WO2011102434A1 - 溶融めっき鋼材及びその製造方法 - Google Patents
溶融めっき鋼材及びその製造方法 Download PDFInfo
- Publication number
- WO2011102434A1 WO2011102434A1 PCT/JP2011/053426 JP2011053426W WO2011102434A1 WO 2011102434 A1 WO2011102434 A1 WO 2011102434A1 JP 2011053426 W JP2011053426 W JP 2011053426W WO 2011102434 A1 WO2011102434 A1 WO 2011102434A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hot
- plating layer
- mass
- steel material
- layer
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 258
- 239000010959 steel Substances 0.000 title claims abstract description 258
- 239000000463 material Substances 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000007747 plating Methods 0.000 claims abstract description 379
- 229910007981 Si-Mg Inorganic materials 0.000 claims abstract description 102
- 229910008316 Si—Mg Inorganic materials 0.000 claims abstract description 102
- 239000011701 zinc Substances 0.000 claims abstract description 49
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 26
- 239000000470 constituent Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000007598 dipping method Methods 0.000 claims description 119
- 229910052751 metal Inorganic materials 0.000 claims description 89
- 239000002184 metal Substances 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 54
- 229910045601 alloy Inorganic materials 0.000 claims description 48
- 239000000956 alloy Substances 0.000 claims description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 229910000838 Al alloy Inorganic materials 0.000 claims description 30
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 25
- 239000008397 galvanized steel Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 230000007797 corrosion Effects 0.000 abstract description 69
- 238000005260 corrosion Methods 0.000 abstract description 69
- 239000010410 layer Substances 0.000 description 443
- 239000012071 phase Substances 0.000 description 127
- 239000011651 chromium Substances 0.000 description 77
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000000126 substance Substances 0.000 description 45
- 230000037303 wrinkles Effects 0.000 description 44
- 238000001816 cooling Methods 0.000 description 42
- 239000011247 coating layer Substances 0.000 description 35
- 239000007789 gas Substances 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 28
- 230000008569 process Effects 0.000 description 27
- 239000003973 paint Substances 0.000 description 26
- 239000000523 sample Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 24
- 230000009471 action Effects 0.000 description 23
- 238000005452 bending Methods 0.000 description 21
- 239000002344 surface layer Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 16
- 238000007665 sagging Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 238000005096 rolling process Methods 0.000 description 14
- 229910052712 strontium Inorganic materials 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000137 annealing Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052790 beryllium Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 229910052747 lanthanoid Inorganic materials 0.000 description 9
- 150000002602 lanthanoids Chemical class 0.000 description 9
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910052706 scandium Inorganic materials 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 238000012937 correction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 210000004894 snout Anatomy 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910007570 Zn-Al Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052705 radium Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 229910018134 Al-Mg Inorganic materials 0.000 description 2
- 229910018467 Al—Mg Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000669 Chrome steel Inorganic materials 0.000 description 2
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- 241000919514 Albuginaceae Species 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- 229910019064 Mg-Si Inorganic materials 0.000 description 1
- 229910019406 Mg—Si Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GQJPVGNFTLBCIQ-UHFFFAOYSA-L sodium;zirconium(4+);carbonate Chemical compound [Na+].[Zr+4].[O-]C([O-])=O GQJPVGNFTLBCIQ-UHFFFAOYSA-L 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/12764—Next to Al-base component
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
- Y10T428/12917—Next to Fe-base component
- Y10T428/12924—Fe-base has 0.01-1.7% carbon [i.e., steel]
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
- Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to a hot dipped plated steel material and a method for manufacturing the same.
- molten Zn—Al-based plated steel materials have been widely used for applications such as building materials, materials for automobiles, and materials for home appliances.
- high aluminum (25 to 75 mass%) and zinc alloy-plated steel sheet represented by 55% aluminum / zinc alloy-plated steel sheet (Galbarium steel sheet (registered trademark)
- Gabarium steel sheet registered trademark
- hot-dip Zn-Al plated steel materials has been achieved by adding Mg and the like to the plating layer (patents). Reference 1 to 4).
- Patent Document 1 discloses that Al by mass contains 3 to 13% Si, 2 to 8% Mg, and 2 to 10% Zn, with the balance being a hot-dip plated layer consisting of Al and inevitable impurities.
- a —Si—Mg—Zn-based hot-dip Al-based plated steel sheet is disclosed.
- the hot-dip plated layer further contains 0.002 to 0.08% Be and 0 to 0.1% Sr, or 3 to 13% Si, 2 to 8% Mg, and Zn.
- Patent Document 1 the corrosion resistance of the hot-dip plated steel material is improved by adding Mg to the plating layer.
- Mg Mg oxidation
- Patent Document 1 also describes that Mg oxidation is suppressed by adding Sr or Be to the plating layer and as a result suppresses wrinkles, but the suppression of wrinkles is not sufficient.
- Such wrinkles formed in the plating layer are difficult to remove sufficiently even by a temper rolling process and the like, causing deterioration of the appearance of the hot-dip plated steel material.
- This invention is made
- the place made into the objective is to provide the hot-dipped steel material with favorable corrosion resistance and workability, and the external appearance of a plating layer, and its manufacturing method. is there.
- Mg is an element that is easily oxidized as compared with other elements constituting the plating layer. It reacts with oxygen to produce an Mg-based oxide. Accordingly, Mg is concentrated on the surface layer of the hot dip metal, and the formation of an Mg-based oxide film (a film made of an oxide of a metal containing Mg) is promoted on the surface layer of the hot dip metal. In the process where the hot dip metal is cooled and solidified, the Mg-based oxide film is formed before the solidification inside the hot dip metal is completed, so there is a difference in fluidity between the surface layer and the inside of the hot dip metal. Occurs. For this reason, even if the inside of the hot dipped metal flows, it is considered that the Mg-based oxide film on the surface layer does not follow, and as a result, wrinkles and sagging occur.
- the present inventors have intensively studied in order to suppress the difference in fluidity in the hot dip metal during the hot dip coating process while ensuring good corrosion resistance and workability of the hot dip steel material. As a result, the present invention has been completed.
- the hot-dipped steel material according to the present invention is a hot-dipped steel material in which an aluminum / zinc alloy plating layer is plated on the surface of the steel material,
- the aluminum / zinc alloy plating layer contains Al, Zn, Si and Mg as constituent elements, and the Mg content is 0.1 to 10% by mass;
- the aluminum / zinc alloy plating layer contains 0.2 to 15% by volume of Si—Mg phase;
- the mass ratio of Mg in the Si—Mg phase to the total amount of Mg is 3% or more.
- the Mg content is preferably less than 60% by mass in any region having a diameter of 4 mm and a depth of 50 nm in the outermost layer having a depth of 50 nm in the aluminum / zinc alloy plating layer.
- the average value of the Mg content in this region is preferably less than 60% by mass.
- the aluminum / zinc alloy plating layer preferably further contains 0.02 to 1.0 mass% of Cr as a constituent element.
- the Cr content in the outermost layer having a depth of 50 nm in the aluminum / zinc alloy plating layer is preferably in the range of 100 to 500 ppm by mass.
- An alloy layer containing Al and Cr is interposed between the aluminum / zinc alloy plating layer and the steel material, and the mass ratio of Cr in the alloy layer is the Cr content in the aluminum / zinc alloy plating layer.
- the ratio to the mass ratio is preferably in the range of 2-50.
- the ratio of the Si—Mg phase on the surface of the aluminum / zinc alloy plating layer is preferably 30% or less in terms of area ratio.
- the Al content in the aluminum / zinc alloy plating layer is 25 to 75% by mass, Si content is 0.5 to 10% by mass with respect to Al, And the mass ratio of Si: Mg is 100: 50 to 100: 300 It is preferable that
- the aluminum / zinc alloy plating layer preferably further contains 1 to 1000 ppm by mass of Sr as a constituent element.
- the aluminum / zinc alloy plating layer further contains a component composed of at least one of Ti and B as a constituent element in a range of 0.0005 to 0.1% by mass.
- the method for producing a hot dipped steel according to the present invention is as follows. Prepare a hot dipping bath containing the following composition, 25-75% by mass of Al, 0.1 to 10% by mass of Mg, 0.02 to 1.0 mass% of Cr, 0.5-10 mass% Si with respect to Al, 1-1000 ppm by mass of Sr, 0.1 to 1.0 mass% Fe, The balance is Zn, And the mass ratio of Si: Mg is 100: 50 to 100: 300. Pass the steel through this hot dipping bath to attach hot dipped metal to its surface, The hot-dip plated metal is solidified to form an aluminum / zinc alloy plating layer on the surface of the steel material.
- the hot dipping bath further contains 100 to 5000 ppm by mass of Ca.
- the hot dipping bath further contains a component composed of at least one of Ti and B in a range of 0.0005 to 0.1% by mass.
- the temperature of the hot dipping bath it is preferable to maintain the temperature of the hot dipping bath at a temperature not higher than 40 ° C. higher than the solidification start temperature.
- the steel material is drawn from the hot dipping bath into a non-oxidizing atmosphere or a low-oxidizing atmosphere, and subsequently the molten metal in the steel material is melted by gas wiping in the atmosphere before the hot dipped metal adhering to the steel material is solidified. It is preferable to adjust the adhesion amount of the plating metal.
- the method for producing a hot dipped steel according to the present invention is as follows. It is preferable to include a step of keeping the steel material on which the aluminum / zinc alloy plating layer is plated at a heat retention temperature t (° C.) and a heat retention time y (hr) defined by the following formula (1).
- a hot-dip plated steel material that has good corrosion resistance and that suppresses the occurrence of wrinkles on the surface of the plating layer and has a good appearance.
- the hot-dip plated steel material according to this embodiment is formed by plating an aluminum / zinc alloy plating layer (hereinafter referred to as a plating layer) on the surface of the steel material 1.
- a plating layer aluminum / zinc alloy plating layer
- Examples of the steel material 1 include various members such as a thin steel plate, a thick steel plate, a die steel, a steel pipe, and a steel wire. That is, the shape of the steel material 1 is not particularly limited.
- the plating layer is formed by a hot dipping process.
- the plating layer contains Al, Zn, Si, and Mg as constituent elements.
- the Mg content in the plating layer is 0.1 to 10% by mass.
- the corrosion resistance of the surface of the plated layer is improved by Al in particular, and the edge creep at the cut end surface of the hot-dip plated steel material is particularly suppressed by the sacrificial anticorrosive action of Zn, thereby imparting high corrosion resistance to the hot-dip plated steel material.
- excessive alloying between Al in the plating layer and the steel material is suppressed by Si, and an alloy layer (described later) interposed between the plating layer and the steel material is prevented from impairing the workability of the hot-dip plated steel material. Is done.
- the sacrificial anticorrosive action of a plating layer is strengthened by containing Mg which is a base metal rather than Zn, and the corrosion resistance of hot dipped steel is further improved.
- the plating layer contains 0.2 to 15% by volume of Si—Mg phase.
- the Si—Mg phase is a phase composed of an intermetallic compound of Si and Mg, and is dispersed in the plating layer.
- the volume ratio of the Si—Mg phase in the plating layer is equal to the area ratio of the Si—Mg phase in the cut surface when the plating layer is cut in the thickness direction.
- the Si—Mg phase on the cut surface of the plating layer can be clearly confirmed by observation with an electron microscope. Therefore, by measuring the area ratio of the Si—Mg phase on the cut surface, the volume ratio of the Si—Mg phase in the plating layer can be indirectly measured.
- the volume ratio of the Si—Mg phase in the plating layer is higher, the generation of wrinkles in the plating layer is suppressed. This is because, in the process of forming a plating layer by cooling the hot-plated metal during cooling of the hot-dip plated steel material, the Si-Mg phase is in the hot-dip metal before the hot-dip metal is completely solidified. It is considered that this Si—Mg phase precipitates and suppresses the flow of the hot dip metal.
- the volume ratio of the Si—Mg phase is more preferably 0.1 to 20%, further preferably 0.2 to 10%, and particularly preferably 0.4 to 5%.
- the plating layer is composed of a Si—Mg phase and other phases containing Zn and Al.
- the phase containing Zn and Al is mainly composed of an ⁇ -Al phase (dendritic structure) and a Zn—Al—Mg eutectic phase (interdendrite structure).
- Phase containing Zn and Al is more Mg-Zn 2 from configured phases depending on the composition of the plating layer (Mg-Zn 2 phase), and phase from the Si (Si phase), between Fe-Al metal
- Various phases such as a phase composed of a compound (Fe—Al phase) may be included.
- the phase containing Zn and Al occupies a portion excluding the Si—Mg phase in the plating layer.
- the volume ratio of the phase containing Zn and Al in the plating layer is in the range of 99.9 to 60%, preferably in the range of 99.9 to 80%, more preferably in the range of 99.8 to 90%, particularly preferably. Is in the range of 99.6 to 95%.
- the mass ratio of Mg in the Si—Mg phase to the total amount of Mg in the plating layer is 1% by mass or more.
- Mg not contained in the Si—Mg phase is contained in the phase containing Zn and Al.
- Mg is contained in the ⁇ -Al phase, in the Zn-Al-Mg eutectic phase, in the Mg-Zn 2 phase, in the Mg-containing oxide film formed on the plating surface, etc. .
- Mg is contained in the ⁇ -Al phase
- Mg is dissolved in the ⁇ -Al phase.
- the mass ratio of Mg in the Si—Mg phase to the total amount of Mg in the plating layer can be calculated after the Si—Mg phase is regarded as having a stoichiometric composition of Mg 2 Si.
- the Si—Mg phase may contain a small amount of elements such as Al, Zn, Cr, and Fe other than Si and Mg, and the composition ratio of Si and Mg in the Si—Mg phase is also stoichiometric. Although there may be some variation from the composition, it is very difficult to strictly determine the amount of Mg in the Si—Mg phase in consideration of these.
- the mass ratio of Mg in the Si—Mg phase to the total amount of Mg in the plating layer is determined, as described above, the stoichiometric composition of the Si—Mg phase is Mg 2 Si. Is considered to have
- the mass ratio of Mg in the Si—Mg phase to the total amount of Mg in the plating layer can be calculated by the following equation (1).
- R A / (M ⁇ CMG / 100) ⁇ 100 (1)
- R is the mass ratio (% by mass) of Mg in the Si—Mg phase to the total amount of Mg in the plating layer, and A is the Mg content contained in the Si—Mg phase in the plating layer per unit area in plan view of the plating layer.
- the amount (g / m 2 ), M is the mass (g / m 2 ) of the plating layer per unit area of the plating layer in plan view, and CMG is the total Mg content (mass%) in the plating layer. Each is shown.
- A can be calculated from the following equation (2).
- V 2 V 2 ⁇ ⁇ 2 ⁇ ⁇ (2)
- V 2 represents the volume (m 3 / m 2 ) of the Si—Mg phase in the plating layer per unit area in plan view of the plating layer.
- ⁇ 2 indicates the density of the Si—Mg phase, and its value is 1.94 ⁇ 10 6 (g / m 3 ).
- ⁇ represents the mass ratio of Mg in the Si—Mg phase, and its value is 0.63.
- V 2 can be calculated from the following equation (3).
- V 2 V 1 ⁇ R 2 /100 ... (3)
- V 1 represents the total volume (m 3 / m 2 ) of the plating layer per unit area in plan view of the plating layer, and R 2 represents the volume ratio (volume%) of the Si—Mg phase in the plating layer.
- V 1 can be calculated from the following equation (4).
- V 1 M / ⁇ 1 (4) ⁇ 1 indicates the density (g / m 3 ) of the entire plating layer. [rho 1 values can be calculated by the density at room temperature of the constituent elements of the plating layer is a weighted average based on the composition of the plating layer.
- Mg in the plating layer is contained in the Si—Mg phase at a high ratio as described above. For this reason, the amount of Mg present in the surface layer of the plating layer is reduced, thereby suppressing the formation of the Mg-based oxide film on the surface layer of the plating layer. Therefore, wrinkles of the plating layer due to the Mg-based oxide film are suppressed.
- This ratio is more preferably 5% by mass or more, further preferably 20% by mass or more, and particularly preferably 50% by mass or more.
- the upper limit of the ratio of Mg in the Si—Mg phase to the total amount of Mg is not particularly limited, and this ratio may be 100% by mass.
- the Mg content is preferably less than 60% by mass in any region having a diameter of 4 mm and a depth of 50 nm.
- the Mg content in the outermost layer of this plating layer is measured by glow discharge emission spectroscopy (GD-OES: Glow Discharge-Optical EmissionSpectroscopy).
- the Mg content in the outermost layer of the plating layer decreases, wrinkles due to the Mg-based oxide film are suppressed.
- the Mg content is more preferably less than 40% by mass, further preferably less than 20% by mass, and particularly preferably less than 10% by mass.
- the area ratio of the Si—Mg phase on the surface of the plating layer is 30% or less.
- the Si—Mg phase is likely to be formed thin and network-like on the surface of the plating layer.
- the area ratio of this Si—Mg phase is large, the appearance of the plating layer changes.
- the distribution surface of the plating surface of the Si—Mg phase is not uniform, uneven gloss is visually observed on the plating layer. This unevenness of gloss is an appearance defect called sagging.
- the area ratio of the Si—Mg phase on the surface of the plating layer is 30% or less, sagging is suppressed and the appearance of the plating layer is improved.
- the fact that there is little Si—Mg phase on the surface of the plating layer is also effective for maintaining the corrosion resistance of the plating layer over a long period of time.
- the amount of precipitation of the Si—Mg phase in the plating layer relatively increases. Therefore, the amount of Mg inside the plating layer increases, and thereby the sacrificial anticorrosive action of Mg in the plating layer is exhibited over a long period of time, so that the high corrosion resistance of the plating layer is maintained over a long period of time. become.
- the area ratio of the Si—Mg phase on the surface of the plating layer is preferably 20% or less, more preferably 10% or less, 5% or less is particularly preferable.
- the Mg content in the plating layer is in the range of 0.1 to 10% by mass.
- the corrosion resistance of the plating layer is not sufficiently ensured.
- this content exceeds 10% by mass, not only the effect of improving the corrosion resistance is saturated, but also dross is likely to occur in the hot dipping bath during the production of hot dipped steel.
- the Mg content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more.
- the Mg content is particularly preferably 5.0% by mass or less, and more preferably 3.0% by mass or less.
- the Mg content is particularly preferably in the range of 1.0 to 3.0% by mass.
- the content of Al in the plating layer is preferably in the range of 25 to 75% by mass. If this content is 25% by mass or more, the Zn content in the plating layer does not become excessive, and the corrosion resistance on the surface of the plating layer is sufficiently ensured. When this content is 75% by mass or less, the sacrificial anticorrosive effect by Zn is sufficiently exhibited, and the hardened plated layer is suppressed, and the bending workability of the hot-dip plated steel material is improved. Furthermore, the content of Al is preferably 75% by mass or less from the viewpoint of further suppressing wrinkling of the plating layer by preventing the fluidity of the hot-dip plated metal from becoming excessively low during the production of hot-dip plated steel. .
- the Al content is particularly preferably 45% by mass or more.
- the Al content is particularly preferably 65% by mass or less. It is particularly preferable if the Al content is in the range of 45 to 65% by mass.
- the Si content in the plating layer is preferably in the range of 0.5 to 10% by mass with respect to the Al content.
- the Si content is particularly preferably 1.0% by mass or more.
- the Si content is particularly preferably 5.0% by mass or less.
- the Si content is particularly preferably in the range of 1.0 to 5.0% by mass.
- the mass ratio of Si: Mg in the plating layer is preferably in the range of 100: 50 to 100: 300. In this case, the formation of the Si—Mg layer in the plating layer is particularly accelerated, and the generation of wrinkles in the plating layer is further suppressed.
- the mass ratio of Si: Mg is preferably 100: 70 to 100: 250, more preferably 100: 100 to 100: 200.
- the plating layer preferably further contains Cr as a constituent element.
- Cr as a constituent element.
- the growth of the Si—Mg phase in the plating layer is promoted by Cr, the volume ratio of the Si—Mg phase in the plating layer is increased, and the amount of Mg in the Si—Mg phase with respect to the total amount of Mg in the plating layer is increased. The ratio is high. Thereby, wrinkles of the plating layer are further suppressed.
- the Cr content in the plating layer is preferably in the range of 0.02 to 1.0 mass%. When the Cr content in the plating layer exceeds 1.0 mass%, not only the action is saturated, but also dross is likely to occur in the hot dipping bath 2 during the production of hot dipped steel.
- the Cr content is particularly preferably 0.05% by mass or more.
- the Cr content is particularly preferably 0.5% by mass or less.
- the Cr content is preferably in the range of 0.07 to 0.2% by mass.
- the content of Cr in the outermost layer having a depth of 50 nm in the plating layer is preferably 100 to 500 ppm by mass. In this case, the corrosion resistance of the plating layer is further improved. This is presumably because, when Cr is present in the outermost layer, a passive film is formed on the plating layer, which suppresses anodic dissolution of the plating layer.
- the Cr content is preferably 150 to 450 ppm by mass, more preferably 200 to 400 ppm by mass.
- An alloy layer containing Al and Cr is preferably interposed between the plating layer and the steel material.
- the alloy layer is regarded as a layer different from the plating layer.
- the alloy layer may contain various metal elements such as Mn, Fe, Co, Ni, Cu, Zn, and Sn in addition to Al and Cr as constituent elements.
- the Cr in the alloy layer promotes the growth of the Si—Mg phase in the plating layer, the volume ratio of the Si—Mg phase in the plating layer increases, and the Mg in the plating layer increases. The ratio of Mg in the Si—Mg phase with respect to the total amount is increased. Thereby, wrinkles and sagging of the plating layer are further suppressed.
- the ratio of the Cr content in the alloy layer to the Cr content in the plating layer is preferably 2 to 50.
- the growth of the Si—Mg phase is promoted in the vicinity of the alloy layer in the plating layer, so that the area ratio of the Si—Mg phase on the surface of the plating layer is reduced, and thus sagging is further suppressed.
- the corrosion resistance of the plating layer is maintained for a longer period.
- the ratio of the Cr content in the alloy layer to the Cr content in the plating layer is preferably 3 to 40, more preferably 4 to 25.
- the amount of Cr in the alloy layer is determined by analyzing the cross section of the plating layer with an energy dispersive X-ray analyzer (EDS). Can be derived by measuring using.
- EDS energy dispersive X-ray analyzer
- the thickness of the alloy layer is preferably in the range of 0.05 to 5 ⁇ m. If this thickness is 0.05 ⁇ m or more, the above-described action by the alloy layer is effectively exhibited. When the thickness is 5 ⁇ m or less, the workability of the hot-dip plated steel material is hardly impaired by the alloy layer.
- the corrosion resistance after bending deformation of the plating layer is also improved.
- the reason is considered as follows.
- cracks may occur in the plating layer and the coating film on the plating layer. At that time, water and oxygen enter the plating layer through the crack, and the alloy in the plating layer is directly exposed to the corrosion factor.
- Cr present in the plating layer, particularly in the surface layer, and Cr present in the alloy layer suppress the corrosion reaction of the plating layer, thereby suppressing the expansion of corrosion starting from cracks.
- the content of Cr in the outermost layer having a depth of 50 nm in the plated layer is preferably 300 ppm by mass or more, particularly 200 to 400 ppm by mass. It is preferable that it is the range of these. Further, in order to particularly improve the corrosion resistance of the plated layer after bending deformation, the ratio of the Cr content in the alloy layer to the Cr content in the plated layer is preferably 20 or more, particularly 20 A range of from 30 to 30 is preferable.
- the plating layer preferably further contains Sr as a constituent element.
- Sr as a constituent element.
- the formation of the Si—Mg layer in the plating layer is particularly promoted by Sr.
- the formation of Mg-based oxide film on the surface layer of the plating layer is suppressed by Sr. This is considered to be because the Sr oxide film is more preferentially formed than the Mg-based oxide film, thereby inhibiting the formation of the Mg-based oxide film. Thereby, generation
- the Sr content in the plating layer is preferably in the range of 1 to 1000 ppm by mass. If the Sr content is less than 1 ppm by mass, the above-described effects will not be exhibited.
- the Sr content is particularly preferably 5 ppm by mass or more.
- the Sr content is particularly preferably 500 ppm by mass or less, and more preferably 300 ppm by mass or less.
- the Sr content is preferably in the range of 20 to 50 ppm by mass.
- the plating layer preferably further contains Fe as a constituent element.
- Fe contributes to the refinement of the microstructure and spangle structure of the plating layer, thereby improving the appearance and workability of the plating layer.
- the Fe content in the plating layer is preferably in the range of 0.1 to 0.6% by mass. When the Fe content is less than 0.1% by mass, the microstructure and spangle structure of the plating layer are coarsened to deteriorate the appearance of the plating layer and the workability.
- the Fe content is particularly preferably 0.2% by mass or more.
- the Fe content is particularly preferably 0.5% by mass or less. It is particularly preferable if the Fe content is in the range of 0.2 to 0.5 mass%.
- the plating layer may further contain an element selected from alkaline earth elements, Sc, Y, lanthanoid elements, Ti and B as constituent elements.
- Alkaline earth elements Be, Ca, Ba, Ra
- Sc Y
- lanthanoid elements La, Ce, Pr, Nd, Pm, Sm, Eu, etc.
- the total content of these components in the plating layer is preferably 1.0% by mass or less in terms of mass ratio.
- the ⁇ -Al phase (dendritic structure) of the plating layer is refined, so that the spangle is refined, thereby improving the appearance of the plated layer by the spangle. Further, the generation of wrinkles in the plating layer is further suppressed by at least one of Ti and B. This is because the Si-Mg phase is also refined by the action of Ti and B, and this refined Si-Mg phase effectively flows the hot-dip metal in the process where the hot-dip metal is solidified to form a plating layer. It is thought that it is to suppress.
- the refinement of the plating structure reduces the concentration of stress in the plating layer during bending, thereby suppressing the occurrence of large cracks and the like, and further improving the bending workability of the plating layer.
- the total content of Ti and B in the hot dipping bath 2 is preferably in the range of 0.0005 to 0.1% by mass.
- the total content of Ti and B is particularly preferably 0.001% by mass or more.
- the total content of Ti and B is particularly preferably 0.05% by mass or less.
- the total content of Ti and B is particularly preferably in the range of 0.001 to 0.05% by mass.
- Zn occupies the remainder excluding constituent elements other than Zn among the constituent elements of the plating layer.
- the plating layer does not contain an element other than the above as a constituent element.
- the plating layer contains only Al, Zn, Si, Mg, Cr, Sr, and Fe as constituent elements, or Al, Zn, Si, Mg, Cr, Sr, and Fe, and alkaline earth elements. It is preferable that only elements selected from Sc, Y, lanthanoid elements, Ti and B are contained as constituent elements.
- the plating layer may contain inevitable impurities such as Pb, Cd, Cu, and Mn.
- the content of the inevitable impurities is preferably as small as possible, and the total content of the inevitable impurities is particularly preferably 1% by mass or less with respect to the plating layer.
- a hot dipping bath having a composition that matches the composition of the constituent elements of the plating layer is prepared during the production of the hot dipped steel.
- an alloy layer is formed between the steel material and the plating layer by the hot dipping process, the variation in the composition is negligibly small.
- a hot dipping bath containing 1-1000 mass ppm Sr, 0.1-1.0 mass% Fe, and Zn is prepared.
- Zn occupies the remainder excluding components other than Zn out of all components in the hot dipping bath.
- the mass ratio of Si: Mg in the hot dipping bath is preferably in the range of 100: 50 to 100: 300.
- the hot dipping bath may further contain a component selected from an alkaline earth element, Sc, Y, a lanthanoid element, Ti, and B. These components are contained in the hot dipping bath 2 as necessary.
- the total content of alkaline earth elements (Be, Ca, Ba, Ra), Sc, Y, and lanthanoid elements (La, Ce, Pr, Nd, Pm, Sm, Eu, etc.) in the hot dipping bath 2 is The mass ratio is preferably 1.0% or less.
- the hot dipping bath 2 contains a component composed of at least one of Ti and B
- the total content of Ti and B in the hot dipping bath 2 is in the range of 0.0005 to 0.1% by mass ratio. It is preferable.
- the hot dipping bath does not contain components other than those described above.
- the hot dipping bath preferably contains only Al, Zn, Si, Mg, Cr, Sr, and Fe. It is also preferable that the hot dipping bath contains only elements selected from Al, Zn, Si, Mg, Cr, Sr, and Fe, and alkaline earth elements, Sc, Y, lanthanoid elements, Ti, and B.
- the hot dipping bath 2 is preferably 25 to 75% Al, 0.02 to 1.0% Cr, and 0.5 to 0.5% Si relative to Al. 10%, Mg 0.1-0.5%, Fe 0.1-0.6%, Sr in the range of 1-500 ppm, or further from alkaline earth elements, lanthanoid elements, Ti and B It is preferable that the selected component is contained and the balance is Zn.
- the hot dipping bath may contain inevitable impurities such as Pb, Cd, Cu, and Mn.
- the content of the inevitable impurities is preferably as small as possible.
- the total content of the inevitable impurities is preferably 1% by mass or less with respect to the hot dipping bath.
- the corrosion resistance of the surface of the plating layer is improved by Al in particular, and the sacrificial anticorrosive action by Zn is particularly effective for the hot-dip plating steel material. Edge creep at the cut end face is suppressed, and high corrosion resistance is imparted to the hot dipped steel.
- the sacrifice of the sacrificial anticorrosion action of the plating layer is further strengthened and the corrosion resistance of the hot dip plated steel material is further improved by containing Mg which is a base metal than Zn.
- the ⁇ -Al phase first precipitates as primary crystals and grows in a dendritic form.
- the Mg and Si concentrations in the remaining hot-dipped metal that is, in the components that are not yet solidified in the hot-dipped metal
- Si—Mg phase Si-containing phase
- This Si—Mg phase is a phase composed of an alloy of Mg and Si as described above.
- This Si—Mg phase is promoted by Cr, Fe and Sr.
- Mg in the hot-dipped metal By incorporating Mg in the hot-dipped metal into the Si—Mg phase, the movement of Mg to the surface layer of the hot-dipped metal is inhibited, and the concentration of Mg in the surface layer of the hot-dipped metal is suppressed.
- Sr in the hot dipped metal also contributes to suppression of Mg concentration. This is because, in hot-dip plated metal, Sr is an element that is easily oxidized like Mg, so Sr forms an oxide film on the plating surface competitively with Mg, and as a result, formation of an Mg-based oxide film is suppressed. This is probably because of this.
- the Si—Mg phase solidifies and grows in the remaining hot dip metal other than the ⁇ -Al phase which is the primary crystal, so that the hot dip metal becomes a solid-liquid mixed phase. As a result, the generation of wrinkles on the surface of the plating layer is suppressed.
- Fe is important in controlling the microstructure and spangle of the plating layer. The reason why Fe affects the structure of the plating layer is not necessarily clear at the present time, but Fe is alloyed with Si in the hot-dip metal, and this alloy becomes a solidification nucleus during solidification of the hot-dip metal. Conceivable.
- Sr is a base element like Mg
- the sacrificial anticorrosive action of the plating layer is further strengthened by Sr, and the corrosion resistance of the hot dipped steel is further improved.
- Sr also exerts an action of suppressing the acicular formation of the Si phase and Si—Mg phase precipitates. For this reason, the Si phase and the Si—Mg phase are spheroidized, and the occurrence of cracks in the plating layer is suppressed.
- an alloy layer containing a part of Al in the hot dip metal is also formed between the plating layer and the steel material 1.
- an Fe—Al alloy layer mainly composed of Al in the plating bath and Fe in the steel material 1 is formed.
- pre-plating described later is applied to the steel material 1, an alloy layer containing Al in the plating bath and part or all of the constituent elements of the pre-plating, or further containing Fe in the steel material 1 is formed.
- the alloy layer further contains Cr as a constituent element together with Al.
- the alloy layer is made of Si, Mn, Fe, Co, Ni, Cu, Zn, Sn, etc. as constituent elements depending on the composition of the plating bath, the presence or absence of pre-plating, the composition of the steel material 1, and the like. Various metal elements can be contained.
- the alloy layer a part of Cr in the hot dipped metal is contained at a higher concentration than in the plated layer.
- the growth of the Si—Mg phase in the plating layer is promoted by the Cr in the alloy layer, the volume ratio of the Si—Mg phase in the plating layer is increased, and the plating layer The ratio of Mg in the Si—Mg phase to the total amount of Mg becomes higher. Thereby, wrinkles of the plating layer are further suppressed.
- the corrosion resistance of the hot-dip plated steel material is further improved by forming the alloy layer.
- the ratio of the Cr content in the alloy layer to the Cr content in the plating layer is preferably 2 to 50.
- the ratio of the Cr content in the alloy layer to the Cr content in the plating layer is preferably 3 to 40, more preferably 4 to 25.
- the amount of Cr in the alloy layer can be derived by measuring the cross section of the plating layer using an energy dispersive X-ray analyzer (EDS).
- the thickness of the alloy layer is preferably in the range of 0.05 to 5 ⁇ m. When the thickness of the alloy layer is within the above range, the corrosion resistance of the hot-dip plated steel material is sufficiently improved and the workability is also sufficiently improved.
- the Cr concentration is maintained within a certain range near the surface, and accordingly, the corrosion resistance of the plating layer is further improved.
- the reason for this is not clear, but it is presumed that a composite oxide film is formed near the surface of the plating layer by combining Cr with oxygen.
- the content of Cr in the outermost layer having a depth of 50 nm in the plating layer is preferably 100 to 500 ppm by mass.
- the corrosion resistance after bending deformation of the plating layer is also improved.
- the reason is considered as follows. When subjected to severe bending deformation, cracks may occur in the plating layer and the coating film on the plating layer. At that time, water and oxygen enter the plating layer through the crack, and the alloy in the plating layer is directly exposed to the corrosion factor.
- Cr present in the plating layer, particularly in the surface layer, and Cr present in the alloy layer suppress the corrosion reaction of the plating layer, thereby suppressing the expansion of corrosion starting from cracks.
- the hot-dip plated metal treated in the preferred embodiment is a multi-component molten metal containing elements of seven or more components, and its solidification process is extremely complicated and difficult to predict theoretically.
- the Al content in the hot dipping bath 2 is less than 25%, the Zn content in the plating layer becomes excessive, the corrosion resistance on the surface of the plating layer becomes insufficient, and the content exceeds 75%.
- the sacrificial anticorrosive effect due to Zn is lowered, and the plating layer is hardened, and the bending workability of the hot-dip plated steel material is lowered.
- the content is more than 75%, the fluidity of the hot-dip plated metal is increased, and wrinkles may be generated in the plating layer.
- the Al content is particularly preferably 45% or more.
- the Al content is particularly preferably 65% or less. In particular, the Al content is preferably in the range of 45 to 65%.
- the Cr content in the hot dipping bath 2 is less than 0.02%, it is difficult to sufficiently secure the corrosion resistance of the plating layer, and it is difficult to sufficiently suppress wrinkles and sagging of the plating layer. If it exceeds 0.0%, not only the corrosion resistance improving action is saturated, but also dross is likely to occur in the hot dipping bath 2.
- the Cr content is particularly preferably 0.05% or more.
- the Cr content is particularly preferably 0.5% or less.
- the Cr content is preferably in the range of 0.07 to 0.2%.
- the Si content is particularly preferably 1.0% or more.
- the Si content is particularly preferably 5.0% or less. Further, the Si content is preferably in the range of 1.0 to 5.0%.
- the Mg content in the hot dip plating bath 2 is less than 0.1%, the corrosion resistance of the plating layer will not be sufficiently secured, and if this content exceeds 10%, the corrosion resistance improving action will be saturated. Dross is likely to occur in the hot dipping bath 2.
- the Mg content is preferably 0.5% or more, and more preferably 1.0% or more. Further, the Mg content is particularly preferably 5.0% or less, and more preferably 3.0% or less. In particular, the Mg content is preferably in the range of 1.0 to 3.0%.
- the content of Fe in the hot dipping bath 2 is less than 0.1%, the microstructure and spangle structure of the plating layer may be coarsened, and the appearance of the plating layer may be deteriorated and workability may be deteriorated. If it exceeds 0.6%, spangles in the plating layer become too fine or disappear, and the appearance is not improved by spangles, and dross is likely to occur in the hot dipping bath 2.
- the Fe content is particularly preferably 0.2% or more.
- the Fe content is particularly preferably 0.5% or less. In particular, the Fe content is preferably in the range of 0.2 to 0.5%.
- the Sr content is particularly preferably 5 ppm or more.
- the Sr content is particularly preferably 300 ppm or less.
- the Sr content is preferably in the range of 20 to 50 ppm.
- the hot dipping bath 2 contains a component selected from alkaline earth elements and lanthanoid elements, alkaline earth elements (Be, Ca, Ba, Ra), Sc, Y, and lanthanoid elements (La, Ce, Pr, Nd, Pm, Sm, Eu, etc.) exhibit the same action as Sr.
- alkaline earth elements Be, Ca, Ba, Ra
- Sc Sc
- Y lanthanoid elements
- La Ce, Pr, Nd, Pm, Sm, Eu, etc.
- the total content of these components in the hot dipping bath 2 is preferably 1.0% or less.
- the hot dipping bath 2 contains Ca in particular, the generation of dross in the hot dipping bath is remarkably suppressed.
- the hot dipping bath contains Mg, it is unavoidable that some dross is generated even if the Mg content is 10% by mass or less.
- the hot dipping bath further contains Ca, generation of dross due to Mg is remarkably suppressed. This further suppresses deterioration of the appearance of the hot dipped steel material due to dross and reduces the effort required to remove dross from the hot dipping bath.
- the Ca content in the hot dipping bath 2 is preferably in the range of 100 to 5000 ppm by mass.
- the spangle of the plating layer is refined due to the refinement of the ⁇ -Al phase (dendritic structure) of the plating layer.
- the appearance is improved.
- the generation of wrinkles in the plating layer is further suppressed.
- the Si-Mg phase is also refined by the action of Ti and B, and this refined Si-Mg phase effectively flows the hot-dip metal in the process where the hot-dip metal is solidified to form a plating layer. It is thought that it is to suppress.
- the refinement of the plating structure reduces the concentration of stress in the plating layer during bending, thereby suppressing the occurrence of large cracks and the like, thereby further improving bending workability.
- the total content of Ti and B in the hot dipping bath 2 is preferably in the range of 0.0005 to 0.1% by mass ratio.
- the total content of Ti and B is particularly preferably 0.001% or more.
- the total content of Ti and B is particularly preferably 0.05% or less.
- the total content of Ti and B is preferably in the range of 0.001 to 0.05%.
- a plating layer is formed by a hot dipping process using such a hot dipping bath 2.
- the concentration of Mg in the surface layer is suppressed as described above.
- the Mg content is preferably less than 60% by mass in any region having a diameter of 4 mm and a depth of 50 nm in the outermost layer having a depth of 50 nm in the plating layer.
- the amount of the Mg-based oxide film in the outermost layer of the plating layer is particularly reduced, and wrinkles due to the Mg-based oxide film are further suppressed.
- wrinkles due to the Mg-based oxide film are suppressed.
- the Mg content is more preferably less than 40% by mass, even more preferably less than 20% by mass, and particularly preferably less than 10% by mass.
- the portion where the Mg content is 60% by mass or more is preferably absent, and it is preferable that the portion where the Mg content is 40% by mass or more is not present, It is more preferable if there is no portion where the Mg content is 20% by mass or more.
- the physical meaning of Mg content will be described.
- the Mg content in the stoichiometric MgO oxide is about 60% by mass. That is, when the Mg content is less than 60% by mass, the stoichiometric MgO (MgO single oxide film) does not exist in the outermost layer of the plating layer, or the formation of MgO having this stoichiometric composition is not possible. It means that it is remarkably suppressed. In this embodiment, excessive oxidation of Mg in the outermost layer of the plating layer is suppressed, whereby formation of an oxide film of MgO alone is suppressed.
- a composite oxide containing a small amount or a large amount of an oxide of an element other than Mg such as Al, Zn, Sr, etc. is formed, so that the Mg content in the surface layer of the plating layer is relatively lowered. it seems to do.
- the Mg content in the outermost layer of the plating layer can be analyzed using a glow discharge emission spectrometer (Glow Discharge spectrometer).
- glow discharge emission spectrometer Glow Discharge spectrometer
- the oxide film of MgO alone should not be recognized in the outermost layer of the plating layer by comparing the concentration curves of multiple elements contained in the plating layer Please confirm.
- the volume ratio of the Si—Mg phase in the plating layer is preferably in the range of 0.2 to 15% by volume.
- the volume ratio of the Si—Mg phase is more preferably 0.2 to 10%, further preferably 0.3 to 8%, and particularly preferably 0.4 to 5%.
- the steepness is a value defined by (height of the ridge ( ⁇ m)) ⁇ (width of the bottom of the ridge ( ⁇ m)).
- the bottom surface of the ridge is a portion where a virtual plane including a flat surface around the ridge and the ridge intersect.
- the height of the ridge is the height from the bottom of the ridge to the tip of the ridge.
- the hot-dip plating steel material can exhibit the further outstanding corrosion resistance etc. by the chemical conversion treatment layer and the coating-film layer.
- the adjustment of the degree of concentration of Mg, the state of the Si—Mg phase, the thickness of the alloy layer, and the steepness of the bulge on the surface of the plating layer is performed by hot dip plating using the hot dip plating bath 2 having the above composition on the steel material 1. It can be achieved by applying a treatment.
- the steel material 1 on which a pre-plating layer containing at least one component selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, and Sn is formed is used to form a plating layer.
- a hot dipping process may be performed.
- a pre-plating layer is formed on the surface of the steel sheet 1 by performing a pre-plating process on the steel material 1 before being subjected to the hot dipping process. This pre-plated layer improves the wettability between the steel material 1 and the hot-dip plated metal during the hot-dipping process, and improves the adhesion between the steel material 1 and the plated layer.
- the pre-plating layer depends on the type of metal constituting the pre-plating layer, but also contributes to further improvement of the surface appearance and corrosion resistance of the plating layer. For example, when a pre-plated layer containing Cr is formed, formation of an alloy layer containing Cr is promoted between the steel material 1 and the plated layer, and the corrosion resistance of the hot-dip plated steel material is further improved. For example, when a pre-plated layer containing Fe or Ni is formed, the wettability between the steel material 1 and the hot-dip plated metal is improved, the adhesion of the plated layer is greatly improved, and the precipitation of the Si—Mg phase is further promoted. Further, the surface appearance of the plating layer is further improved. The acceleration of precipitation of the Si—Mg phase is considered to occur due to the reaction between the pre-plated layer and the hot-dip plated metal.
- the adhesion amount of the pre-plated layer is not particularly limited, but the adhesion amount on one surface of the steel material 1 is preferably in the range of 0.1 to 3 g / m 2 . If this adhesion amount is less than 0.1 g / m 2 , it is difficult to cover the steel surface with the pre-plating layer, and the improvement effect by the pre-plating is not sufficiently exhibited. Moreover, when this adhesion amount exceeds 3 g / m ⁇ 2 >, not only the improvement effect is saturated but also the manufacturing cost becomes high.
- the steel material 1 to be treated is a member made of steel such as carbon steel, alloy steel, stainless steel, nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, manganese steel.
- Examples of the steel material 1 include various members such as a thin steel plate, a thick steel plate, a die steel, a steel pipe, and a steel wire. That is, the shape of the steel material 1 is not particularly limited.
- the steel material 1 may be subjected to a flux treatment before the hot dipping treatment.
- a flux treatment By this flux treatment, the wettability and adhesion of the steel material 1 to the hot dipping bath 2 can be improved.
- the steel material 1 may be subjected to a heat annealing / reduction treatment before being immersed in the hot dipping bath 2, or this treatment may be omitted. As described above, the steel material 1 may be pre-plated before the hot dipping process.
- the transport device includes a feeder 3, a winder 12, and a plurality of transport rolls 15.
- the feeder 3 holds the coil 13 (first coil 13) of the long steel plate 1a.
- the first coil 13 is unwound by the feeding machine 3, and the steel plate 1 a is conveyed to the winder 12 while being supported by the conveyance roll 15. Further, the winder 12 winds the steel plate 1a, and the winder 12 holds the coil 12 (second coil 12) of the steel plate 1a.
- the heating furnace 4 heats the steel plate 1a.
- the heating furnace 4 is constituted by a non-oxidizing furnace or the like.
- the annealing / cooling unit 5 heat-anneales the steel sheet 1a and subsequently cools it.
- the annealing / cooling section 5 is connected to the heating furnace 4, and an annealing furnace is provided on the upstream side, and a cooling zone (cooler) is provided on the downstream side.
- the annealing / cooling section 5 is maintained in a reducing atmosphere.
- the snout 6 is a cylindrical member in which the steel plate 1 a is conveyed. One end of the snout 6 is connected to the annealing / cooling unit 5 and the other end is disposed in the hot dipping bath 2 in the pot 7. The inside of the snout 6 is maintained in a reducing atmosphere as in the annealing / cooling section 5.
- the pot 7 is a container for storing the hot dipping bath 2, and a sink roll 8 is disposed therein.
- the injection nozzle 9 injects gas toward the steel plate 1a.
- the injection nozzle 9 is disposed above the pot 7.
- the injection nozzle 9 is disposed at a position where gas can be injected toward both surfaces of the steel plate 1 a pulled up from the pot 7.
- the cooling device 10 cools the hot dip plated metal adhering to the steel plate.
- an air cooler, a mist cooler, or the like is provided, and the steel plate 1 a is cooled by the cooling device 10.
- the temper rolling / shape correcting device 11 performs temper rolling and shape correction of the steel sheet 1a on which the plating layer is formed.
- the temper rolling / shape correcting device 11 includes a skin pass mill for performing temper rolling on the steel plate 1a, a tension leveler for performing shape correction on the steel plate 1a after temper rolling, and the like.
- the steel plate 1a is first unwound from the paying machine 3 and continuously drawn. After this steel plate 1a is heated in the heating furnace 4, it is transferred to the annealing / cooling section 5 in a reducing atmosphere and simultaneously annealed in the annealing furnace, and at the same time, removing rolling oil or the like adhering to the surface of the steel plate 1a. Then, after the surface is cleaned, such as reduction and removal of the oxide film, it is cooled in a cooling zone. Next, the steel plate 1 a passes through the snout 6 and further enters the pot 7 and is immersed in the hot dipping bath 2 in the pot 7. The steel plate 1a is supported by the sink roll 8 in the pot 7 so that its conveying direction is changed upward, and is drawn out from the hot dipping bath 2. Thereby, the hot dip metal adheres to the steel plate 1a.
- the amount of adhesion of the hot dipped metal adhering to the steel plate 1a is adjusted by injecting gas from the injection nozzle 9 onto both surfaces of the steel plate 1a.
- a gas wiping method Such a method for adjusting the amount of adhesion by gas injection is called a gas wiping method.
- the adhesion amount of the hot dip metal is preferably adjusted in the range of 40 to 200 g / m 2 on both sides of the steel plate 1a.
- Examples of the type of gas (wiping gas) injected into the steel sheet 1a in the gas wiping method include air, nitrogen, argon, helium, and water vapor. These wiping gases may be preheated and then injected to the steel sheet 1a.
- the hot dipping bath 2 having a specific composition by using the hot dipping bath 2 having a specific composition, the surface oxidation concentration of Mg in the hot dipped metal (oxidation of Mg on the surface of the hot dipped metal and an increase in the Mg concentration) is essentially suppressed. The Therefore, even if oxygen is included in the wiping gas or oxygen is included in the air flow accompanying the injection of the wiping gas, the plating adhesion amount (deposited on the steel plate 1a does not deteriorate the effect of the invention). It is possible to adjust the amount of hot-dip plated metal).
- the method for adjusting the plating adhesion amount is of course not limited to the gas wiping method, and various adhesion amount control methods can be applied.
- Examples of the adhesion amount control method other than the gas wiping method include a roll drawing method in which the steel plate 1a is passed between a pair of rolls arranged immediately above the bath surface of the hot dipping bath 2, and a steel plate 1a drawn from the hot dipping bath 2.
- a method of adjusting the plating adhesion amount by using natural gravity drop without applying external force Two or more plating adhesion amount adjusting methods may be combined.
- the steel plate 1a is transported further upward than the position where the injection nozzle 9 is disposed, and then supported by two transport rolls 15 so as to be folded downward. That is, the steel plate 1a is conveyed along an inverted U-shaped path. In this inverted U-shaped path, the steel plate 1a is cooled by the cooling device 10 by air cooling, mist cooling, or the like. Thereby, the hot dip plating metal adhering on the surface of the steel plate 1a solidifies, and a plating layer is formed.
- the cooling device 10 In order to complete the solidification of the hot dipped metal by being cooled by the cooling device 10, until the surface temperature of the hot dipped metal (or plating layer) reaches 300 ° C. or less by the cooling device 10 on the steel plate 1 a. Preferably it is cooled.
- the surface temperature of the hot dip metal is measured with a radiation thermometer, for example.
- the cooling rate from when the steel plate 1a is drawn from the plating bath 2 to when the surface of the hot-dip plated metal on the steel plate 1a is cooled to 300 ° C. is 5 to 5.
- the range is preferably 100 ° C./sec.
- the cooling device 10 has a temperature control function for adjusting the temperature of the steel plate 1a along the conveying direction and the plate width direction.
- the cooling device 10 may be divided into a plurality along the conveying direction of the steel plate 1a.
- a primary cooling device 101 that cools the steel plate 1 a in a path that is transported further upward than the arrangement position of the injection nozzle 9, and a secondary cooling device 102 that cools the steel plate 1 a on the downstream side of the primary cooling device 101. And are provided.
- the primary cooling device 101 and the secondary cooling device 102 may be further divided into a plurality.
- the primary cooling device 101 cools the steel plate 1a until the surface of the hot-dip metal reaches 300 ° C. or lower, and the secondary cooling device 102 further heats the steel plate 1a to the temper rolling / shape correcting device 11.
- the hot dip plated metal while the surface temperature of the hot dip metal on the steel plate 1a is 500 ° C. or higher.
- the surface cooling rate is preferably 50 ° C./sec or less. In this case, the precipitation of the Si—Mg phase on the surface of the plating layer is particularly suppressed, so that the occurrence of sagging is suppressed.
- the cooling rate in this temperature range is more preferably 40 ° C./sec or less, and particularly preferably 35 ° C./sec or less.
- the steel sheet 1a after cooling is subjected to temper rolling by the temper rolling / shape correcting device 11 and then subjected to shape correction.
- the rolling reduction by temper rolling is preferably in the range of 0.3 to 3%. It is preferable that the elongation rate of the steel sheet 1a by shape correction is 3% or less.
- the steel plate 1a is wound up by the winder 12, and the coil 14 of the steel plate 1a is held by the winder 12.
- the temperature of the hot dipping bath 2 in the pot 7 is a temperature not higher than the solidification start temperature of the hot dipping bath 2 and 40 ° C. higher than the start solidification temperature. Is preferred. More preferably, the temperature of the hot dipping bath 2 in the pot 7 is not higher than the solidification start temperature of the hot dipping bath 2 and not more than 25 ° C. higher than the start of solidification temperature.
- the upper limit of the temperature of the hot dipping bath 2 is limited in this way, the time required for the hot dipped metal adhering to the steel plate 1a to solidify after the steel plate 1a is drawn from the hot dipping bath 2 is shortened. .
- the time during which the hot-dip plated metal adhering to the steel plate 1a is in a flowable state is also shortened, so that wrinkles are less likely to occur in the plated layer. If the temperature of the hot dipping bath 2 is not higher than 20 ° C. higher than the solidification start temperature of the hot dipping bath 2, the generation of wrinkles in the plating layer is remarkably suppressed.
- the steel plate 1a When the steel plate 1a is drawn out from the hot dipping bath 2, it may be drawn into a non-oxidizing atmosphere or a low-oxidizing atmosphere, and gas is further applied to the steel plate 1a in this non-oxidizing atmosphere or low-oxidizing atmosphere. Adjustment of the adhesion amount of the hot dip metal by the wiping method may be performed.
- the steel material 1 drawn from the hot dipping bath 2 has a transport path upstream of the hot dipping bath 2 (a transport path going upward from the hot dipping bath 2). It is preferable that the hollow member 22 is surrounded and the inside of the hollow member 22 is filled with a non-oxidizing gas such as nitrogen gas or a low oxidizing gas.
- a non-oxidizing gas or a low oxidizing gas means a gas having a lower oxygen concentration than the atmosphere.
- the oxygen concentration of the non-oxidizing gas or the low oxidizing gas is preferably 1000 ppm or less.
- the atmosphere filled with the non-oxidizing gas or the low-oxidizing gas is the non-oxidizing atmosphere or the low-oxidizing atmosphere, and the oxidation reaction is suppressed in this atmosphere.
- the injection nozzle 9 is disposed inside the hollow member 22.
- the hollow member 22 is provided so as to surround the conveyance path of the steel material 1 from the inside of the hot dipping bath 2 (upper part of the hot dipping bath 2) to the upper side of the hot dipping bath 2.
- the gas injected from the injection nozzle 9 is also preferably a non-oxidizing gas such as nitrogen gas or a low oxidizing gas.
- a non-oxidizing gas such as nitrogen gas or a low oxidizing gas.
- an overaging treatment is further applied to the steel plate 1a after the hot dipping treatment.
- the overaging treatment is performed by holding the steel sheet 1a within a certain temperature range for a certain time.
- FIG. 3 shows an apparatus used for the overaging treatment, among which FIG. 3 (a) shows a heating apparatus and FIG. 3 (b) shows a heat retaining container 20.
- a heating apparatus is provided with the conveying apparatus with which the steel plate 1a after a hot dipping process is conveyed continuously. Similar to the conveying device in the hot dipping treatment apparatus, the conveying device includes a feeding machine 16, a winder 17, and a plurality of conveying rolls 21.
- a heating furnace 18 such as an induction heating furnace is provided in the transport path of the steel plate 1a by the transport device.
- the heat retaining container 20 is not particularly limited as long as it can hold the coil 19 of the steel plate 1a and has heat insulation.
- the heat retaining container 20 may be a large container (a warming chamber).
- the coil 14 of the steel plate 1a after the hot dipping treatment is first transported from the winder 12 of the hot dipping treatment device by a crane, a carriage, or the like, and the heating device 16 is fed. Retained. In the heating device, the steel plate 1a is first unwound from the feeder 16 and continuously fed out. The steel plate 1a is heated to a temperature suitable for the overaging treatment in the heating furnace 18, and then wound up by the winder 17, and the coil 19 of the steel plate 1a is held by the winder 17.
- the coil 19 of the steel plate 1a is transported from the winder 17 by a crane, a carriage or the like and held in the heat retaining container 20. Since the coil 19 of the steel plate 1a is held in the heat retaining container 20 for a certain period of time, the overaging treatment is performed on the steel plate 1a.
- the plating layer formed on the surface of the steel sheet 1a according to the present embodiment contains Mg and a slight amount of Mg-based oxide film exists on the surface of the plating layer, the plating layer in the coil of the steel sheet 1a during overaging treatment. Even if they are overlapped, seizure and welding hardly occur between the plating layers. For this reason, even if the heat retention time at the time of the overaging treatment is long, or even if the heat retention temperature is high, seizure hardly occurs, and sufficient overaging treatment can be performed on the steel sheet 1a. This greatly improves the workability of the hot-dip galvanized steel sheet and improves the efficiency of the overaging treatment.
- the temperature of the steel plate 1a after being heated by the heating device is in the range of 180 to 220 ° C., that is, the steel plate 1a is in the above range within the above range. Is preferably transferred to. It is preferable that the retention time y (hr) of the steel plate 1a in the heat insulation container satisfies the following formula (1).
- t (° C.) is the temperature (holding temperature) of the steel plate 1a during the holding time y (hr), and is the lowest temperature when temperature fluctuation occurs in the steel plate 1a.
- the hot dip treatment apparatus and the heating apparatus are separate apparatuses, but the hot dip treatment apparatus may include the heating furnace 21 so that the hot dip treatment apparatus may also serve as the heating apparatus.
- the design may be changed as appropriate by adding, removing, or replacing various elements as necessary.
- the hot dip treatment apparatus and the heating apparatus according to the present embodiment are suitable when the steel material 1 is the steel plate 1a, the design of the hot dip treatment apparatus, the heating apparatus, and the like can be variously changed according to the shape of the steel material 1 and the like. is there.
- the pretreatment for plating is performed on the steel material 1, the pretreatment for plating can be variously changed according to the type, shape and the like of the steel material 1.
- the steel material 1 that has been subjected to the hot dipping treatment or further subjected to the overaging treatment may have a chemical conversion treatment layer formed on the plating layer.
- a coating layer made of a paint or a film may be formed on the chemical conversion treatment layer or without the chemical conversion treatment layer.
- the chemical conversion treatment layer is a layer formed by a known chemical conversion treatment.
- the treatment agent (chemical conversion treatment agent) for forming the chemical conversion treatment layer include chromium such as a chromate treatment agent, a trivalent chromic acid treatment agent, a chromate treatment agent containing a resin, and a trivalent chromic acid treatment agent.
- Treatment agents Phosphate treatment agents such as zinc phosphate treatment agents and iron phosphate treatment agents; Oxide treatment agents containing metal oxides such as cobalt, nickel, tungsten, zirconium alone or in combination; Corrosion Treatment agent containing an inhibitor component for preventing oxidization; treatment agent in which a binder component (organic, inorganic, organic-inorganic composite, etc.) and inhibitor component are combined; treatment agent in which an inhibitor component and metal oxide are combined; binder component and silica And a treatment agent in which a sol such as titania or zirconia is combined; a treatment agent in which the components of the exemplified treatment agents are further combined.
- a chromium-containing treatment agent prepared by blending water and water-dispersible acrylic resin, a silane coupling agent having an amino group, and a source of chromium ions such as ammonium chromate and ammonium dichromate Treatment agents to be used.
- the water-dispersible acrylic resin is obtained, for example, by copolymerizing a carboxyl group-containing monomer such as acrylic acid and a glycidyl group-containing monomer such as glycidyl acrylate.
- the chemical conversion treatment layer formed from this chemical conversion treatment agent has high water resistance, corrosion resistance, and alkali resistance, and this chemical conversion treatment layer suppresses the occurrence of white rust and black rust in the hot-dip plated steel material, thereby improving the corrosion resistance.
- the chromium content in the chemical conversion treatment layer is preferably in the range of 5 to 50 mg / m 2 .
- oxide treating agents containing zirconium oxide include water and water-dispersible polyester urethane resins, water-dispersible acrylic resins, zirconium compounds such as sodium zirconium carbonate, and hindered amines. And a treatment agent prepared in this manner.
- the water-dispersible polyester-based urethane resin is synthesized, for example, by reacting a polyester polyol with hydrogenated isocyanate and self-emulsifying by copolymerizing dimethylol alkyl acid.
- Such a water-dispersible polyester-based urethane resin imparts high water resistance to the chemical conversion treatment layer without using an emulsifier, leading to improvement in corrosion resistance and alkali resistance of the hot-dip plated steel material.
- a nickel plating treatment or a cobalt plating treatment may be performed under the chemical conversion treatment layer or instead of the chemical conversion treatment.
- Mg-based oxide films are easily dissolved when in contact with an acidic aqueous solution.
- an acidic aqueous solution For example, when the surface of a hot-dip plated steel material is exposed to an acidic wet state in a corrosive environment, the Mg-based oxide film dissolves and peels.
- the chemical conversion treatment layer or the coating layer is in close contact with the Mg-based oxide film on the surface of the plating layer, the adhesion between the plating layer and the chemical conversion treatment layer or the coating layer may be greatly reduced. Accordingly, it is preferable that the Mg-based coating layer is positively removed as necessary in the base treatment.
- the chemical conversion treatment layer may be formed by a known method such as a roll coating method, a spray method, a dipping method, an electrolytic treatment method, or an air knife method using a chemical conversion treatment agent. After application of the chemical conversion treatment agent, a step such as standing at room temperature or drying or baking with a heating device such as a hot air furnace, an electric furnace, or an induction heating furnace may be added as necessary. A curing method using energy rays such as infrared rays, ultraviolet rays and electron beams may be applied. The temperature and drying time during drying are appropriately determined according to the type of chemical conversion treatment agent used and the required productivity. The chemical conversion treatment layer thus formed becomes a continuous or discontinuous film on the plating layer. The thickness of the chemical conversion treatment layer is appropriately determined according to the type of treatment, required performance, and the like.
- a coating layer formed from a paint or a film can also be formed by a known method.
- the coating layer is formed from paint
- examples of the paint include polyester resin paint, epoxy resin paint, acrylic resin paint, fluororesin paint, silicon resin paint, amino resin paint, urethane resin paint, A vinyl chloride resin-based paint or a composite paint obtained by combining these paints is used.
- a coating method of the paint known methods such as a roll coating method, a curtain coating method, a spray method, a dipping method, an electrolytic treatment method, and an air knife method can be employed.
- the coating material is applied on the plating layer or on the chemical conversion treatment layer or the like when a chemical conversion treatment layer or the like is formed.
- the coating layer is formed by subjecting the coating to drying at normal temperature, drying or baking with a heating device such as a hot air furnace, an electric furnace, or an induction heating furnace, if necessary.
- a heating device such as a hot air furnace, an electric furnace, or an induction heating furnace.
- the coating layer is cured. Good.
- the temperature at which the paint is dried and the drying time are appropriately determined according to the type of paint used and the required productivity.
- the coating layer is a continuous or discontinuous film.
- the thickness of the coating layer formed from the paint is appropriately determined according to the kind of paint and the required performance. For example, when a hot-dip steel sheet is used as a pre-coated metal sheet product (a product that is mechanically processed after painting), an undercoat coating layer having a thickness of about 2 to 15 ⁇ m is formed as a coating layer through a chemical conversion treatment layer. It is preferable to form an overcoat layer of about 5 to 200 ⁇ m.
- the coating layer has a greater thickness, for example, The thickness is preferably several mm.
- the coating layer is formed from a film
- examples of the film include a vinyl chloride film, a polyester resin film, an acrylic resin film, a fluororesin film, a composite film in which these resins are combined, and these films are laminated.
- examples include laminated films.
- the coating layer is formed on the chemical conversion treatment layer or the like by, for example, heat-sealing or bonding with an adhesive. It is formed.
- the thickness of the coating layer formed from the film is appropriately determined according to the type of film, required performance, cost, etc., and is, for example, in the range of 5 to 500 ⁇ m.
- the thickness of the coating layer may be on the order of mm depending on the use of the hot dip plated steel material.
- the coating layer formed from a paint or a film may be formed directly on the plating layer, or may be formed via another layer, for example, a chemical conversion treatment layer.
- the coating layer may be formed of only a paint or a film, or may be formed by combining and laminating a layer formed of a paint and a layer formed of a film.
- the clear layer may be formed on the coating layer by, for example, applying a clear paint on the coating layer to form a film.
- the hot-dip plated steel manufactured by this embodiment has suppressed the formation of the Mg-based oxide film on the surface layer of the plating layer, and further suppressed the unevenness of the plating surface due to the occurrence of wrinkles and sagging, Compared to the Mg-containing plated steel material, it is possible to exhibit a good chemical conversion treatment property, a good adhesion of the coating layer, and a good surface appearance after the coating layer formability. Furthermore, this hot-dip plated steel material exhibits good corrosion resistance.
- This hot-dip galvanized steel material can be used for building materials, materials for automobiles, materials for home appliances, and other various uses, and can be suitably used particularly for applications requiring corrosion resistance.
- Examples and Comparative Examples As the steel material 1, a long steel plate 1a (made of low carbon aluminum killed steel) having a thickness of 0.80 mm and a width of 1000 mm was used. In Examples 62 and 63, Ni pre-plating is performed before the steel plate 1a is subjected to the hot dipping process. In Example 62, the adhesion amount (one side) is 0.5 g / m 2 , and in Example 63, the adhesion is performed. A pre-plated layer having an amount (one side) of 2.0 g / m 2 was formed.
- Example 64 a Zn-10% Cr pre-plating process was performed to form a pre-plated layer having an adhesion amount (one surface) of 1.0 g / m 2 . In other examples and comparative examples, no pre-plating treatment was performed.
- the steel sheet 1a was subjected to a hot dipping process using the hot dipping apparatus shown in FIG.
- the processing conditions are as shown in Tables 1 to 4.
- the solidification start temperatures shown in Tables 1 to 3 are values derived from the liquid phase curve of the phase diagram of the Zn—Al binary system, and the Al content in each hot dipping bath composition shown in Tables 1 to 3 Is a value corresponding to.
- the temperature when the steel sheet 1a entered the hot dipping bath 2 was 580 ° C.
- Example 65 the transport path of the steel plate 1a upstream from the hot dipping bath 2 is surrounded by a seal box (hollow member 22), and an injection nozzle 9 is disposed inside the seal box.
- the inside of the chamber was set to a nitrogen atmosphere, and gas wiping with nitrogen gas was performed inside the hollow member 22.
- the steel plate 1a was cooled until the surface temperature of the hot dip metal (plating layer) reached 300 ° C.
- the cooling rate during cooling was 45 ° C./sec.
- the cooling rate in the temperature range where the surface temperature of the hot-dip metal was 500 ° C. or higher was changed, and in this process, the cooling rate in Example 70 was 38 ° C./sec.
- the cooling rate at 71 was 28 ° C./sec.
- the rolling reduction during temper rolling was 1%, and the elongation of the steel sheet 1a during shape correction was 1%.
- FIG. 4A shows an image obtained by photographing the cut surface of the hot-dip plated steel sheet obtained in Example 5 with an electron microscope. Furthermore, elemental analysis was performed on the portion where precipitation of the Si—Mg phase was observed using an energy dispersive X-ray analyzer (EDS). The result is shown in FIG. According to this result, it can be seen that only two elements of Mg and Si are strongly detected. O (oxygen) is also detected because oxygen adsorbed on the sample was detected in the sample preparation stage.
- EDS energy dispersive X-ray analyzer
- the area ratio (%) of the Si—Mg phase in the cut surface was measured by performing image analysis based on the captured image in the range where the length in the direction orthogonal to the thickness direction in the cut surface of the plating layer was 20 mm. . Since the Si—Mg phase has a dark gray color tone and is clearly distinguished from other phases, it can be easily discriminated by image analysis.
- the volume ratio of the Si—Mg phase was evaluated on the assumption that the area ratio (%) obtained thereby coincided with the volume ratio of the Si—Mg phase. The results are shown in Tables 5-8.
- Elemental analysis in the depth direction (thickness direction of the plating layer) of the components contained in the plating layer in the hot dip plated steel sheet was performed by glow discharge emission optical spectroscopy (GD-OES).
- GD-OES glow discharge emission optical spectroscopy
- the diameter of the measurement area is 4 mm ⁇
- the output is 35 W
- the measurement atmosphere is Ar gas
- the measurement pressure is 600 Pa
- the discharge mode is normal sputtering
- Duty Cycle 0.1 the analysis time is 80 seconds
- sampling time is 0.02 sec /
- the emission intensity of the element contained in the plating layer was measured under the condition of point.
- the sputter depth is measured by observing the cross section of the sample after the measurement is completed, and this sputter depth is divided by the total sputter time.
- the sputtering rate was calculated, and the depth position of the plating layer in the GD-OES depth profile was specified.
- Example 44 the analysis results are shown in FIGS. 5 (a) and 5 (b), respectively. According to this, in Example 44, it can confirm that the density
- FIG. 7A shows a photograph of the surface of the plating layer in Example 5.
- FIG. 7B shows a photograph of the surface of the plating layer in Example 9.
- FIG. 8A shows an optical micrograph of the surface of the plating layer in Example 56.
- FIG. 8B shows an optical micrograph of the surface of the plating layer in Example 5.
- FIG. 9 shows a photograph of the appearance of the plating layer in Example 44.
- Example 72 when the appearance characteristics of the plating layer excluding wrinkles, sagging, and dross were observed, coarsening of spangles was observed in Example 72 (see “Others” column).
- the hot dip plated steel sheet was cut to obtain a sample having a size of 100 ⁇ 50 mm in plan view.
- the salt spray test based on JISZ2371 was done for 20 days.
- the plating corrosion weight loss was measured.
- the sample after the salt spray test was immersed in a treatment bath having a CrO 3 concentration of 200 g / L and a temperature of 80 ° C. for 3 minutes to dissolve and remove the corrosion products from the sample.
- the weight loss from the sample before the salt spray test of the sample after this treatment was defined as the plating corrosion weight loss.
- Plating corrosion weight loss is 5 g / m 2 or less.
- ⁇ Plating corrosion weight loss is greater than 5 g / m 2 and 10 g / m 2 or less.
- ⁇ Plating corrosion weight loss is larger than 10 g / m 2 and 20 g / m 2 or less.
- X Plating corrosion weight loss is larger than 20 g / m 2 .
- a chemical conversion treatment agent made by Nippon Parkerizing Co., Ltd., product number 1300AN
- a chromate-containing chemical conversion treatment agent is applied on both sides of a hot-dip plated steel sheet, and then dried, so that the amount of chromium deposited is 30 to 50 mg / m 2 .
- a treatment layer was formed.
- an epoxy undercoat (Nippon Paint Co., Ltd., product number P • 152S) was applied to a thickness of 5 ⁇ m and baked to form an undercoat coating layer.
- a polyester-based topcoat coating (Nippon Paint Co., Ltd., trade name Nippe Super Coat 300HQ) was applied to a thickness of 20 ⁇ m, and baked by heating to form a topcoat coating layer.
- the coated hot-dip steel sheet was cut to obtain a sample having a size of 100 ⁇ 50 mm in plan view. After exposing this sample to the coastal area of Okinawa for one year outdoors, the cut end face and painted surface of this sample were observed, and the corrosion status was evaluated according to the following criteria. The results are shown in Tables 9-12.
- Blister width is less than 2 mm.
- Blister width is 2 mm or more and less than 5 mm.
- X Blister width is 5 mm or more.
- production of the white rust in a coating surface arises because the thickness of a coating layer becomes thin partially due to the protrusion of a plating layer, or the dross adhering to a plating layer, or the said protrusion and dross penetrate a coating layer. It is considered a thing.
- the hot dip plated steel sheet was cut to obtain a sample having a size of 30 mm ⁇ 40 mm in plan view. This sample was subjected to 8T bending. The top of the bent portion of this sample was observed with a microscope. Based on this result, bending workability was evaluated according to the following criteria.
- the 8T bending corresponds to the case where the “inner bending interval” in Table 17 of 13.2.2 of JIS G3322 is “8 sheets of display thickness”. The results are shown in Tables 9-12.
- Double-circle A crack is not recognized.
- ⁇ The number of cracks is 1 or more and less than 5.
- ⁇ The number of cracks is 5 or more and less than 20.
- X The number of cracks is 20 or more.
- the hot dip plated steel sheet was cut to obtain a sample having a size of 30 mm ⁇ 40 mm in plan view. This sample was subjected to 4T bending.
- the 4T bending corresponds to the case where the “inner bending interval” in Table 17 of 13.2.2 of JIS G3322 is “four plates of display thickness”.
- the horizontal axis indicates the test conditions of the heat retention temperature t (° C.) and the vertical axis indicates the heat retention time y (hr).
- the evaluation results for the heat retention temperature and the heat retention time are shown at positions corresponding to the heat retention temperature t (° C.) and the heat retention time y (hr) during the test.
- a region sandwiched by broken lines in the graph is a region where the heat retention temperature t (° C.) and the heat retention time y (hr) satisfy the following formula (1).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
前記アルミニウム・亜鉛合金めっき層が構成元素としてAl、Zn、Si及びMgを含み、且つMg含有量が0.1~10質量%であり、
前記アルミニウム・亜鉛合金めっき層が0.2~15体積%のSi―Mg相を含み、
前記Si-Mg相中のMgの、Mg全量に対する質量比率が3%以上であることを特徴とする。
前記アルミニウム・亜鉛合金めっき層における50nm深さの最外層内で、大きさが直径4mm、深さ50nmとなるいかなる領域において、Mg含有量が60質量%未満であることが好ましい。
前記アルミニウム・亜鉛合金めっき層が構成元素として更に
0.02~1.0質量%のCrを含むことが好ましい。
前記アルミニウム・亜鉛合金めっき層における50nm深さの最外層内でのCrの含有量が100~500質量ppmの範囲であることが好ましい。
前記アルミニウム・亜鉛合金めっき層と前記鋼材との間に、AlとCrとを含有する合金層が介在し、この合金層中のCrの質量割合の、前記アルミニウム・亜鉛合金めっき層内のCrの質量割合に対する比が、2~50の範囲であることが好ましい。
前記アルミニウム・亜鉛合金めっき層の表面におけるSi―Mg相の割合が、面積比率で、30%以下であることが好ましい。
前記アルミニウム・亜鉛合金めっき層中の
Alの含有量が25~75質量%、
Siの含有量がAlに対して0.5~10質量%、
であり、且つ
Si:Mgの質量比が100:50~100:300
であることが好ましい。
前記アルミニウム・亜鉛合金めっき層が構成元素として更に
1~1000質量ppmのSrを含むことが好ましい。
前記アルミニウム・亜鉛合金めっき層が、構成元素として更にTi及びBのうち少なくとも一方からなる成分を、0.0005~0.1質量%の範囲で含有することが好ましい。
下記組成を含む溶融めっき浴を準備し、
25~75質量%のAl、
0.1~10質量%のMg、
0.02~1.0質量%のCr、
Alに対して0.5~10質量%のSi、
1~1000質量ppmのSr、
0.1~1.0質量%のFe、
残部がZn、
且つ
Si:Mgの質量比が100:50~100:300
鋼材をこの溶融めっき浴に通過させてその表面に溶融めっき金属を付着させ、
この溶融めっき金属を凝固させて前記鋼材の表面にアルミニウム・亜鉛合金めっき層を形成することを特徴とする。
前記溶融めっき浴が、更に、100~5000質量ppmのCaを含有することが好ましい。
前記溶融めっき浴が、更にTi及びBのうち少なくとも一方からなる成分を、0.0005~0.1質量%の範囲で含有することが好ましい。
前記溶融めっき浴の温度を、凝固開始温度よりも40℃高い温度以下の温度に保持することが好ましい。
前記鋼材を前記溶融めっき浴から非酸化性雰囲気又は低酸化性雰囲気中へ引き出し、続いてこの鋼材に付着している溶融めっき金属が凝固する前に前記雰囲気中でガスワイピング法により前記鋼材における溶融めっき金属の付着量を調整することが好ましい。
前記アルミニウム・亜鉛合金めっき層がめっきされた鋼材を下記式(1)で規定される保温温度t(℃)及び保温時間y(hr)で保温する工程を含むことが好ましい。
(但し、150≦t≦250)
本実施形態に係る溶融めっき鋼材は、鋼材1の表面上にアルミニウム・亜鉛合金めっき層(以下、めっき層という)がめっきされてなる。鋼材1としては、薄鋼板、厚鋼板、型鋼、鋼管、鋼線等の種々の部材が挙げられる。すなわち、鋼材1の形状は特に制限されない。めっき層は、溶融めっき処理により形成される。
Rはめっき層中のMg全量に対するSi-Mg相中のMgの質量比率(質量%)を、Aはめっき層の平面視単位面積当たりの、めっき層中のSi-Mg相に含まれるMg含有量(g/m2)を、Mはめっき層の平面視単位面積当たりの、めっき層の質量(g/m2)を、CMGはめっき層中の全Mgの含有量(質量%)を、それぞれ示す。
V2はめっき層の平面視単位面積当たりの、めっき層中のSi-Mg相の体積(m3/m2)を示す。ρ2はSi-Mg相の密度を示し、その値は1.94×106(g/m3)である。αはSi-Mg相中のMgの含有質量比率を示し、その値は0.63である。
V1はめっき層の平面視単位面積あたりの、めっき層の全体体積(m3/m2)を、R2はめっき層中のSi-Mg相の体積比率(体積%)を、それぞれ示す。
ρ1は、めっき層全体の密度(g/m3)を示す。ρ1の値は、めっき層の組成に基づいてめっき層の構成元素の常温での密度を加重平均することで算出され得る。
を用いて測定することで導出され得る。
好ましい実施形態では、溶融めっき鋼材の製造時に、めっき層の構成元素の組成と一致する組成を有する溶融めっき浴が準備される。溶融めっき処理により鋼材とめっき層との間に合金層が形成されるが、それによる組成の変動は無視し得るほどに小さい。
鋼板1aが冷却される過程では、鋼板1a上の溶融めっき金属の表面温度が500℃以上である間の溶融めっき金属の表面の冷却速度が50℃/sec以下であることが好ましい。この場合、めっき層の表面におけるSi-Mg相の析出が特に抑制され、このためタレの発生が抑制される。この温度域での冷却速度がSi-Mg相の析出挙動に影響する理由は現時点で必ずしも明確ではないが、この温度域での冷却速度が速いと溶融めっき金属における厚み方向の温度勾配が大きくなり、このため温度がより低い溶融めっき金属の表面で優先的にMg-Si層の析出が促進されてしまい、その結果、めっき最表面でのSi-Mg相の析出量が多くなってしまうと考えられる。この温度域での冷却速度は、40℃/sec以下であれば更に好ましく、35℃/sec以下であれば特に好ましい。
(但し、150≦t≦250)
式(1)中のt(℃)は、前記保持時間y(hr)中における鋼板1aの温度(保持温度)であり、鋼板1aに温度変動が生じる場合にはその最低温度である。
鋼材1として厚み0.80mm、幅1000mmの長尺の鋼板1a(低炭素アルミニウムキルド鋼製)を用いた。尚、実施例62,63では、鋼鈑1aに溶融めっき処理を施す前に、Niプレめっきを施すことで、実施例62では付着量(片面)0.5g/m2、実施例63では付着量(片面)2.0g/m2のプレめっき層を形成した。実施例64では、Zn-10%Crプレめっき処理を施し、付着量(片面)1.0g/m2のプレめっき層を形成した。他の実施例及び比較例ではプレめっき処理を施さなかった。
各実施例及び比較例で得られた溶融めっき鋼材(溶融めっき鋼板)について、次の評価試験をおこなった。
溶融めっき鋼板を切断してサンプルを得た。このサンプルを、その切断面が表出するように樹脂に埋め込んだ後、切断面を鏡面状に研磨した。この切断面を電子顕微鏡により観察したところ、この切断面には、めっき層にSi-Mg相が分布している様子が明瞭に現れた。
上述の式(1)~(3)により、めっき層における全Mg量に対するSi-Mg相中のMg量の質量比率を算出した。その結果を表4~6に示す。
溶融めっき鋼板におけるめっき層に含まれる成分の、深さ方向(めっき層の厚み方向)の元素分析を、グロー放電発光分光分析(GD-OES:Glow Discharge - Optical Emission Spectroscopy)によりおこなった。測定にあたっては、測定領域の直径を4mmφ、出力を35W、測定雰囲気をArガス、測定圧力を600Pa、放電モードをノーマルスパッタ、Duty Cycle0.1、分析時間を80秒、サンプリング時間を0.02sec/pointとする条件で、めっき層に含まれる元素の発光強度を測定した。得られた発光強度値を定量濃度値(質量%濃度)に換算する為、成分濃度が既知の7000系Al合金、鉄鋼材料等の標準試料の元素分析も別途おこなった。尚、通常、GD-OESデータは、発光強度のスパッタ時間に対する変化の形であるため、測定終了後のサンプルの断面観察によりスパッタ深さを測定し、このスパッタ深さを合計スパッタ時間で除することでスパッタ速度を算出し、GD-OES深さ方向プロファイルにおけるめっき層の深さ位置を特定した。
表層Mg量評価の場合と同様にして、GD-OESにより、大きさが直径4mmで、めっき層最表面から深さ50nmとなる領域におけるCr発光強度の積分値を測定した。同様に、めっき層全体のCr発光強度の積分値も測定し、更にこの値に対する、前記領域におけるCr発光強度の積分値の比を求めた。このCr発光強度の積分値の比と、ICPによるめっき層全体のCr量の化学分析値とに基づいて、大きさが直径4mmで、めっき層最表面から深さ50nmとなる領域における、Crの含有量を算出した。その結果を表5~8に示す。
めっき層の表面を電子顕微鏡により観察した。実施例5について、めっき層の表面を電子顕微鏡により撮影した写真を図6に示す。この観察結果によれば、めっき層の表面にSi-Mg相が分布している様子が確認できる。この結果に基づいて、めっき層の表面におけるSi-Mg相の面積を測定し、これに基づいて、めっき層表面におけるSi-Mg相の面積比率を算出した。その結果を表5~8に示す。
溶融めっき鋼板を切断してサンプルを得た。このサンプルを、その切断面が表出するように樹脂に埋め込んだ後、切断面を鏡面状に研磨した。この切断面には、めっき層と鋼板1aとの界面に介在する合金層が現れた。この合金層の厚みを測定した。さらに研磨面から収束イオンビーム装置により、研磨面の10μm×20μm部分をサンプリングし、50nm厚み以下に加工したマイクロサンプルを作製した。このマイクロサンプルについて、エネルギー分散型X線分析装置(EDS)を用い、加速電圧200kV、プローブ径1nmの条件で、合金層内のCr濃度を定量分析した。
溶融めっき鋼板におけるめっき層の表面の外観を目視及び光学顕微鏡により観察した。図7(a)は実施例5におけるめっき層の表面を撮影した写真を示す。図7(b)は実施例9におけるめっき層の表面を撮影した写真を示す。図8(a)は実施例56におけるめっき層の表面の光学顕微鏡写真を示す。図8(b)は実施例5におけるめっき層の表面の光学顕微鏡写真を示す。図9は実施例44におけるめっき層の外観を撮影した写真を示す。
◎:しわが認められない。
○:しわが軽微(図7(a)に示される程度のしわ)。
△:しわが中程度(図7(b)に示されるよりは良好)。
×:しわが著しい(図7(b)に示される程度のしわ)。
○:タレが認められない。
×:タレが認められる(図9に示される程度のタレ)。
○:めっき層の表面に、凹凸を伴うドロスの付着がなく、或いは凹凸を伴うドロスの付着が1m2あたり5箇所未満認められる。
×:めっき層の表面に、凹凸を伴うドロスの付着が1m2あたり5箇所以上認められる。
溶融めっき鋼板を切断して、平面視100×50mmの寸法のサンプルを得た。このサンプルについて、JIS Z2371に準拠した塩水噴霧試験を20日間行った。塩水噴霧試験後のサンプルについて、めっき腐食減量を測定した。このめっき腐食減量の測定時には、塩水噴霧試験後のサンプルを、CrO3濃度200g/L、温度80℃の処理浴に3分間浸漬することで、このサンプルから腐食生成物を溶解除去した。この処理後のサンプルの、塩水噴霧試験前のサンプルからの重量減少分を、めっき腐食減量とした。
◎:めっき腐食減量が5g/m2以下。
○:めっき腐食減量が5g/m2より大きく、10g/m2以下。
△:めっき腐食減量が10g/m2より大きく、20g/m2以下。
×:めっき腐食減量が20g/m2より大きい。
溶融めっき鋼板の両面上に、クロメート含有化成処理剤からなる化成処理剤(日本パーカライジング株式会社製、品番1300AN)を塗布した後、乾燥させることで、クロム付着量が30~50mg/m2の化成処理層を形成した。この化成処理層上に、エポキシ系下塗り塗料(日本ペイント株式会社製、品番P・152S)を5μmの厚みに塗布し、加熱焼き付けすることで、下塗り被覆層を形成した。この下塗り被覆層上に、ポリエステル系上塗り塗料(日本ペイント株式会社製、商品名ニッペスーパーコート300HQ)を20μmの厚みに塗布し、加熱焼き付けすることで、上塗り被覆層を形成した。
◎:ブリスターが全く認められない。
○:ブリスター幅が2mm未満。
△:ブリスター幅が2mm以上、5mm未満。
×:ブリスター幅が5mm以上。
○:白さびの発生が認められない。
△:白錆が点在している。
×:多数の白錆が認められる。
溶融めっき鋼板を切断して、平面視30mm×40mmの寸法のサンプルを得た。このサンプルに8T曲げ加工を施した。このサンプルにおける折り曲げられている部分の頂上を顕微鏡で観察した。この結果に基づき、下記基準により折り曲げ加工性を評価した。なお、8T曲げとは、JIS G3322の13.2.2の表17における「曲げの内側間隔」が、「表示厚さの板8枚」の場合に相当する。その結果を表9~12に示す。
◎:クラックが認められない。
○:クラックの個数が1以上5未満。
△:クラックの個数が5以上20未満。
×:クラックの個数が20個以上。
溶融めっき鋼板を切断して、平面視30mm×40mmの寸法のサンプルを得た。このサンプルに4T曲げ加工を施した。なお、4T曲げとは、JIS G3322の13.2.2の表17における「曲げの内側間隔」が、「表示厚さの板4枚」の場合に相当する。
◎:折り曲げられている部分に白錆発生が認められない。
○:折り曲げられている部分のクラックが生じている部分にのみ白錆発生が認められる。
△:折り曲げられている部分全体を覆う様に白錆が発生し、一部は折り曲げられている部分以外へも錆が流れて拡がっている。
×:折り曲げられている部分に白錆が発生し、更に赤錆発生も認められる。
実施例5の溶融めっき鋼板のコイルに対し、保温温度t(℃)及び保温時間y(hr)を変化させて、過時効処理を施した。その結果を下記のように評価した。
◎:コイルにめっき層間で凝着が生じず、且つ加工性が向上した。
○:コイルにめっき層間で凝着が生じないが、加工性は改善しない。
×:コイルにめっき層間で凝着が生じた。
(但し、150≦t≦250)
2 溶融めっき浴
Claims (15)
- 鋼材の表面上にアルミニウム・亜鉛合金めっき層がめっきされてなる溶融めっき鋼材であって、
前記アルミニウム・亜鉛合金めっき層が構成元素としてAl、Zn、Si及びMgを含み、且つMg含有量が0.1~10質量%であり、
前記アルミニウム・亜鉛合金めっき層が0.2~15体積%のSi―Mg相を含み、
前記Si-Mg相中のMgの、Mg全量に対する質量比率が3%以上であることを特徴とする溶融めっき鋼材。 - 前記アルミニウム・亜鉛合金めっき層における50nm深さの最外層内で、大きさが直径4mm、深さ50nmとなるいかなる領域において、Mg含有量が60質量%未満であることを特徴とする請求項1記載の溶融めっき鋼材。
- 前記アルミニウム・亜鉛合金めっき層が構成元素として更に
0.02~1.0質量%のCrを含むことを特徴とする請求項1又は2に記載の溶融めっき鋼材。 - 前記アルミニウム・亜鉛合金めっき層における50nm深さの最外層内でのCrの含有量が100~500質量ppmの範囲であることを特徴とする請求項3に記載の溶融めっき鋼材。
- 前記アルミニウム・亜鉛合金めっき層と前記鋼材との間に、AlとCrとを含有する合金層が介在し、この合金層中のCrの質量割合の、前記アルミニウム・亜鉛合金めっき層内のCrの質量割合に対する比が、2~50の範囲である請求項3又は4に記載の溶融めっき鋼材。
- 前記アルミニウム・亜鉛合金めっき層の表面におけるSi―Mg相の割合が、面積比率で、30%以下であることを特徴とする請求項1乃至5のいずれか一項に記載の溶融めっき鋼材。
- 前記アルミニウム・亜鉛合金めっき層中の
Alの含有量が25~75質量%、
Siの含有量がAlに対して0.5~10質量%、
であり、且つ
Si:Mgの質量比が100:50~100:300
であることを特徴とする請求項1乃至6のいずれか一項に記載の溶融めっき鋼材。 - 前記アルミニウム・亜鉛合金めっき層が構成元素として更に
1~1000質量ppmのSrを含むことを特徴とする請求項1乃至7のいずれか一項に記載の溶融めっき鋼材。 - 前記アルミニウム・亜鉛合金めっき層が、構成元素として更にTi及びBのうち少なくとも一方からなる成分を、0.0005~0.1質量%の範囲で含有する請求項1乃至8のいずれか一項に記載の溶融めっき鋼材。
- 溶融めっき鋼材の製造方法であって、
下記組成を含む溶融めっき浴を準備し、
25~75質量%のAl、
0.1~10質量%のMg、
0.02~1.0質量%のCr、
Alに対して0.5~10質量%のSi、
1~1000質量ppmのSr、
0.1~1.0質量%のFe、
残部がZn、
且つ
Si:Mgの質量比が100:50~100:300
鋼材をこの溶融めっき浴に通過させてその表面に溶融めっき金属を付着させ、
この溶融めっき金属を凝固させて前記鋼材の表面にアルミニウム・亜鉛合金めっき層を形成することを特徴とする溶融めっき鋼材の製造方法。 - 前記溶融めっき浴が、更に、100~5000質量ppmのCaを含有する請求項10に記載の溶融めっき鋼材の製造方法。
- 前記溶融めっき浴が、更にTi及びBのうち少なくとも一方からなる成分を、0.0005~0.1質量%の範囲で含有する請求項10又は11に記載の溶融めっき鋼材の製造方法。
- 前記溶融めっき浴の温度を、凝固開始温度よりも40℃高い温度以下の温度に保持することを特徴とする請求項10乃至12のいずれか一項に記載の溶融めっき鋼材の製造方法。
- 前記鋼材を前記溶融めっき浴から非酸化性雰囲気又は低酸化性雰囲気中へ引き出し、続いてこの鋼材に付着している溶融めっき金属が凝固する前に前記雰囲気中でガスワイピング法により前記鋼材における溶融めっき金属の付着量を調整することを特徴とする請求項10乃至13のいずれか一項に記載の溶融めっき鋼材の製造方法。
- 前記アルミニウム・亜鉛合金めっき層がめっきされた鋼材を下記式(1)で規定される保温温度t(℃)及び保温時間y(hr)で保温する工程を含むことを特徴とする請求項10乃至14のいずれか一項に記載の溶融めっき鋼材の製造方法。
5.0×1022×t-10.0≦y≦7.0×1024×t-10.0 …(1)
(但し、150≦t≦250)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112012013190A BR112012013190B1 (pt) | 2010-02-18 | 2011-02-17 | aço por imersão a quente e método para produzir o mesmo |
KR1020147030933A KR101678538B1 (ko) | 2010-02-18 | 2011-02-17 | 용해 도금 강재 및 그 제조 방법 |
KR1020167031923A KR101692684B1 (ko) | 2010-02-18 | 2011-02-17 | 용해 도금 강재 및 그 제조 방법 |
US13/513,025 US9080231B2 (en) | 2010-02-18 | 2011-02-17 | Hot-dipped steel and method of producing same |
AU2011216352A AU2011216352B2 (en) | 2010-02-18 | 2011-02-17 | Hot-dipped steel and method for producing same |
CN201180004914.XA CN102762759B (zh) | 2010-02-18 | 2011-02-17 | 热浸镀钢及其制造方法 |
JP2012500648A JP5118782B2 (ja) | 2010-02-18 | 2011-02-17 | 溶融めっき鋼材及びその製造方法 |
ES11744720.1T ES2657614T3 (es) | 2010-02-18 | 2011-02-17 | Material de acero metalizado por inmersión en caliente y método para producir el mismo |
EP11744720.1A EP2537954B1 (en) | 2010-02-18 | 2011-02-17 | Hot-dipped steel material and method for producing same |
MX2012005996A MX2012005996A (es) | 2010-02-18 | 2011-02-17 | Acero elaborado por inmersion en caliente y metodo para producirlo. |
CA2780445A CA2780445C (en) | 2010-02-18 | 2011-02-17 | Hot-dipped steel and method of producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-033502 | 2010-02-18 | ||
JP2010033502 | 2010-02-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011102434A1 true WO2011102434A1 (ja) | 2011-08-25 |
Family
ID=44483020
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/053426 WO2011102434A1 (ja) | 2010-02-18 | 2011-02-17 | 溶融めっき鋼材及びその製造方法 |
Country Status (13)
Country | Link |
---|---|
US (1) | US9080231B2 (ja) |
EP (1) | EP2537954B1 (ja) |
JP (1) | JP5118782B2 (ja) |
KR (3) | KR101678538B1 (ja) |
CN (1) | CN102762759B (ja) |
AU (1) | AU2011216352B2 (ja) |
BR (1) | BR112012013190B1 (ja) |
CA (1) | CA2780445C (ja) |
ES (1) | ES2657614T3 (ja) |
MX (1) | MX2012005996A (ja) |
MY (1) | MY180909A (ja) |
TW (1) | TWI438302B (ja) |
WO (1) | WO2011102434A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140037856A1 (en) * | 2012-08-01 | 2014-02-06 | Union Steel Co., Ltd. | Method and apparatus for producing zinc-aluminum alloy-coated steel sheet with superior workability and corrosion resistance |
JP2014031578A (ja) * | 2012-08-01 | 2014-02-20 | Union Steel Co Ltd | 加工性及び耐食性に優れた亜鉛−アルミニウム系合金めっき鋼板の製造方法及びそのための装置 |
WO2016140370A1 (ja) * | 2015-03-02 | 2016-09-09 | Jfe鋼板株式会社 | 溶融AI-Zn-Mg-Siめっき鋼板とその製造方法 |
JP6087461B1 (ja) * | 2016-04-26 | 2017-03-01 | 日本ペイント・インダストリアルコ−ティングス株式会社 | 表面処理鋼材 |
JP2017190472A (ja) * | 2016-04-11 | 2017-10-19 | 新日鐵住金株式会社 | 合金化溶融亜鉛めっき鋼板の製造方法 |
US9863029B2 (en) | 2012-08-01 | 2018-01-09 | Dongkuk Steel Mill Co., Ltd. | Apparatus for forming nitrogen cloud to produce hot dip coated steel sheet |
DE112016006868T5 (de) | 2016-05-17 | 2019-03-07 | Dongkuk Steel Mill Co., Ltd. | Vorrichtung zum Bilden einer Stickstoffwolke zur Herstellung eines schmelzbadbeschichteten Stahlblechs mit hervorragender Oberflächenqualität und Verfahren zur Herstellung eines mit Zink-Aluminium schmelztauchbeschichteten Stahlblechs unter Verwendung desselben |
JP2020139224A (ja) * | 2019-03-01 | 2020-09-03 | Jfe鋼板株式会社 | 溶融Al−Zn−Mg−Si系めっき鋼板の製造方法及び塗装鋼板の製造方法 |
WO2021235363A1 (ja) * | 2020-05-20 | 2021-11-25 | 日鉄鋼板株式会社 | 被覆めっき鋼板 |
JP7475162B2 (ja) | 2019-03-01 | 2024-04-26 | Jfe鋼板株式会社 | 塗装鋼板及び塗装鋼板の製造方法 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101349612B1 (ko) * | 2012-03-22 | 2014-01-09 | 포스코강판 주식회사 | 용융도금욕, 도금강재 및 도금강재의 제조방법 |
WO2013160566A1 (fr) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante. |
WO2014059475A1 (en) | 2012-10-17 | 2014-04-24 | Bluescope Steel Limited | Method of producing metal-coated steel strip |
US20150267287A1 (en) | 2012-10-18 | 2015-09-24 | Bluescope Steel Limited | Method of producing metal coated steel strip |
WO2014125173A1 (fr) * | 2013-02-18 | 2014-08-21 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de préparation d'une tôle à revêtement znmg ou znaimg comprenant l'application d'une solution basique d'un agent complexant les ions magnésium et tôle obtenue |
WO2014156073A1 (ja) * | 2013-03-25 | 2014-10-02 | Jfeスチール株式会社 | Al-Zn系めっき鋼板 |
KR101758529B1 (ko) * | 2014-12-24 | 2017-07-17 | 주식회사 포스코 | 인산염 처리성과 스폿 용접성이 우수한 아연합금도금강판 및 그 제조방법 |
KR101629260B1 (ko) * | 2015-09-25 | 2016-06-10 | 포스코강판 주식회사 | 용융도금욕 조성물 |
CN105671469B (zh) * | 2016-03-22 | 2018-08-21 | 首钢集团有限公司 | 一种热浸镀钢及其制造方法 |
KR20190045297A (ko) * | 2016-09-05 | 2019-05-02 | 제이에프이 스틸 가부시키가이샤 | 용융 Al-Zn계 도금 강판 |
US10913994B2 (en) * | 2017-09-08 | 2021-02-09 | Nippon Steel Corporation | Zn—Al—Mg-based plated steel sheet |
CN108914033B (zh) * | 2018-08-08 | 2020-02-14 | 湖南恒力通电气设备科技有限公司 | 一种钢板镀锌生产线及该生产线的镀锌工艺 |
JP7335960B2 (ja) | 2018-12-18 | 2023-08-30 | ポスコ カンパニー リミテッド | 合金コーティング鋼板およびその製造方法 |
CN113383105A (zh) * | 2019-04-19 | 2021-09-10 | 日本制铁株式会社 | 镀层钢板 |
CN111705286A (zh) * | 2020-06-12 | 2020-09-25 | 靖江新舟合金材料有限公司 | 一种含镁锶钛的铝锌硅钢板及其生产方法 |
CN111560607B (zh) * | 2020-06-24 | 2022-08-09 | 攀钢集团攀枝花钢铁研究院有限公司 | 热镀锌铝镁钢板表面处理液及热镀锌铝镁无铬钝化板的制备方法 |
CN117265445A (zh) * | 2022-06-13 | 2023-12-22 | 宝山钢铁股份有限公司 | 一种热浸镀锌铝镁钙合金镀层钢板及其制造方法 |
CN115558877A (zh) * | 2022-09-15 | 2023-01-03 | 首钢集团有限公司 | 一种锌铝镁镀层、锌铝镁镀层钢板 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09316618A (ja) * | 1996-05-22 | 1997-12-09 | Nkk Corp | 耐エッジクリープ性に優れた塗装Al−Zn系合金めっ き鋼板 |
JP2000328214A (ja) * | 1999-05-19 | 2000-11-28 | Nisshin Steel Co Ltd | 表面外観の良好な高耐食性Mg含有溶融Zn−Al系合金めっき鋼板 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4897124A (en) * | 1987-07-02 | 1990-01-30 | Sky Aluminium Co., Ltd. | Aluminum-alloy rolled sheet for forming and production method therefor |
JP2996251B2 (ja) * | 1988-10-31 | 1999-12-27 | 本田技研工業株式会社 | 成形加工用アルミニウム合金圧延板およびその製造方法 |
JPH11279735A (ja) | 1998-03-27 | 1999-10-12 | Nisshin Steel Co Ltd | Al−Si−Mg−Zn系溶融Al基めっき鋼板 |
US6465114B1 (en) * | 1999-05-24 | 2002-10-15 | Nippon Steel Corporation | -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same |
JP4136286B2 (ja) * | 1999-08-09 | 2008-08-20 | 新日本製鐵株式会社 | 耐食性に優れたZn−Al−Mg−Si合金めっき鋼材およびその製造方法 |
EP1193323B1 (en) * | 2000-02-29 | 2016-04-20 | Nippon Steel & Sumitomo Metal Corporation | Plated steel product having high corrosion resistance and excellent formability and method for production thereof |
JP3718479B2 (ja) | 2001-03-30 | 2005-11-24 | 新日本製鐵株式会社 | 耐食性に優れる溶融Zn−Al−Cr合金めっき鋼材 |
JP2002322527A (ja) * | 2001-04-25 | 2002-11-08 | Nippon Steel Corp | Al−Zn−Mg系合金めっき鉄鋼製品 |
AU2003275688B2 (en) * | 2002-10-28 | 2006-12-14 | Nippon Steel Corporation | High corrosion-resistant hot dip coated steel product excellent in surface smoothness and formability, and method for producing hot dip coated steel product |
TWM296548U (en) | 2005-04-04 | 2006-08-21 | Interdigital Tech Corp | Apparatus for improving responsiveness in exchanging frames in a wireless local area network |
JP4470874B2 (ja) | 2005-11-30 | 2010-06-02 | Jfeスチール株式会社 | 表面処理亜鉛系めっき鋼板 |
JP4584179B2 (ja) | 2006-04-13 | 2010-11-17 | Jfe鋼板株式会社 | 耐食性および加工性に優れた溶融Zn−Al合金めっき鋼板の製造方法 |
CN101535521B (zh) | 2006-08-29 | 2015-08-19 | 蓝野钢铁有限公司 | 具有金属合金镀层的钢带及在钢带上形成该镀层的方法 |
KR20100131417A (ko) * | 2008-03-13 | 2010-12-15 | 블루스코프 스틸 리미티드 | 금속 코팅된 강철 스트립 |
-
2011
- 2011-02-17 BR BR112012013190A patent/BR112012013190B1/pt active IP Right Grant
- 2011-02-17 AU AU2011216352A patent/AU2011216352B2/en active Active
- 2011-02-17 MX MX2012005996A patent/MX2012005996A/es active IP Right Grant
- 2011-02-17 WO PCT/JP2011/053426 patent/WO2011102434A1/ja active Application Filing
- 2011-02-17 MY MYPI2012002404A patent/MY180909A/en unknown
- 2011-02-17 ES ES11744720.1T patent/ES2657614T3/es active Active
- 2011-02-17 US US13/513,025 patent/US9080231B2/en active Active
- 2011-02-17 KR KR1020147030933A patent/KR101678538B1/ko active IP Right Grant
- 2011-02-17 EP EP11744720.1A patent/EP2537954B1/en active Active
- 2011-02-17 KR KR1020167031923A patent/KR101692684B1/ko active IP Right Grant
- 2011-02-17 CN CN201180004914.XA patent/CN102762759B/zh active Active
- 2011-02-17 CA CA2780445A patent/CA2780445C/en active Active
- 2011-02-17 JP JP2012500648A patent/JP5118782B2/ja active Active
- 2011-02-17 KR KR1020127014630A patent/KR20120112450A/ko not_active Application Discontinuation
- 2011-02-18 TW TW100105485A patent/TWI438302B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09316618A (ja) * | 1996-05-22 | 1997-12-09 | Nkk Corp | 耐エッジクリープ性に優れた塗装Al−Zn系合金めっ き鋼板 |
JP2000328214A (ja) * | 1999-05-19 | 2000-11-28 | Nisshin Steel Co Ltd | 表面外観の良好な高耐食性Mg含有溶融Zn−Al系合金めっき鋼板 |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9863029B2 (en) | 2012-08-01 | 2018-01-09 | Dongkuk Steel Mill Co., Ltd. | Apparatus for forming nitrogen cloud to produce hot dip coated steel sheet |
CN103572189A (zh) * | 2012-08-01 | 2014-02-12 | 联合铁钢株式会社 | 可加工性和耐蚀性优良的锌-铝合金镀敷钢板的生产方法及装置 |
JP2014031578A (ja) * | 2012-08-01 | 2014-02-20 | Union Steel Co Ltd | 加工性及び耐食性に優れた亜鉛−アルミニウム系合金めっき鋼板の製造方法及びそのための装置 |
AU2013209303B2 (en) * | 2012-08-01 | 2015-05-07 | Dongkuk Coated Metal Co., Ltd. | Method and apparatus for producing zinc-aluminum alloy-coated steel sheet with superior workability and corrosion resistance |
CN103572189B (zh) * | 2012-08-01 | 2015-11-18 | 联合铁钢株式会社 | 可加工性和耐蚀性优良的锌-铝合金镀敷钢板的生产方法及装置 |
JP2016027210A (ja) * | 2012-08-01 | 2016-02-18 | ユニオン スティール カンパニーリミテッド | 窒素帳膜形成装置 |
US20140037856A1 (en) * | 2012-08-01 | 2014-02-06 | Union Steel Co., Ltd. | Method and apparatus for producing zinc-aluminum alloy-coated steel sheet with superior workability and corrosion resistance |
TWI641722B (zh) * | 2012-08-01 | 2018-11-21 | 東國製鋼股份有限公司 | 一種可加工性和耐蝕性優良的鋅-鋁合金鍍敷鋼板製造設備 |
WO2016140370A1 (ja) * | 2015-03-02 | 2016-09-09 | Jfe鋼板株式会社 | 溶融AI-Zn-Mg-Siめっき鋼板とその製造方法 |
JP6059408B1 (ja) * | 2015-03-02 | 2017-01-11 | Jfe鋼板株式会社 | 溶融Al−Zn−Mg−Siめっき鋼板とその製造方法 |
US10662516B2 (en) | 2015-03-02 | 2020-05-26 | Jfe Steel Corporation | Hot-dip Al—Zn—Mg—Si coated steel sheet and method of producing same |
JP2017057502A (ja) * | 2015-03-02 | 2017-03-23 | Jfe鋼板株式会社 | 溶融Al−Zn−Mg−Siめっき鋼板とその製造方法 |
JP2017190472A (ja) * | 2016-04-11 | 2017-10-19 | 新日鐵住金株式会社 | 合金化溶融亜鉛めっき鋼板の製造方法 |
JP6087461B1 (ja) * | 2016-04-26 | 2017-03-01 | 日本ペイント・インダストリアルコ−ティングス株式会社 | 表面処理鋼材 |
KR101868530B1 (ko) * | 2016-04-26 | 2018-06-19 | 닛테쓰 스미킨 고한 가부시키가이샤 | 표면처리강재 |
KR20180025877A (ko) * | 2016-04-26 | 2018-03-09 | 닛테쓰 스미킨 고한 가부시키가이샤 | 표면처리강재 |
JP2017197795A (ja) * | 2016-04-26 | 2017-11-02 | 日本ペイント・インダストリアルコ−ティングス株式会社 | 表面処理鋼材 |
US11136659B2 (en) | 2016-04-26 | 2021-10-05 | Nippon Steel Coated Sheet Corporation | Surface-treated steel material |
DE112016006868T5 (de) | 2016-05-17 | 2019-03-07 | Dongkuk Steel Mill Co., Ltd. | Vorrichtung zum Bilden einer Stickstoffwolke zur Herstellung eines schmelzbadbeschichteten Stahlblechs mit hervorragender Oberflächenqualität und Verfahren zur Herstellung eines mit Zink-Aluminium schmelztauchbeschichteten Stahlblechs unter Verwendung desselben |
DE112016006868B4 (de) | 2016-05-17 | 2022-10-20 | Dongkuk Steel Mill Co., Ltd. | Vorrichtung zum Bilden einer Stickstoffwolke zur Herstellung eines schmelztauchbeschichteten Stahlblechs mit hervorragender Oberflächenqualität und Verfahren zur Herstellung eines mit Zink-Aluminium schmelztauchbeschichteten Stahlblechs unter Verwendung desselben |
JP2020139224A (ja) * | 2019-03-01 | 2020-09-03 | Jfe鋼板株式会社 | 溶融Al−Zn−Mg−Si系めっき鋼板の製造方法及び塗装鋼板の製造方法 |
JP7475162B2 (ja) | 2019-03-01 | 2024-04-26 | Jfe鋼板株式会社 | 塗装鋼板及び塗装鋼板の製造方法 |
WO2021235363A1 (ja) * | 2020-05-20 | 2021-11-25 | 日鉄鋼板株式会社 | 被覆めっき鋼板 |
JP7417473B2 (ja) | 2020-05-20 | 2024-01-18 | 日鉄鋼板株式会社 | 被覆めっき鋼板 |
Also Published As
Publication number | Publication date |
---|---|
CA2780445A1 (en) | 2011-08-25 |
TW201144481A (en) | 2011-12-16 |
KR101692684B1 (ko) | 2017-01-03 |
KR20120112450A (ko) | 2012-10-11 |
TWI438302B (zh) | 2014-05-21 |
BR112012013190B1 (pt) | 2020-04-07 |
MX2012005996A (es) | 2012-08-08 |
EP2537954A1 (en) | 2012-12-26 |
CA2780445C (en) | 2014-02-04 |
AU2011216352B2 (en) | 2013-06-20 |
JP5118782B2 (ja) | 2013-01-16 |
AU2011216352A1 (en) | 2012-06-21 |
JPWO2011102434A1 (ja) | 2013-06-17 |
ES2657614T3 (es) | 2018-03-06 |
EP2537954A4 (en) | 2016-04-27 |
CN102762759A (zh) | 2012-10-31 |
KR20140146167A (ko) | 2014-12-24 |
MY180909A (en) | 2020-12-11 |
EP2537954B1 (en) | 2017-11-01 |
BR112012013190A2 (pt) | 2016-03-01 |
KR101678538B1 (ko) | 2016-11-22 |
KR20160137650A (ko) | 2016-11-30 |
US9080231B2 (en) | 2015-07-14 |
CN102762759B (zh) | 2015-11-25 |
US20120282488A1 (en) | 2012-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5118782B2 (ja) | 溶融めっき鋼材及びその製造方法 | |
CN111989420B (zh) | 镀覆钢材 | |
WO2012070694A1 (ja) | 溶融Al-Zn系めっき鋼板およびその製造方法 | |
JP5408384B2 (ja) | 塗装めっき鋼材 | |
CN117026132A (zh) | 熔融Al-Zn-Mg-Si-Sr镀覆钢板及其制造方法 | |
US20120135261A1 (en) | Metal-coated steel strip | |
WO2010137736A1 (ja) | 溶融Al-Zn系めっき鋼板 | |
US20230279534A1 (en) | Metal coated steel strip | |
JP2020143370A (ja) | 溶融Al−Zn−Mg−Si系めっき鋼板及びその製造方法、並びに、塗装鋼板及びその製造方法 | |
JP5751093B2 (ja) | 表面処理溶融めっき鋼材 | |
JP5527293B2 (ja) | 表面処理溶融めっき鋼材 | |
CN116324004B (zh) | 镀覆钢材 | |
KR102527548B1 (ko) | 도금 강재 | |
JP4629138B2 (ja) | 合金化溶融亜鉛めっき鋼板 | |
JP2023146981A (ja) | めっき鋼材及びその製造方法並びに表面処理鋼材 | |
WO2021199373A1 (ja) | 溶融Al-Zn-Mg-Si系めっき鋼板の製造方法及び塗装鋼板の製造方法 | |
WO2024048646A1 (ja) | めっき鋼材 | |
AU2011204744B2 (en) | Metal coated steel strip |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180004914.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11744720 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012500648 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 2780445 Country of ref document: CA |
|
REEP | Request for entry into the european phase |
Ref document number: 2011744720 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011744720 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 4571/DELNP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2012/005996 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011216352 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 20127014630 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2011216352 Country of ref document: AU Date of ref document: 20110217 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13513025 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201002554 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012013190 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012013190 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120531 |