms to 150 ° C. may take any form as long as the expression (1) is satisfied.
- the cooling may be performed linearly from Ms to room temperature at a constant cooling rate, or the cooling rate may be changed during cooling. Or you may hold
- the martensitic transformation in the present invention occurs after the ferrite transformation and the bainite transformation. C distributes to austenite with ferrite transformation and bainite transformation. Therefore, it does not correspond to Ms when heated to an austenite single phase and rapidly cooled.
- Ms in the present invention is determined by using, for example, a thermal expansion measuring device such as a Formaster tester, the heat cycle (heating temperature, heating rate, heating time, cooling rate, cooling temperature range, cooling residence time) of the galvanizing line. Thermal expansion during the cooling process when heat treatment simulating the same heating temperature as the plating bath temperature, heating time equivalent to the plating time, and cooling conditions after plating until the start of martensite transformation) It can be determined by measuring the temperature.
- temper rolling may be performed for flattening the steel sheet and adjusting the surface roughness.
- the elongation is 2% or less.
- the conditions in the examples are one example of conditions adopted to confirm the feasibility and effects of the present invention.
- the present invention is not limited to this one condition example.
- the present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
- a steel having the chemical composition shown in Table 1 was melted to produce a slab.
- This slab was hot-rolled under the conditions shown in Table 2 to produce a hot-rolled steel sheet. Thereafter, the hot-rolled steel sheet was pickled and the surface scale was removed. Then, it cold-rolled on the conditions shown in Table 2. Furthermore, the obtained steel plate was subjected to heat treatment and continuous hot dip galvanizing treatment under the conditions shown in Table 3.
- a JIS No. 5 tensile test piece was taken from the steel sheet thus obtained from a direction perpendicular to the rolling direction, subjected to structural analysis, and subjected to a tensile test in accordance with JIS Z2241, to determine the tensile strength (TS) and total elongation (El). ) was measured.
- JFS T 1001 hole expansion test method of the Japan Iron and Steel Federation standard was performed, and the hole expansion ratio ( ⁇ ) was measured.
- a material having a tensile strength of 980 MPa or more, an elongation of 10% or more, and a hole expansion ratio of 30% or more was considered to have good mechanical properties.
- Table 4 Note that fine MA and cementite of less than 0.2 ⁇ m are included in bainite and martensite grains and are difficult to separate and quantitate, and thus are counted as bainite and martensite.
- Formula (1) exceeds the range defined by the present invention. As a result, the hardness of martensite was reduced and the strength was below 980 MPa. In Experimental Example 14, Formula (1) is below the range defined by the present invention. As a result, the hardness of martensite was increased and the hole expansion rate was inferior. In Experimental Example 11, the residence time of 480 to 600 ° C. is below the range specified by the present invention. As a result, the number density of MA or cementite having a crystal grain size of 0.2 ⁇ m or more present in isolation in the ferrite or bainite grains was increased, and the hole expansion rate was inferior. In Experimental Example 12, the residence time of 440 to 480 ° C. exceeds the range specified by the present invention.
- the area percentage of martensite is less than that of the present invention, the strength is less than 980 MPa, and the number density of MA or cementite having a crystal grain size of 0.2 ⁇ m or more that is present in isolation in ferrite or bainite grains is increased.
- the hole expansion rate was inferior.
- the winding temperature exceeds the range defined by the present invention.
- the area percentage of martensite was below the range defined by the present invention, so the strength was below 980 MPa.
- the alloying temperature exceeds the range defined by the present invention.
- pearlite exceeding the provisions of the present invention was produced, and the hole expansion rate was inferior.
- the maximum heating temperature exceeds the range defined by the present invention.
- Experimental Examples 1 to 9, 15, 17, 18, 22 to 44, 51, and 52 have a chemical composition and manufacturing conditions that match the range defined by the present invention, and thus have a structure defined by the present invention and are good. Mechanical properties were obtained.
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Abstract
Description
(1)質量%で、
C:0.050%~0.130%
Si:0.010%~2.00%
Mn:1.50%~3.50%
P:0.10%以下
S:0.010%以下
N:0.010%以下
O:0.010%以下
sol.Al:0.001%~1.0%
Ti:0.005%~0.20%
B:0.0005%~0.010%
Cr+2×Mo:0.10%~1.50%
残部がFeおよび不可避的不純物からなる化学組成を有し、
表面から1/4厚を中心とした1/8厚~3/8厚の範囲における鋼組織が、面積%で、
フェライト:1~50%
マルテンサイト:20~70%
残留オーステナイト:0~5%
パーライト:0~5%
粒径0.2μm以上のMAとセメンタイトの合計:0~5%
ベイナイト:残部
であり、かつ、フェライトまたはベイナイト粒内に孤立して存在する粒径0.2μm以上のMAまたはセメンタイトの個数密度が、100個/1000μm2以下であり、かつ、マルテンサイトの平均硬さが330Hv~500Hvであることを特徴とする、高強度溶融亜鉛めっき鋼板。
(2)前記化学組成が、Feの一部に代えて、
V:0.001%~1.00%
Nb:0.001%~0.200%
のうち一種以上を含有することを特徴とする、本発明の高強度溶融亜鉛めっき鋼板。
(3)前記化学組成が、Feの一部に代えて、
Ni:0.001%~1.00%
Cu:0.001%~1.00%
Co:0.001%~1.00%
W:0.001%~1.00%
Sn:0.001%~1.00%
Sb:0.001%~0.50%
のうち一種以上を含有することを特徴とする、本発明の高強度溶融亜鉛めっき鋼板。
(4)前記化学組成が、Feの一部に代えて、
Ca:0.0001%~0.0100%
Mg:0.0001%~0.0100%
Ce:0.0001%~0.0100%
Zr:0.0001%~0.0100%
La:0.0001%~0.0100%
Hf:0.0001%~0.0100%
Bi:0.0001%~0.0100%
ミッシュメタル:0.0001%~0.0100%
のうち一種以上を含有することを特徴とする、本発明の、高強度溶融亜鉛めっき鋼板。
(5)下記工程(A)~(C)を順に満足することを特徴とする、本発明の高強度溶融亜鉛めっき鋼板の製造方法。
(A)以下の(A1)~(A5)を備える熱間圧延工程
(A1)スラブ加熱温度:1150℃以上
(A2)1150~1050℃での総圧下率:50%以上
(A3)1050℃未満となった時点~仕上げ圧延最終パス前までの総圧下率:66~95%
(A4)仕上げ最終パスの圧下率:10%~30%、仕上げ最終パス温度:850℃~1000℃
(A5)巻取り温度:450~700℃
(B)20%以上80%以下の冷間圧延を行う工程
(C)以下の工程を備える溶融亜鉛めっき工程
(C-1)最高加熱温度:Ac3-50℃~Ac3+50℃、当該温度域での保持時間:1秒~500秒
(C-2)600℃~720℃の間の冷却速度:5℃/秒以上
(C-3)480℃~600℃での滞留時間:5~500秒
(C-4)440℃~480℃での滞留時間:5~60秒
(C-5)めっき・合金化処理後、室温まで冷却する工程において、Ms~150℃の温度域について、以下の式(1)が、30000を超え、150000未満となるように冷却
fM(T)=1-exp{-0.011×(Ms-T)}
TP(T)=(T+273)×{Log10(Δt/3600)+6}
Ms:マルテンサイト変態開始温度(℃)
T:温度(℃)
Δt:T(℃)からT-1(℃)に冷却するのに要した時間(秒)
『化学組成』
まず、本発明にかかる高強度鋼板(以下、単に鋼板とも称する)の化学組成を上述のように規定した理由について説明する。なお、本明細書において化学組成を規定する「%」
は特に断りのない限り全て「質量%」である。
C(炭素)は、鋼板の高強度化のために必須の元素であるため、0.050%以上添加する。一方、Cの0.130%を超える過度の添加は溶接性を劣化させる。従って、Cの含有量は0.050%~0.130%とする。好ましくは0.060%~0.100%であり、より好ましくは0.065~0.090%である。
Si(ケイ素)は固溶強化元素であり、鋼板の高強度化に有効な元素であるため、0.010%以上添加する。一方、Siの2.00%を超える過度の添加は溶融亜鉛めっきとの濡れ性を劣化させる。また、Siの2.00%を超える過度の添加は、マルテンサイトの焼き戻し軟化抵抗を上昇させるため、マルテンサイトの硬さを上昇させる。従って、Siの含有量は0.010%~2.00%とする。好ましくは0.10~1.00%であり、より好ましくは0.30~0.70%である。
Mn(マンガン)は強力なオーステナイト安定化元素であり、鋼板の高強度化に有効な元素であるため、1.50%以上添加する。一方、Mnの3.50%を超える過度の添加は、粒径0.2μm以上のセメンタイトとMA分率の合計を大きし、穴広げ性が低下する。従って、Mnの含有量は1.50~3.50%とする。好ましくは2.00~3.00%であり、より好ましくは2.20~2.80%である。
P(リン)は鋼中に不可避的不純物として含有される固溶強化元素であり、鋼板の高強度化に有効な元素であるが、過度の添加は溶接性および靱性を劣化させる。従って、P含有量は0.10%以下と制限する。好ましくは0.05%以下、より好ましくは0.02%以下である。ただし、P含有量を極度に低減させるには、脱Pコストが高くなるため、経済性の観点から下限を0.001%とすることが好ましい。
S(硫黄)は鋼中に不可避的不純物として含有される元素であり、鋼中でMnSを形成して靱性や穴広げ性を劣化させる。従って、靱性や穴広げ性の劣化が顕著でない範囲として、S含有量を0.010%以下と制限する。好ましくは0.006%以下、より好ましくは0.003%以下である。ただし、S含有量を極度に低減させるには、脱硫コストが高くなるため、経済性の観点から下限を0.0005%とすることが好ましい。
N(窒素)は鋼中に不可避的不純物として含有される元素であり、その含有量が0.010%を超えると鋼中に粗大な窒化物を形成して曲げ性や穴広げ性を劣化させる。従って、N含有量は0.010%以下と制限する。好ましくは0.006%以下、より好ましくは0.003%以下である。ただし、N含有量を極度に低減させるには、脱Nコストが高くなるため、経済性の観点から下限を0.0005%とすることが好ましい。
O(酸素)は鋼中に不可避的不純物として含有される元素であり、その含有量が0.010%を超えると鋼中に粗大な酸化物を形成して曲げ性や穴広げさせる。従って、O含有量は0.010%以下と制限する。好ましくは0.006%以下、より好ましくは0.003%以下である。ただし、製造コストの観点から、下限を0.0001%とすることが好ましい。
Al(アルミニウム)は、鋼の脱酸のため少なくともsol.Alで、0.001%を添加する。好ましくは0.005%以上である。しかし、過剰に添加しても効果が飽和し徒にコスト上昇を招くばかりか、鋼の変態温度を上昇させ熱間圧延時の負荷を増大させる。従ってsol.Al量は1.0%を上限とする。好ましくは0.50%以下であり、より好ましくは0.20%以下である。なお、sol.Alは、アルミニウム窒化物等のアルミニウム化合物の形態で鋼中に析出分散しているAl量は含まず、鋼中に合金成分として固溶しているAlの量を示す。
Ti(チタン)は鋼中でTiNとしてNを固定することで、焼入性低下因子となるBNの形成を抑制する。また加熱時のオーステナイト粒径を微細化し靱性を向上させるため、Tiは、少なくとも0.005%を添加する。好ましくは0.010%以上である。一方、過剰に添加すると鋼板の延性が低下する。従ってTi含有量の上限値は0.20%とする。好ましくは0.050%以下である。
B(ホウ素)は鋼板の加熱時にオーステナイト粒界、またはフェライト/オーステナイト粒界に偏析し、粒界を安定化することで鋼の焼入性を高め、焼入によるマルテンサイト量を確保するため、本発明では必須の元素である。その効果を十分に得るには、Bは、0.0005%以上の添加を必要とする。好ましくは0.0010%以上である。一方、過度の添加はホウ化物を形成することにより、鋼の焼入性を損なう結果となる。従ってB含有量の上限値は0.010%とする。好ましくは0.0060%以下、より好ましくは0.0040%以下である。
Cr、Moはいずれもベイナイト変態を抑制する元素であり、本発明においては、Cr+2×Moが0.10%以上となるように添加する。Cr+2×Moが0.10%を下回ると、ベイナイト変態が過剰に進行してしまい、焼戻しマルテンサイトの量が減少する。また、ベイナイト中に孤立して存在する0.2μm以上のマルテンサイトおよびオーステナイトの混合組織であるMAまたはセメンタイトの個数密度が増加する。一方、Cr+2×Moが必要以上に大きい場合、溶接性の劣化や冷間圧延性の劣化を招くため、1.50%を上限とする。好ましいCr+2×Moの範囲は0.20~1.0%であり、より好ましくは0.30~0.70%である。なお、Cr+2×Moを上記の範囲とすることは前提であるが、Cr、Moの各々の添加範囲は、CrやMoの鋼板の高強度化に対する効果や、コスト等を勘案し、Cr:0.001%~1.00%、Mo:0.001%~1.00%から適宜選択することが好ましい。
V(バナジウム)、Nb(ニオブ)は炭化物形成元素であり、鋼板の高強度化に有効な元素であることから必要に応じて添加してもよい。しかし、過度に添加しても効果が飽和し徒にコストを上昇させる。従ってその含有量はそれぞれV:0.001%~1.00%、Nb:0.001%~0.200%とする。より好ましいVの含有量は、V:0.01%~0.200%であり、より好ましいNbの含有量は、Nb:0.005%~0.10
0%である。
Ni(ニッケル)、Cu(銅)、Co(コバルト)、W(タングステン)、Sn(スズ)、Sb(アンチモン)はいずれも鋼板の高強度化に有効な元素であるため必要に応じて添加してもよい。しかしこれらの元素を過度に添加すると効果が飽和し徒にコストの増大を招く。従って、その含有量はNi:0.001%~1.0%、Cu:0.001%~1.0%、Co:0.001%~1.0%、W:0.001%~1.0%、Sn:0.001%~1.0%、Sb:0.001~0.50%とする。より好ましくは、Ni:0.1%~0.8%、Cu:0.1%~0.5%、Co:0.1%~0.5%、W:0.1%~0.3%、Sn:0.05%~0.2%、Sb:0.01~0.10%である。
Ca(カルシウム)、Mg(マグネシウム)、Ce(セリウム)、Zr(ジルコニウム)、La(ランタン)、Hf(ハフニウム)、ミッシュメタルは鋼中介在物の微細分散化に寄与する元素であり、Bi(ビスマス)は鋼中におけるMn、Si等の置換型合金元素のミクロ偏析を軽減する元素であり、それぞれ鋼板の加工性向上に寄与することから、必要に応じて添加することが好ましい。その効果を得るには、それぞれ0.0001%以上の添加を要する。一方、過度の添加は延性の劣化を引き起こす。従ってその含有量は0.0100%を上限とする。ミッシュメタルは、その主成分をランタノイド金属とする混合希土類金属の混合合金である。
次に、本発明に係る高強度鋼板の鋼組織を規定した理由について説明する。なお、対象の鋼組織は、鋼板の表面から1/4厚を中心とした1/8厚~3/8厚の範囲における鋼組織とし、本明細書において鋼組織を規定する「%」は特に断りのない限り全て「面積%」である。
フェライトは延性に優れる組織であるため、鋼板の伸びを向上させる。一方、軟質であるため、過度に含有すると強度の確保が困難となる。従って、その含有量は1~50%とする。好ましくは10%~40%であり、より好ましくは15~35%である。
本発明に係る鋼板は、20%~70%のマルテンサイトを含む。マルテンサイトが20%以下であると、鋼板の強度が確保できない。一方、70%を超えると鋼板の伸びが劣化する。より好ましいマルテンサイトの含有量は30%~60%である。
なお、本明細書において、「マルテンサイト」とは、焼き戻されていないマルテンサイトであるフレッシュマルテンサイト、および焼き戻しマルテンサイトの両方の意味を含む。但し、本発明においては、後述の通り、めっき合金化処理後にマルテンサイトの自己焼き戻しが発生する。そのため、本発明におけるマルテンサイトの大部分は、事実上、ある程度以上焼き戻されたマルテンサイトである。
但し、後述するフェライトまたはベイナイト粒内に孤立して存在するマルテンサイトおよびオーステナイトの混合組織であるMA(Martensite-Austenite Constituent)中のマルテンサイトは、「マルテンサイト」から除外する。
残留オーステナイトは、鋼板の変形中に加工誘起変態により硬質なマルテンサイトへと変態するので、鋼板の穴広げ性を劣化させる。従って、その含有率は0~5%とする。好ましくは0~3%である。
パーライトは硬質かつ粗大なセメンタイトを含む金属組織であるので、穴広げ時にボイドの発生起点となり、鋼板の穴広げ性を劣化させる。従って、その含有率は0~3%とする。
セメンタイトおよびMA(Martensite-Austenite Constituent)は極めて硬質な組織であり、鋼板を加工した際の破壊の起点となり、穴広げ性の劣化因子として作用するため、その含有量は小さいほど好ましい。また、その粒径が大きいほど、鋼板を加工した際に破壊の起点として働き易い。粒径が小さい場合、具体的には0.2μm未満であれば、その影響は軽微である。従って、本発明においては、粒径0.2μm以上のMAとセメンタイトの合計を0~5%とする。好ましくは0~3%である。一方、下限に関しては、特に制限されるものではないが、強度を向上させるためには1%以上が好ましい。
MAおよびセメンタイトは極めて硬質な組織であり、鋼板加工時の破壊の起点となる。面積分率に加えて、面積当たりの個数密度を制限することにより、破壊の起点を低減することができるため、穴広げ性が向上する。本発明においては、フェライトまたはベイナイト粒内に孤立して存在する粒径0.2μm以上のMAまたはセメンタイトの個数密度を、100個/1000μm2以下とする。好ましくは50個/1000μm2以下であり、より好ましくは20個/1000μm2以下である。
ここで、「フェライトまたはベイナイト粒内に孤立して存在」とは、方位差15°以上の結晶粒界に接していないMAまたはセメンタイトをさす。従って、方位差15°未満の粒界(たとえば、ベイナイトを形成するラス等の下部組織境界など)にのみ接し、方位差15°以上の結晶粒界と接していないMAまたはセメンタイトは、「粒内に孤立して存在」しているものとする。
穴広げ性の改善のためには、硬質組織であるマルテンサイトと、軟質組織であるフェライトおよびベイナイトとの硬度差を小さくする事が重要である。従って、本発明に係るマルテンサイトの平均硬さは500Hv以下とする。好ましくは450Hv以下である。一方、マルテンサイトの硬度が低すぎると、引張強度980MPa以上の強度が確保できないため、マルテンサイトの平均硬さは330Hv以上とする。
マルテンサイトの平均硬さ(マルテンサイトの平均硬さ)は、板厚1/4部のマルテンサイトの硬さをビッカース硬度計を用いて測定することにより求める。荷重は、ビッカース硬度測定において形成される圧痕が、測定対象とするマルテンサイトの結晶粒内に含まれるように決定する。50個のマルテンサイト粒の硬度を測定し、これら硬度の平均値を、マルテンサイトの平均硬さとする。
フェライト、マルテンサイト、パーライト、粒径0.2μm以上のMAとセメンタイトの面積%については、鋼板の圧延方向断面を切出し、鏡面研磨後、ナイタール液により鋼組織を現出し、走査型電子顕微鏡を用いて二次電子像を撮影する。粒内に下部組織を有し、かつ、炭化物が複数のバリアントを持って析出している領域をマルテンサイトと判断する。また、セメンタイトがラメラ状に析出している領域をパーライトと判断する。輝度が小さく、かつ下部組織が認められない領域をフェライトと判断する。輝度が大きく、かつ下部組織がエッチングにより現出されていない領域をMAまたはセメンタイトと判断する。各々の面積%を、ポイントカウンティング法によって算出することで、マルテンサイトおよびパーライトの面積%とする。ポイントカウンティング法により、測定する総格子点数は視野面積1000um2あたり1000点以上とすることが好ましい。
残留オーステナイトの面積%は、X線回折法により測定する。板厚の表面から1/4厚を中心とした1/8厚~3/8厚の範囲において、板面に平行な面を鏡面に仕上げ、X線回折法によってFCC鉄の面積率を測定し、それをもって残留オーステナイトの面積%とする。
[有効結晶粒径:好ましくは5μm以下]
穴広げ性をさらに優れた水準とするには、有効結晶粒径を5μm以下とすることが好ましい。なお、有効結晶粒径とは、後述の手法にて述べる結晶方位差15°以上の粒界に囲まれた領域の結晶粒径を意味する。
平均有効結晶粒径は、EBSP-OIM法により測定する。鋼の結晶粒界を、一般的に結晶粒界として認識されている大角粒界の閾値である15°と定義し、方位差15°以上の粒界をマッピングした画像より粒を可視化することにより、その平均結晶粒径を測定する。
[引張強度が980MPa以上]
本発明における高強度鋼板の引張強度は980MPa以上となる。
[1150℃以上にスラブを加熱する工程]
ホウ化物や炭化物を十分溶解するため、スラブ加熱温度は以上のように規定する。なお使用する鋼スラブは、製造性の観点から連続鋳造法にて鋳造することが好ましいが、造塊法、薄スラブ鋳造法でもよい。また、鋳造したスラブは一旦室温まで冷却してもよく、室温まで冷却することなく加熱炉に直送しても構わない。
粗圧延工程、仕上げ圧延工程からなる熱間圧延工程での圧下率および圧延温度は以上の条件が好ましい。
1050℃以上、1150℃以下での総圧下率が50%未満であると、熱間圧延中の再結晶が不十分となりやすいため、熱延鋼板組織が不均質化しやすい。その結果、Mn偏析帯が不均質化し、最終組織のMA分率が増加しやすい。
1050℃未満となった時点~仕上げ最終パス前までの総圧下率が95%を超える場合、熱延鋼板の集合組織が発達するため、最終製品板における異方性が顕在化しやすい。一方、1050℃未満となった時点~仕上げ最終パス前までの総圧下率が66%を下回ると、熱延鋼板組織の粗大化を招き、最終製品板組織の粗大化ひいては加工性の劣化に繋がりやすい。
1150~1050℃での総圧下率は、粗圧延工程のみで、50%以上としてもよいし、粗圧延工程と、仕上げ圧延工程にまたがっても、1150~1050℃での総圧下率が50%以上であればよい。より好ましくは60%以上である。1050℃未満となった時点~仕上げ圧延最終パス前までの総圧下率も、1050℃未満となった時点が仕上げ圧延工程ならば、仕上げ延工程のみで、66~95%としてもよいし、1050℃未満となった時点が粗圧延工程ならば、粗圧延工程と、仕上げ圧延工程にまたがっても、1050℃未満となった時点~仕上げ圧延最終パス前までの総圧下率が66~95%であればよい。より好ましくは70%以上である。
仕上げ圧延工程での圧下配分および圧延温度は以上の条件が好ましい。仕上げ最終パスの圧下率が30%を超える、または仕上げ最終パスの上がり温度(圧延完了温度)が850℃を下回った場合、熱延鋼板の集合組織が発達するため、最終製品板における異方性が顕在化しやすい。一方、仕上げ最終パスの圧下率が10%を下回る、または仕上げ最終パスの上がり温度が1000℃を上回ると、熱延鋼板組織の粗大化を招き、最終製品板組織の粗大化ひいては加工性の劣化に繋がりやすい。
巻取り温度は450~700℃とする。巻取り温度は450℃を下回ると、熱延鋼板強度が過大となり、冷間圧延性を損なう。一方、巻取り温度が700℃を上回ると、最終製品のマルテンサイトの量が所定量を下回り、製品板強度を得ることが困難となる。
熱延コイルの酸洗方法は常法に従えばよい。また、熱延コイルの形状矯正および酸洗性向上のためにスキンパス圧延を行ってもよい。
[20%以上80%以下の冷間圧延]
連続溶融亜鉛めっきライン工程において加熱中のオーステナイト粒径を微細化するため冷間圧延率は20%以上とすることが好ましい。一方、過度の圧下は圧延加重が過大となり冷延ミルの負荷増大を招くため、その上限は80%とする。より好ましくは30%~70%である。
『連続溶融亜鉛めっきライン工程における製造条件』
[600℃~最高加熱温度までの加熱速度:0.2~10℃/秒]
加熱速度は上記の条件が好ましい。加熱速度が10℃/秒を超えると、フェライトの再結晶が十分進行せず、鋼板の伸びが劣化しやすい。一方、加熱速度が0.2℃/秒を下回ると、この加熱の段階でオーステナイトが粗大化するため、最終的に得られる鋼組織が粗大なものとなりやすい。より好ましくは、0.5℃/秒以上である。
必要な量のマルテンサイト組織が得られ、必要な程度にオーステナイト化を進行させるため、最高加熱温度は少なくともAc3-50℃以上とする。一方、過剰に加熱温度を上げると、フェライト分率を確保することが困難となる。また、オーステナイト粒径の粗大化による靭性の劣化や化成処理性の劣化を招くばかりか、焼鈍設備の損傷にも繋がる。そのため加熱温度の上限はAc3+50℃とする。好ましくはAc3-30℃~Ac3である。加熱時間は短いと必要な程度にオーステナイト化が十分進行しないため、少なくとも1秒以上とする。より好ましくは30秒以上である。一方、加熱時間は長すぎると生産性を阻害することから上限は500秒とする。
上記加熱後、480~600℃の間まで冷却する。また、720℃から600℃までの間の冷却速度は5℃/秒以上とする。冷却速度が5℃/秒未満の場合、フェライト分率が本発明において規定する上限を上回る。好ましくは10℃/秒以上である。冷却速度の上限は特に規定する必要はないが、一般的な連続焼鈍炉の冷却能力では冷却速度が100℃/秒を上回ることは困難である。
上記冷却温度範囲まで冷却後、480℃~600℃の温度域で5秒以上、滞留させる。この処理により、後述する溶融亜鉛めっきラインで不可避的に発生する440~480℃近辺でのベイナイト変態の進行を抑制することができる。そのメカニズムの詳細は明らかでないが、480℃~600℃での保持中に、鋼中のB原子の結晶粒界への偏析度が強まり、その結果、440~480℃でのベイナイト変態の進行が抑制されると考えられる。溶融亜鉛めっきラインでベイナイトが発生することにより、最終的に、フェライトまたはベイナイト粒内に孤立して存在する粒径0.2μm以上のMAまたはセメンタイトの個数密度:100個/1000μm2以上となる。滞留時間は10秒以上が好ましく、30秒以上がより好ましい。一方、滞留時間が長すぎると、パーライト変態が生じるため、500秒以下とする。好ましくは300秒以下である。なお、上記滞留は、規定する条件を満足する限り、一定の温度で保持してもよいし、480℃~600℃の間で徐冷する場合等、変動しても構わない。
鋼板に亜鉛めっきを施すために、上記工程の後、鋼板を440~480℃に冷却する。ここで、440℃~480℃における滞留時間は60秒以下とする。当該温度域はベイナイト変態の進行が速い温度域であるため、この温度域での滞留時間が長いと、ベイナイト変態が過度に進行し、本発明が規定するマルテンサイト分率が得られなくなる。また、当該温度域で生成したベイナイトの粒内には、480℃~600℃で生成したベイナイトと比べて、MAやセメンタイトを多く含有する。そのため、当該温度域での滞留時間は短いほど好ましい。しかしながら、溶融亜鉛めっきラインにおいては、亜鉛ポット浴に鋼板を浸漬させる必要があるため、当該温度域での滞留時間は不可避的に発生する。そのため、440~480℃での滞留時間は5秒を下限とする。
めっき・合金化処理後は、Ms~150℃の温度域について、以下の式(1)が、30000を超え、150000未満となるように冷却する。
fM(T)=1-exp{-0.011×(Ms-T)}
TP(T)=(T+273)×{Log10(Δt/3600)+6}
Msはマルテンサイト変態開始温度、Tは温度(℃)、ΔtはT(℃)からT-1(℃)に冷却するのに要した時間(秒)である。本発明において、マルテンサイト変態はめっき合金化処理の後の冷却中に生じる。また、マルテンサイトの自己焼戻し(オートテンパー)が生じ、マルテンサイトが軟質化する。式(1)はマルテンサイトの自己焼戻しの進行の程度を表したパラメータであり、式(1)が大きいほど、自己焼戻しが進行し、マルテンサイトが軟質化する。一方、式(1)が小さいほど、自己焼戻しが抑制され、マルテンサイトが硬質化する。マルテンサイトの平均硬さを330Hv~500Hvとするためには、式(1)を満たす条件で冷却する必要がある。
式(1)中のfM(T)は、T℃におけるマルテンサイト変態率であり、Tが小さいほど、すなわちMsからの過冷却度が大きいほど、fM(T)は大きくなる。TP(T)はT℃におけるマルテンサイトの焼戻しの度合いを表したパラメータであり、Tが大きいほど大きくなる。また、T℃における滞留時間Δtが大きいほど、大きくなる。また、鋼板のMsが高いほど、式(1)の値は大きくなる。
Msから150℃までの冷却パターンは、式(1)を満足する限り、どのような形態であってもよい。例えば、Msから室温まで一定の冷却速度で直線的に冷却してもよいし、冷却中に冷却速度を変更してもよい。あるいは、ある温度で保持を行っても構わない。
なお、本発明におけるマルテンサイト変態は、フェライト変態およびベイナイト変態の後に生じる。フェライト変態およびベイナイト変態に伴い、オーステナイトにCが分配する。そのため、オーステナイト単相に加熱し、急冷した際のMsとは一致しない。本発明におけるMsは、例えば、フォーマスタ試験機などの熱膨張測定装置を用いて、上記溶融亜鉛めっきラインのヒートサイクル(加熱温度、加熱速度、加熱時間、冷却速度、冷却温度範囲、冷却滞留時間、めっき浴温と同様の加熱温度、めっき時間と同等の加熱時間、マルテンサイト変態開始までのめっき後の冷却条件)を同様なものに模擬した熱処理を施した場合に、冷却過程での熱膨張温度を測定することにより、求めることができる。
実験例14は、式(1)が本発明の規定する範囲を下回る。その結果、マルテンサイトの硬さが大きくなり、穴広げ率が劣位となった。
実験例11は、480~600℃の滞留時間が本発明の規定する範囲を下回る。その結果、フェライトまたはベイナイト粒内に孤立して存在する結晶粒径0.2μm以上のMAまたはセメンタイトの個数密度が大きくなり、穴広げ率が劣位となった。
実験例12は、440~480℃の滞留時間が本発明の規定する範囲を上回る。その結果、マルテンサイトの面積%が本発明の規定を下回り、強度が980MPaを下回り、フェライトまたはベイナイト粒内に孤立して存在する結晶粒径0.2μm以上のMAまたはセメンタイトの個数密度が大きくなり、穴広げ率が劣位となった。
実験例13は、巻き取り温度が本発明の規定する範囲を上回る。その結果、マルテンサイトの面積%が本発明の規定する範囲を下回ったため、強度が980MPaを下回った。
実験例16は、合金化処理温度が本発明の規定する範囲を上回る。その結果、本発明の規定を上回るパーライトが生成し、穴広げ率が劣位となった。
実験例19は、最高加熱温度が本発明の規定する範囲を上回る。その結果、フェライトの面積%が減少し、伸びが劣位となった。
実験例20および21は、720℃~600℃の冷却速度が本発明の規定する範囲を下回る。その結果、フェライトの面積%が増加し、強度あるいは穴広げ率のいずれかが劣位となった。
実験例45はCが本発明の規定する範囲を上回るため、マルテンサイトの硬さが大きくなり、穴広げ率が劣位となった。
実験例46は、Bが本発明の規定する範囲を下回るため、マルテンサイト分率が減少し、引張強度が劣位となった。
実験例47は、Cr+2×Moが本発明の規定する範囲を下回るため、マルテンサイト分率が減少し、引張強度が劣位となった。
実験例49は、Cr+2×Moが本発明の規定する範囲を上回るため、マルテンサイト分率が大きくなり、伸びが劣位となった。
実験例48は、Mnが本発明の規定する範囲を上回るため、粒径0.2μm以上のセメンタイトとMA分率の合計が大きくなり、穴広げ率が劣位となった。
実験例50は、Siが本発明の規定する範囲を上回るため、マルテンサイトの硬さが大きくなり、穴広げ率が劣位となった。
Claims (5)
- 質量%で、
C:0.050%~0.130%
Si:0.010%~2.00%
Mn:1.50%~3.50%
P:0.10%以下
S:0.010%以下
N:0.010%以下
O:0.010%以下
sol.Al:0.001%~1.0%
Ti:0.005%~0.20%
B:0.0005%~0.010%
Cr+2×Mo:0.10%~1.50%
残部がFeおよび不可避的不純物からなる化学組成を有し、
表面から1/4厚を中心とした1/8厚~3/8厚の範囲における鋼組織が、面積%で、
フェライト:1~50%
マルテンサイト:20~70%
残留オーステナイト:0~5%
パーライト:0~5%
粒径0.2μm以上のMAとセメンタイトの合計:0~5%
ベイナイト:残部
であり、かつ、フェライトまたはベイナイト粒内に孤立して存在する粒径0.2μm以上のMAまたはセメンタイトの個数密度が、100個/1000μm2以下であり、かつ、マルテンサイトの平均硬さが330Hv~500Hvであることを特徴とする、高強度溶融亜鉛めっき鋼板。 - 前記化学組成が、Feの一部に代えて、
V:0.001%~1.00%
Nb:0.001%~0.200%
のうち一種以上を含有することを特徴とする、請求項1に記載の高強度溶融亜鉛めっき鋼板。 - 前記化学組成が、Feの一部に代えて、
Ni:0.001%~1.00%
Cu:0.001%~1.00%
Co:0.001%~1.00%
W:0.001%~1.00%
Sn:0.001%~1.00%
Sb:0.001%~0.50%
のうち一種以上を含有することを特徴とする、請求項1または請求項2に記載の高強度溶融亜鉛めっき鋼板。 - 前記化学組成が、Feの一部に代えて、
Ca:0.0001%~0.0100%
Mg:0.0001%~0.0100%
Ce:0.0001%~0.0100%
Zr:0.0001%~0.0100%
La:0.0001%~0.0100%
Hf:0.0001%~0.0100%
Bi:0.0001%~0.0100%
ミッシュメタル:0.0001%~0.0100%
のうち一種以上を含有す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、高強度溶融亜鉛めっき鋼板。 - 下記工程(A)~(C)を順に満足することを特徴とする、請求項1~4のいずれか1項に記載の高強度溶融亜鉛めっき鋼板の製造方法。
(A)以下の(A1)~(A5)を備える熱間圧延工程
(A1)スラブ加熱温度:1150℃以上
(A2)1150~1050℃での総圧下率:50%以上
(A3)1050℃未満となった時点~仕上げ圧延最終パス前までの総圧下率:66~95%
(A4)仕上げ最終パスの圧下率:10%~30%、仕上げ最終パス温度:850℃~1000℃
(A5)巻取り温度:450~700℃
(B)20%以上80%以下の冷間圧延を行う工程
(C)以下の工程を備える溶融亜鉛めっき工程
(C-1)最高加熱温度:Ac3-50℃~Ac3+50℃、当該温度域での保持時間:1秒~500秒
(C-2)600℃~720℃の間の冷却速度:5℃/秒以上
(C-3)480℃~600℃での滞留時間:5~500秒
(C-4)440℃~480℃での滞留時間:5~60秒
(C-5)めっき・合金化処理後、室温まで冷却する工程において、Ms~150℃の温度域について、以下の式(1)が、30000を超え、150000未満となるように冷却
fM(T)=1-exp{-0.011×(Ms-T)}
TP(T)=(T+273)×{Log10(Δt/3600)+6}
Ms:マルテンサイト変態開始温度(℃)
T:温度(℃)
Δt:T(℃)からT-1(℃)に冷却するのに要した時間(秒)
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WO2013051238A1 (ja) | 2011-10-04 | 2013-04-11 | Jfeスチール株式会社 | 高強度鋼板およびその製造方法 |
JP6323618B1 (ja) * | 2017-01-06 | 2018-05-16 | Jfeスチール株式会社 | 高強度冷延鋼板およびその製造方法 |
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JP6763479B2 (ja) | 2020-09-30 |
CN110520550A (zh) | 2019-11-29 |
US11332803B2 (en) | 2022-05-17 |
BR112019020644A2 (pt) | 2020-05-05 |
US20200115771A1 (en) | 2020-04-16 |
MX2019012243A (es) | 2019-11-28 |
EP3613868B1 (en) | 2021-11-17 |
KR102336669B1 (ko) | 2021-12-07 |
EP3613868A4 (en) | 2020-09-09 |
TW201839151A (zh) | 2018-11-01 |
KR20190126854A (ko) | 2019-11-12 |
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CN110520550B (zh) | 2021-08-17 |
TWI666332B (zh) | 2019-07-21 |
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