CN115261852A - 热浸镀锌系钢板 - Google Patents
热浸镀锌系钢板 Download PDFInfo
- Publication number
- CN115261852A CN115261852A CN202210554110.7A CN202210554110A CN115261852A CN 115261852 A CN115261852 A CN 115261852A CN 202210554110 A CN202210554110 A CN 202210554110A CN 115261852 A CN115261852 A CN 115261852A
- Authority
- CN
- China
- Prior art keywords
- hot
- oxide
- steel sheet
- dip galvanized
- terms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 70
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 70
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 127
- 239000010959 steel Substances 0.000 claims abstract description 127
- 239000010410 layer Substances 0.000 claims abstract description 103
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 238000007731 hot pressing Methods 0.000 claims abstract description 87
- 239000011701 zinc Substances 0.000 claims abstract description 60
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 57
- 239000011787 zinc oxide Substances 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 109
- 239000002335 surface treatment layer Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 42
- 239000011651 chromium Substances 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims 6
- 238000000576 coating method Methods 0.000 abstract description 38
- 239000011248 coating agent Substances 0.000 abstract description 37
- 238000005260 corrosion Methods 0.000 abstract description 36
- 230000007797 corrosion Effects 0.000 abstract description 36
- 239000002344 surface layer Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 55
- 238000007747 plating Methods 0.000 description 36
- 239000007788 liquid Substances 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 238000005246 galvanizing Methods 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910000734 martensite Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 zirconium carbonate compound Chemical class 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 150000008040 ionic compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- DIZZIOFQEYSTPV-UHFFFAOYSA-N [I].CO Chemical compound [I].CO DIZZIOFQEYSTPV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005244 galvannealing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 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
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- 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
- B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0272—After-treatment with ovens
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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Abstract
本发明提供更简便地抑制热压后的表层的锌氧化物的过度生成，无涂装部的耐腐蚀性优异的热浸镀锌系钢板。本发明所述的热浸镀锌系钢板具备作为基材的基底钢板，在前述基底钢板上设置的热浸镀锌系层，和至少在单面的前述热浸镀锌系层上形成的表面处理层，前述表面处理层含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的粒状的氧化物，所述粒状的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化锌的标准生成自由能(ΔG0 Zn)小、并且比氧化铝的标准生成自由能(ΔG0 Al)大，前述粒状的氧化物的粒径为3nm以上且100nm以下。
Description
本申请是申请日为2016年3月31日、申请号为201680017777.6、发明名称为“热浸镀锌系钢板”的申请的分案申请。
技术领域
本发明涉及热浸镀锌系钢板。
背景技术
近年来为了环境的保护与防止地球温暖化，抑制化石燃料的消耗的要求高，所述要求对于各种制造业产生影响。例如，对于作为移动手段，日常生活、活动中不可欠缺的汽车也不例外，要求基于车身的轻量化等的燃油效率提高等。然而，在汽车中，简单地实现车身的轻量化在制品功能上不允许，需要确保适当的安全性。
汽车的结构多由铁系材料、特别是钢板形成，减少所述钢板的重量对于车身的轻量化而言是重要的。然而，如上所述，简单地减少钢板的重量是不允许的，同时要求确保钢板的机械强度。对于这样的钢板的要求不仅汽车制造业在各种制造业中也是同样的。因此，对于通过提高钢板的机械强度，从而即便与以往所使用的钢板相比进行薄壁化，也可以维持或提高机械强度的钢板进行了研究开发。
通常，具有高机械强度的材料在弯曲加工等成形加工中，存在形状冻结性降低的倾向，难以成形加工为复杂的形状。作为解决对于所述成形性的问题的手段之一，可以列举出所谓“热压法(也称为热冲压法(hot stamping method)、热压成形法(hot pressingmethod)或模压淬火法(die quenching method))”。在热压方法中，将作为成形对象的材料暂时加热到高温，对通过加热而软化了的钢板进行冲压加工而成形之后、进行冷却。根据所述热压方法，由于暂时将材料加热到高温而使其软化，因此能够容易地对作为对象的材料进行冲压加工。进而，通过成形后的基于冷却的淬火效果，能够提高材料的机械强度。因此，通过热压方法，能够得到兼具良好的形状冻结性和高机械强度的成形品。
然而，将所述热压方法应用于钢板时，钢板被加热到800℃以上的高温，从而使钢板的表面氧化，生成氧化皮(化合物)。因此，在进行热压加工之后，需要去除所述氧化皮的工序(所谓除氧化皮工序)，生产率降低。此外，在需要耐腐蚀性的部件等中，需要在加工后对部件表面进行防锈处理、金属包覆，需要表面清洁化工序以及表面处理工序，进而生产率降低。
作为抑制这样的生产率的降低的方法，例如，可以列举出预先对进行热压的钢板实施包覆的方法。作为钢板上的包覆，通常使用有机系材料、无机系材料等各种材料。其中，对于钢板具有牺牲防腐蚀作用的锌(Zn)系镀覆钢板从其的防腐蚀性能和钢板生产技术的观点出发，广泛用于汽车钢板等。
通过实施锌系的金属包覆，从而可以防止对钢板表面的氧化皮的生成，不需要除氧化皮等工序，因此成形品的生产率提高。此外，对于锌系的金属包覆也具有防锈效果，因此耐腐蚀性也提高。对镀覆钢板进行热压的方法公开于下述专利文献1～专利文献4中，所述镀覆钢板是对具有规定的成分组成的钢板实施锌系的金属包覆而成的。
在下述专利文献1～专利文献3中，作为热压用钢板，使用热浸镀锌钢板或合金化热浸镀锌钢板。通过将热浸镀锌钢板或合金化热浸镀锌钢板用于热压，从而可以对结构部件进行成形而不使铁氧化物(即、氧化皮)在表面形成。此外，在下述专利文献4中公开了在对锌系镀覆钢板进行了热压的热处理钢材的表面较厚地形成氧化锌层时，对热处理钢材的涂膜密合性、涂装后耐腐蚀性产生坏影响，因此对热处理钢材进行喷丸而去除氧化锌层、或降低氧化锌层的厚度之后进行涂装的发明。
此外，在下述专利文献5以及专利文献6中公开了改善对锌系镀覆钢板进行了热压的热处理钢材的涂膜密合性、涂装后耐腐蚀性的发明。在下述专利文献5中公开了将利用有机硅树脂覆膜而包覆表面的热浸镀锌钢板用作热压用钢板的发明，此外，在下述专利文献6中公开了将利用含有磷(P)以及硅(Si)的阻隔层(作为P例示出磷酸盐、作为Si例示出胶态二氧化硅)包覆的热浸镀锌钢板用作热压用钢板的发明。
此外，在下述专利文献7中公开了在锌镀覆层中添加与Zn相比容易氧化的元素(易氧化性元素)，在热压时的升温中在锌镀覆层的表层形成这些易氧化性元素的氧化物层从而防止锌的挥发的技术。
根据由下述专利文献5～专利文献7所公开的发明，锌镀覆层被前述的阻隔层包覆，因此抑制锌的蒸发，由此，中涂层涂膜、上涂层涂膜的密合性、涂装后耐腐蚀性良好。
现有技术文献
专利文献
专利文献1:日本特开2003－73774号公报
专利文献2:日本特开2003－129209号公报
专利文献3:日本特开2003－126921号公报
专利文献4:日本特开2004－323897号公报
专利文献5:日本特开2007－63578号公报
专利文献6:日本特开2007－291508号公报
专利文献7:日本特开2004－270029号公报
发明内容
发明要解决的问题
然而，在锌系镀覆钢板中，特别是对热浸镀锌钢板或合金化热浸镀锌钢板进行热压时，不能避免热压的加热中的锌的氧化，热压后的镀覆层中残存的金属锌量减少。金属锌量减少时，存在不仅涂装后耐腐蚀性，而且即便无涂装耐腐蚀性也劣化的情况。
并且，本发明人等对于由专利文献5所公开的、将由有机硅树脂覆膜包覆表面而成的热浸镀锌钢板用作热压用钢板从而得到的热处理钢材进行追加试验，结果明确虽然在重复干湿环境的循环腐蚀试验中的涂装后耐腐蚀性良好，但热压的加热中锌过度地氧化、无涂装的耐腐蚀性也未必良好。因此，对于由上述专利文献5所公开的发明所得到的热处理钢材，例如，不适于直接用于钢材的接合部位、部件(例如，加强件的板结合部、摇臂内部的点焊部附近等)。
另一方面，上述专利文献7中所公开的那样，通过在锌镀覆层中添加易氧化性元素，从而虽然抑制锌的氧化，但需要镀覆浴的温度管理、浮渣对应等操作上的新的研究。
因此，本发明是鉴于上述问题而做出的，作为本发明的目的在于提供更简便地抑制热压后的表层的锌氧化物的过度生成，无涂装部的耐腐蚀性优异的热浸镀锌系钢板。
用于解决问题的方案
本发明人等对于作为上述目的的热压用的镀覆钢板，进行深入研究，结果基于所得到的见解，想到以下那样的热浸镀锌系钢板。
本发明的主旨如以下所述。
(1)一种热浸镀锌系钢板，其具备：作为基材的基底钢板、在前述基底钢板上设置的热浸镀锌系层、和至少在单面的前述热浸镀锌系层上形成的表面处理层，前述表面处理层含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的粒状的氧化物，所述粒状的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化锌的标准生成自由能(ΔG0 Zn)小、并且比氧化铝的标准生成自由能(ΔG0 Al)大，前述粒状的氧化物的粒径为3nm以上且100nm以下。
(2)根据(1)记载的热浸镀锌系钢板，其中，前述表面处理层以每单面的含量计在以下示出的范围还含有含磷化合物、含钒化合物、含铜化合物、含铝化合物或含铬化合物的至少任一者。
含磷化合物：以P换算计0.0g/m2以上且0.01g/m2以下
含钒化合物：以V换算计0.0g/m2以上且0.01g/m2以下
含铜化合物：以Cu换算计0.0g/m2以上且0.02g/m2以下
含铝化合物：以Al换算计0.0g/m2以上且0.005g/m2以下
含铬化合物：以Cr换算计0.0g/m2以上且0.01g/m2以下
(3)根据(1)或(2)记载的热浸镀锌系钢板，其中，前述基底钢板具有如下化学组成：以质量％计含有C：0.05～0.4％、Si：0.5％以下、Mn：0.5～2.5％、P：0.03％以下、S：0.01％以下、酸可溶Al：0.1％以下、N：0.01％以下、B：0～0.005％、Ti：0～0.1％、Cr：0～0.5％、Nb：0～0.1％、Ni：0～1.0％、以及Mo：0～0.5％，余量为Fe以及杂质。
(4)根据(1)或(2)记载的热浸镀锌系钢板，其中，前述基底钢板具有如下化学组成：以质量％计含有C：0.05～0.4％、Si：0.5％以下、Mn：0.5～2.5％、P：0.03％以下、S：0.01％以下、酸可溶Al：0.1％以下、N：0.01％以下、B：0～0.005％、Ti：0～0.1％、Cr：超过0％且0.5％以下、Nb：0～0.1％、Ni：0～1.0％、Mo：0～0.5％，余量为Fe以及杂质，并且，满足Mn+Cr：0.5～3.0％的关系。
(5)根据(1)～(4)的任一项记载的热浸镀锌系钢板，其中，前述粒状的氧化物为金属氧化物。
(6)根据(1)～(5)的任一项记载的热浸镀锌系钢板，其中，前述粒状的氧化物为钛的氧化物或硅的氧化物。
(7)根据(1)～(6)的任一项记载的热浸镀锌系钢板，其中，前述粒状的氧化物的粒径为5nm以上且30nm以下。
(8)根据(1)～(7)的任一项记载的热浸镀锌系钢板，其中，前述粒状的氧化物的含量以金属换算计每单面为0.2g/m2以上且0.8g/m2以下。
(9)根据(1)～(8)的任一项记载的热浸镀锌系钢板，其中，前述表面处理层还含有以金属换算计每单面为0.05g/m2以上且0.35g/m2以下的碱土金属的氧化物，所述碱土金属的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化铝的标准生成自由能(ΔG0 Al)小。
(10)根据(9)记载的热浸镀锌系钢板，其中，前述碱土金属的氧化物为钙的氧化物或镁的氧化物。
(11)根据(9)或(10)记载的热浸镀锌系钢板，其中，前述碱土金属的氧化物的含量以金属换算计每单面为0.05g/m2以上且0.2g/m2以下。
(12)根据(1)～(11)的任一项记载的热浸镀锌系钢板，其为热压用热浸镀锌系钢板。
发明的效果
如以上说明的那样，根据本发明，抑制在热压中的表层的锌氧化物的生成，确保在热压后在镀覆层中残存的金属锌量，从而可以提高特别是无涂装部的耐腐蚀性。
具体实施方式
以下，对于本发明的适宜的实施方式进行详细地说明。
＜1.热浸镀锌系钢板＞
本发明的实施方式所述的热浸镀锌系钢板在基底钢板上具备热浸镀锌系层，进而，在所述热浸镀锌系层上的至少单面具备在以下详细叙述的表面处理层。该表面处理层含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的粒状的氧化物，所述粒状的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化锌的标准生成自由能(ΔG0 Zn)小、并且比氧化铝的标准生成自由能(ΔG0 Al)大，粒状的氧化物的粒径为3nm以上且100nm以下。具有所述构成的热浸镀锌系钢板可以适宜地用于之前说明的热压法。以下，对于所述热浸镀锌系钢板的构成进行详细地说明。
(1)基底钢板
对于本实施方式所述的热浸镀锌系钢板中所使用的基底钢板没有特别限定，可以使用具有公知的特性、化学组成的各种钢板。钢板的化学组成没有特别限定，优选为通过淬火而得到高强度的化学组成。例如，希望得到拉伸强度为980MPa以上的热处理钢材时，例如基底钢板由具有如下化学组成的淬火用钢形成：以质量％计含有C：0.05～0.4％、Si：0.5％以下、Mn：0.5～2.5％、P：0.03％以下、S：0.01％以下、酸可溶Al：0.1％以下、N：0.01％以下、B：0～0.005％、Ti：0～0.1％、Cr：0～0.5％、Nb：0～0.1％、Ni：0～1.0％、以及Mo：0～0.5％，余量为Fe以及杂质。
希望得到在淬火时强度不足980MPa的强度较低的热处理钢材时，基底钢板的化学组成也可以不在上述的范围。
从上述淬火时的淬火性的观点以及形成加热后的氧化锌层中所含的Mn、Cr氧化物的观点出发，优选以Mn、Cr量计为Mn+Cr：0.5～3.0％。更优选为Mn+Cr：0.7～2.5％。
作为钢板的化学组成，含有Mn、Cr时，在热压后在表层所形成的氧化锌层的一部分成为含有Mn、Cr的复合氧化物。通过形成这些含有Mn、Cr的复合氧化物，从而提高与覆膜成分、镀覆成分的密合性，耐模具凝结性优异。详细情况不明确，但认为通过形成这些复合氧化物，与氧化锌相比，所形成的覆膜致密，从而表现出良好的耐模具凝结性(mold-adhesionresistance)。
作为钢板的化学组成，含有Mn、Cr时，其含量优选以Mn+Cr计在质量％为0.5％以上且3.0％以下的范围含有，更优选为0.7％以上且2.5％以下的范围。Mn+Cr的含量不足0.5％时，有时在热压后在表层所形成的氧化锌和含有Mn、Cr的复合氧化物的形成不充分，难以表现出更良好的耐模具凝结性。另一方面，Mn+Cr的含量超过3.0％时，有时关于涂装密合性没有问题，但成本变高，并且，点焊部的韧性显著降低、镀覆的润湿性的劣化变得显著。
(2)热浸镀锌系层
作为本实施方式所述的热浸镀锌系层没有特别限定，可以使用通常已知的热浸镀锌系。具体而言，作为本实施方式所述的热浸镀锌系层，可以列举出热浸镀锌、合金化热浸镀锌、热浸镀Zn－55％Al、热浸镀Zn－11％Al、热浸镀Zn－11％Al－3％Mg、热浸镀Zn－7％Al－3％Mg、热浸镀Zn－11％Al－3％Mg－0.2％Si等。
需要说明的是，对于本发明作为对象的热浸镀锌系，即便除了以铝(Al)为主要成分的Zn－Al系合金镀覆以外，在镀覆浴以及镀覆层中也含有Al。其理由如以下所述。即、镀覆浴的温度为440～480℃左右，在所述温度区域，Zn与Fe接触时，Fe与Zn继续地合金化，从而产生浮渣。在镀覆浴中含有Al，从而在引起Fe与Zn的反应之前，引起Fe与Al的反应，结果，抑制浮渣的产生。根据所述理由，通常，在热浸镀锌浴中含有Al。
通常，对于热浸镀锌，在镀覆浴中含有0.2～0.3％的Al，在镀覆层中含有0.2～1.0质量％的Al，在合金化热浸镀锌中，在镀覆浴中含有0.1～0.2％的Al，在镀覆层中含有0.1～0.5质量％的Al。
镀覆层中的Al在镀覆覆膜形成时的基础上，在热压的加热时扩散，移动到镀覆层的表层。此时，Al与Zn相比优先氧化，形成由Al2O3形成的Al氧化膜。
作为本实施方式中的具体的镀覆操作，实施在保持处于熔融的状态的Zn或Zn合金的镀覆浴中使钢板浸渍，从所述镀覆浴提拉钢板的操作。对钢板的镀覆附着量的控制通过钢板的提拉速度、自设置于镀覆浴的上方的擦拭喷嘴喷出的擦拭气体的流量、流速调整等来进行。此外，合金化处理通过在如上所述的镀覆处理后，用瓦斯炉、感应加热炉、并用它们的加热炉等对镀覆后的钢板追加加热来进行。对于所述镀覆操作，可以通过卷材的连续镀覆法、或者切片单体的镀覆法的任意来进行镀覆。
所述热浸镀锌系层的厚度(即、热浸镀锌系层的附着量)优选为每单面20g/m2～100g/m2的范围。热浸镀锌系层的厚度为每单面不足20g/m2时，不能确保热压后的有效Zn量，耐腐蚀性不充分，故不优选。此外，热浸镀锌系层的厚度为每单面超过100g/m2时，镀覆层的加工性、密合性降低，因此不优选。更优选热浸镀锌系层的厚度为每单面30g/m2～90g/m2的范围。
(3)表面处理层
在如上所述的热浸镀锌系层上还形成有含有粒状的氧化物的表面处理层，所述粒状的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化锌的标准生成自由能(ΔG0 Zn)小、并且比氧化铝的标准生成自由能(ΔG0 Al)大。认为所述氧化物被锌系镀覆层中所含的Al所还原，与Zn相比优先氧化，从而抑制氧化锌的生成。
其中，“粒状的氧化物”意味着以如下氧化物为主体的物质：如硝酸盐、硫酸盐、锂盐等化合物那样、在作为以一次粒径计为数nm以上的固体在处理液中分散的状态下存在，而不在溶解于处理液中的状态下存在的氧化物。使用在这样的固体状态下在处理液中分散，在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化锌(ZnO)的标准生成自由能(ΔG0 Zn)小、并且比氧化铝(Al2O3)的标准生成自由能(ΔG0 Al)大的粒状的氧化物，从而可以提供特别是在涂装未蔓延的钢板结合部环境下的耐久性优异的热处理钢材。需要说明的是，所述粒状的氧化物在表面处理层中以颗粒的状态存在。
其中，900～1300K的温度区域的氧化锌(ZnO)、氧化铝(Al2O3)的标准生成自由能的具体的值可以通过参照“腐蚀防腐蚀协会编：腐蚀·防腐蚀手册”等公知的数据集而知。例如，900K以及1300K的氧化锌(ZnO)的标准生成自由能(ΔG0 Zn)分别约为-535kJ/mol、-460kJ/mol，900K以及1300K的氧化铝(Al2O3)的标准生成自由能(ΔG0 Al)分别约为-945kJ/mol、-880kJ/mol。
作为在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比ZnO的标准生成自由能(ΔG0 Zn)小、并且比Al2O3的标准生成自由能(ΔG0 Al)大的粒状的氧化物，例如，可以列举出硅(Si)的氧化物、钛(Ti)的氧化物、铬(Cr)的氧化物、钒(V)的氧化物、锰(Mn)的氧化物、硼(B)的氧化物等。
其中，金属元素的氧化物(即、金属氧化物)是稳定的，从容易获得等观点出发，是适宜的。作为所述金属氧化物，可以列举出Si氧化物、Ti氧化物、Cr氧化物、V氧化物等。需要说明的是，如Si那样，根据晶体结构成为半导体或金属的元素的氧化物也包含在金属氧化物中。
其中，Cr氧化物鉴于最近强烈谋求关照环境保护的倾向，自然不含6价铬，优选也不含有包含3价铬的铬成分、即为无铬，因此作为满足涉及上述的标准生成自由能的条件的粒状的氧化物，优选使用Si氧化物、Ti氧化物。
此外，满足涉及上述的标准生成自由能的条件的粒状的氧化物的粒径(一次粒径)为3nm以上且100nm以下。从涂装后耐腐蚀性的方面出发，氧化物粒径越小越有利，但颗粒径不足3nm时难以获得，在成本方面不利。此外，上述粒状的氧化物的粒径超过500nm时，担心由于表面积降低，因此在加热时与下层镀覆的反应性降低，故不优选。上述粒状的氧化物更优选的粒径为5nm以上且30nm以下。
需要说明的是，如上所述粒状氧化物的粒径(一次粒径)可以通过公知的方法测定，例如，可以通过如下方法测定：制作涂装后截面嵌入样品，测定多个点的覆膜中的氧化物颗粒的粒径，将所得到的测定结果平均而得到的值作为粒径的方法。
本实施方式所述的表面处理层由含有满足关于上述的标准生成自由能的条件的粒状氧化物的处理液形成。在本实施方式所述的表面处理层中含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的满足关于上述标准生成自由能的条件的粒状的氧化物。
所述的表面处理层中含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的粒状氧化物的热浸镀锌系钢板，由于在热压前存在于热浸镀锌层中并且在热压时所形成的Al氧化物，在表面处理层中所含有的氧化物被还原。该氧化物所还原成的金属颗粒与Zn相比容易形成氧化物，因此与Zn相比优先被氧化。认为其结果，抑制氧化锌的生成。
表面处理层中的粒状氧化物的附着量以金属换算计每单面不足0.1g/m2时，在热压中抑制氧化锌的生成所需要的氧化物还原而成的金属颗粒未充分地存在，不能抑制氧化锌的生成，不能确保足够的耐腐蚀性。另一方面，认为表面处理层中的粒状氧化物的附着量以金属换算计每单面超过1.2g/m2时，本实施方式中所述的热浸镀锌系钢板的成本上升、并且表面处理层的凝集力变弱，在热压后在表面处理层上形成的涂膜容易剥离。
所述的表面处理层中的粒状氧化物的附着量优选以金属换算计每单面为0.2g/m2以上且0.8g/m2以下。
其中，表面处理层中上述粒状氧化物的金属换算的附着量可以通过公知的方法而测定，例如，可以通过溶解表面处理层，使用电感耦合等离子体(Inductively CoupledPlasma：ICP)发射光谱分析法等来测定。
作为含有满足关于上述的标准生成自由能的条件的粒状氧化物的处理液，可以使用分散有硅、钛、锰等的氧化物粉末的处理液。此外，作为预先分散的处理液，更优选使用二氧化钛溶胶、二氧化硅溶胶。作为二氧化钛溶胶的具体的市售制品，例示出TaycaCorporation制的TKS(注册商标)系列。作为二氧化硅溶胶的具体的市售制品，例示日产化学株式会社制的Snowtex(注册商标)系列。
在表面处理层的形成中，可以将如上所述的二氧化钛溶胶、二氧化硅溶胶直接在热浸镀锌钢板上涂布，但为了改善处理液的稳定性、表面处理层的密合性，优选在混合有树脂、交联剂的处理液的基础上，在热浸镀锌系钢板上进行涂布。
作为所述树脂，使用如上所述的二氧化钛溶胶、二氧化硅溶胶时，优选使用水溶性或水分散性的树脂，作为树脂的种类，可以列举出聚氨酯树脂、聚酯树脂、环氧树脂、(甲基)丙烯酸系树脂、聚烯烃树脂、酚醛树脂、或这些树脂的改性物等。对于使用钛白粉末、二氧化硅粉末的情况，在上述的水系树脂的基础上，也可以使用将各种溶剂作为溶媒的溶剂系树脂。
作为所述交联剂，可以列举出硅烷偶联剂、碳酸锆化合物、有机钛化合物、噁唑啉聚合物、水溶性环氧化合物、水溶性三聚氰胺树脂、水分散嵌段异氰酸酯、水系氮丙叮化合物等。
需要说明的是，即便在混合如上所述的树脂、交联剂的情况下，满足关于上述的标准生成自由能的条件的粒状氧化物的含量也如上所述，在表面处理层中以金属换算计每单面设为0.1g/m2以上且1.2g/m2以下。
此外，作为优选在本实施方式所述的表面处理层中还含有的其它成分，例如，可以列举出在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能(ΔG0)比氧化铝的标准生成自由能(ΔG0 Al)小的、广义的碱土金属(即、作为第2族元素的铍、镁、钙、锶、钡、镭)的氧化物。
推测在表面处理层中含有如上所述的碱土金属的氧化物时，在热压时以通常的金属氧化物的状态稳定地存在，但与在热压的加热时所形成的氧化锌反应，形成与氧化锌的复合氧化物，从而抑制过度的锌氧化、蒸发。作为可以更高效地得到所述效果的碱土金属的氧化物，优选使用氧化镁或氧化钙。
表面处理层含有氧化镁或氧化钙时，其含量以金属换算计每单面优选设为0.05g/m2以上且0.35g/m2以下，更优选以金属换算计每单面为0.05g/m2以上且0.2g/m2以下。氧化镁或氧化钙的含量以金属换算计每单面不足0.05g/m2时，有时不能形成与足够的氧化锌的复合氧化物，难以高效地抑制Zn的氧化、蒸发。另一方面，氧化镁或氧化钙的含量以金属换算计每单面超过0.35g/m2时，有时产生由表面处理层的凝集力降低导致的对于密合性的不良。
本实施方式所述的表面处理层在如上所述的氧化物的基础上，可以以规定的含量范围内含有在以下详细叙述的含P化合物、含V化合物、含Cu化合物、含Al化合物或含Cr化合物的至少任一者。
含P化合物为含有磷作为构成元素的化合物。作为所述含P化合物，例如，可以列举出：磷酸、亚磷酸、膦酸、亚膦酸、次膦酸、三价膦酸、氧化膦、磷化氢等化合物、使这些化合物成为阴离子的离子化合物等。这些含P化合物均以试剂或制品的形式而被市售，可以容易地获得。这些含P化合物以在处理液中溶解的状态、或在处理液中以粉末的形式分散的状态存在，在表面处理层中以作为固体而分散的状态存在。
含V化合物为含有钒作为构成元素的化合物。作为所述含V化合物，例如，可以列举出包含五氧化钒的钒氧化物、包含偏钒酸铵的偏钒酸系化合物、包含钒酸钠的钒化合物、以及其它的含有V的化合物等。这些含V化合物均以试剂或制品的形式而被市售，能够容易地获得。这些含V化合物以在处理液中溶解的状态、或在处理液中以粉末的形式分散的状态存在，在表面处理层中以作为固体而分散的状态存在。
本实施方式所述的表面处理层优选以P以及V换算计分别在每单面为0.0g/m2以上且0.01g/m2以下的范围含有如上所述的选自含P化合物以及含V化合物的1种或2种以上的化合物。
如上所述的选自含P化合物以及含V化合物的1种或2种以上的化合物在热压时被氧化而成为氧化物，在热浸镀Zn系层与表面处理层的界面不均匀分布，形成含有P或V的至少任一者的凝集力弱的氧化物层。选自含P化合物以及含V化合物的1种或2种以上的化合物的含量以P以及V换算计分别为每单面在0.0g/m2以上且0.01g/m2以下的范围，从而在热压时所形成的如上所述的凝集力弱的氧化物层的厚度变薄，热压后的热浸镀Zn系层与表面处理层的密合性进一步提高。
表面处理层中的选自含P化合物以及含V化合物的1种或2种以上的含量为每单面超过0.01g/m2时，在热压时所形成的凝集力弱的氧化物层的厚度变厚，热浸镀Zn系层与表面处理层的密合性降低。其结果，产生在热压后表面处理层容易剥离，剥离的表面处理层在热压用的模具凝结的可能性。从热压后的热浸镀Zn系层与表面处理层的密合性的观点出发，表面处理层中的选自含P化合物以及含V化合物的1种或2种以上的化合物的含量更优选以P以及V换算计分别为每单面0.0g/m2以上且0.003g/m2以下。
含Cu化合物为含有铜作为构成元素的化合物。作为所述含Cu化合物，例如，可以列举出金属Cu、氧化铜、各种有机铜化合物、各种无机铜化合物、各种铜络合物等。这些含Cu化合物均以试剂或制品的形式而被市售，能够容易地获得。这些含Cu化合物以在处理液中溶解的状态、或在处理液中以粉末的形式分散的状态存在，在表面处理层中以作为固体而分散的状态存在。
本实施方式中所述的表面处理层优选在以Cu换算计每单面为0.0g/m2以上且0.02g/m2以下的范围含有如上所述的选自含Cu化合物的1种或2种以上的化合物。
如上所述的选自含Cu化合物的1种或2种以上的化合物在热压时被氧化而成为氧化物，在Zn系镀覆层与表面处理层的界面不均匀分布，形成含有Cu的凝集力弱的氧化物层。选自含Cu化合物的1种或2种以上的化合物的含量以Cu换算计为每单面0.0g/m2以上且0.02g/m2以下的范围，从而在热压时所形成的如上所述的凝集力弱的氧化物层的厚度变薄，热压后的热浸镀Zn系层与表面处理层的密合性进一步提高。
表面处理层中的选自含Cu化合物的1种或2种以上的含量为每单面超过0.02g/m2时，在热压时所形成的凝集力弱的氧化物层的厚度变厚，热浸镀Zn系层与表面处理层之间的密合性降低。其结果，产生在热压后表面处理层容易剥离，剥离的表面处理层在热压用的模具凝结的可能性。并且，Cu与作为基底钢板的主成分的Fe相比为贵元素，因此对于耐腐蚀性存在降低的倾向。从热压后的热浸镀Zn系层与表面处理层之间的密合性的观点出发，表面处理层中的选自含Cu化合物的1种或2种以上的化合物的含量更优选以Cu换算计为每单面0.0g/m2以上且0.005g/m2以下。
含Al化合物为含有铝作为构成元素的化合物。作为所述含Al化合物，例如，可以列举出金属Al、氧化铝、氢氧化铝、以铝离子为阳离子的离子化合物等。这些含Al化合物均以试剂或制品的形式而被市售，能够容易地获得。这些含Al化合物以在处理液中溶解的状态、或在处理液中以粉末的形式分散的状态存在，在表面处理层中以作为固体而分散的状态存在。
本实施方式所述的表面处理层优选以Al换算计每单面为0.0g/m2以上且0.005g/m2以下的范围含有如上所述的选自含Al化合物的1种或2种以上的化合物。
如上所述的选自含Al化合物的1种或2种以上的化合物在热压时被氧化而成为氧化物，在表面处理层的表面稠化。选自含Al化合物的1种或2种以上的化合物的含量以Al换算计在每单面为0.0g/m2以上且0.005g/m2以下的范围，从而在热压时在表面处理层的表面所形成的含有Al的氧化物的存在比率变小，可以防止这些含有Al的氧化物向热压用的模具的凝结。
表面处理层中的选自含Al化合物的1种或2种以上的含量为每单面超过0.005g/m2时，在热压时所形成的含有Al的氧化物的存在比率变大。对于这些含有Al的氧化物，在热压用的模具上凝结，并且阻碍化学转化处理覆膜的形成，因此在热压时所形成的含有Al的氧化物的存在比率变大，从而含有Al的氧化物向热压用的模具的凝结增加，操作性降低。从所述操作性的观点出发，表面处理层中的选自含Al化合物的1种或2种以上的化合物的含量以Al换算计更优选为每单面0.0g/m2以上且0.002g/m2以下。
含Cr化合物为含有铬作为构成元素的化合物。作为所述含Cr化合物，例如，可以列举出金属Cr、具有各种价数的铬化合物、以及将具有各种价数的铬离子作为阳离子的离子化合物等。这些含Cr化合物以在处理液中溶解的状态、或在处理液中以粉末的形式分散的状态存在，在表面处理层中以作为固体而分散的状态存在。
含Cr化合物根据价数在性能以及性质上不同，对于6价铬化合物，大量存在有害的化合物。如先前所述的那样，鉴于最近强烈要求考虑环境保护的倾向，本实施方式所述的表面处理层优选尽力不含有如上所述的含Cr化合物，更优选为无铬。
从如上所述的观点出发，本实施方式所述的表面处理层优选在以Cr换算计每单面为0.0g/m2以上且0.01g/m2以下的范围含有如上所述的选自含Cr化合物的1种或2种以上的化合物，更优选不含含Cr化合物。
对于所述的表面处理层的形成方法，将含有满足关于上述的标准生成自由能的条件的粒状的氧化物的处理液涂布到锌镀覆钢板的表面、进行干燥以及烘烤即可。
涂布方法不限定特定的方法，例示出将基底钢板浸渍到处理液中、或对基底钢板的表面喷雾处理液，之后以成为规定附着量的方式通过辊、气体吹送来控制附着量的方法，用辊涂、棒涂进行涂布的方法。
此外，干燥、烘烤方法若为可以使分散介质(主要是水)挥发的方法即可，并不限定特定的方法。其中，在过度地高温下进行加热时，担心表面处理层的均匀性降低，相反，在过度的低温下进行加热时，担心生产率降低。因此，为了稳定且高效地制造具有优异的特性的表面处理层，优选将涂布后的表面处理层在80℃～150℃程度的温度下进行5秒～20秒左右加热。
此外，表面处理层的形成在镀覆钢板的制造生产线中以在线方式进行是经济的，因此优选，也可以在另外的生产线中形成、或者也可以在用于成形的冲切之后形成。
其中，表面处理层中的上述含P化合物、含V化合物、含Cu化合物、含Al化合物、含Si化合物、以及、含Cr化合物的含量可以通过公知的方法测定，例如，可以事先用截面能量分散型X射线(Energy Dispersive X－ray：EDX)分析等确认表面处理层中的各种化合物为关注的上述含有化合物，在此基础上将覆膜溶解，使用ICP(Inductively Coupled Plasma、电感耦合等离子体)发射光谱分析法等来测定。
＜2.对于热压工序＞
将热压法应用于如先前所说明的那样的热浸镀锌系钢板时，热浸镀锌系钢板加热至规定的温度为止，然后进行压制成形。本实施方式所述的热浸镀锌系钢板的情况下，进行热压成形，之后通常加热到700～1000℃，在快速冷却后制成马氏体单相、或使马氏体以体积率计为90％以上的情况下，加热温度的下限温度设为Ac3点以上是重要的。本发明的情况下，也包含快速冷却后马氏体/铁素体的2相区域的情况，因此作为加热温度优选如上所述设为700～1000℃。
热压法中，存在基于缓慢加热的热压和基于快速加热的热压的2个方法。作为使用的加热方法，可以列举出电炉、瓦斯炉、火焰加热、通电加热、高频加热、感应加热等，加热时的气氛也没有特别限制，作为显著地得到本发明的效果的加热方法，优选使用作为快速加热的通电加热、感应加热等。
基于缓慢加热的热压法中，使用加热炉的辐射加热。首先，将本实施方式所述的热浸镀锌系钢板用作热压用钢板，装入到加热炉(瓦斯炉、电炉等)中。在加热炉内，将热压用钢板加热到700～1000℃，根据条件在该加热温度下进行保持(均热)。由此，热浸镀锌系层中的熔融Zn与Fe键合，成为固相(Fe－Zn固溶体相)。使热浸镀锌系层中的熔融Zn与Fe键合，进行固相化之后，从加热炉抽出钢板。需要说明的是，也可以通过均热使热浸镀锌系层中的熔融Zn与Fe键合，作为Fe－Zn固溶体相以及ZnFe合金相而进行固相化，然后从加热炉抽出钢板。
与之相对，可以将热浸镀锌系钢板加热到700～1000℃而无保持时间、或、将保持时间设为短时间，从加热炉抽出钢板。所述情况下，将钢板加热到700～1000℃之后，至热浸镀锌系层中的熔融Zn与Fe键合而成为固相(Fe－Zn固溶体相或ZnFe合金相)为止进行冷却而不通过压制成形等对钢板赋予应力。具体而言，至少钢板的温度冷却至热浸镀锌系层固相化的温度为止。例如，在热浸镀锌层、合金化热浸镀锌层中，冷却至钢板的温度为782℃以下为止。冷却后，如在以下说明的那样，使用模具而边对钢板进行压制边进行冷却。另一方面，加热温度为782℃以下的情况下，热浸镀锌系层为固相原样，因此可以从加热炉抽出钢板后，快速地进行压制成形。
在基于快速加热的热压中，同样地将本实施方式所述的热浸镀锌系钢板用作热压用钢板，快速加热至700～1000℃为止。快速加热例如通过通电加热或感应加热来实施。所述情况下的平均加热速度为20℃/秒以上。快速加热的情况，将热浸镀锌系钢板加热至700～1000℃，然后，至热浸镀锌系层中的熔融Zn与Fe键合成为固相(Fe－Zn固溶体相或ZnFe合金相)为止进行冷却而不通过压制成形等对钢板赋予应力。具体而言，至少钢板的温度冷却至热浸镀锌系层固相化的温度为止。例如，在热浸镀锌层、合金化热浸镀锌层中，冷却至钢板的温度为782℃以下为止。冷却后，如在以下说明的那样，使用模具而边对钢板进行压制边进行冷却。加热温度为782℃以下的情况下，热浸镀锌系层为固相原样，因此可以从加热炉抽出钢板后，快速地进行压制成形。
抽出的钢板使用模具进行压制。压制钢板时，通过模具使钢板冷却。在模具内，冷却介质(例如水等)循环，模具对钢板进行排热冷却。通过以上的工序，利用通常的加热而制造热压钢材。
使用具有本实施方式所述的表面处理层的热浸镀锌系钢板而制造的热压钢材具有优异的耐久性。
使用以往的镀覆钢板，实施通常基于加热的热压的情况下，在加热炉中使钢板均热。此时，在热压用钢板的镀覆层的表层形成锌氧化膜，但通过长时间的均热加热形成大量的锌氧化膜，在热压后的覆膜中残存的金属锌量减少。因此，存在与加热之前的锌镀覆钢材比较时，热压钢材的无涂装耐腐蚀性显著降低的情况。
然而，对于本实施方式所述的热浸镀锌系钢板，在表面处理层中含有满足关于如上所述的标准生成自由能的条件的粒状的氧化物，从而在热压时抑制氧化锌的生成，在热压后的表层确保金属锌量，因此发挥良好的无涂装耐腐蚀性。
实施例
在以下，边示出实施例边更具体地说明本发明的实施方式所述的热浸镀锌系钢板的作用效果。需要说明的是，在以下示出的实施例仅为本发明所述的热浸镀锌系钢板的一个例子，本发明所述的热浸镀锌系钢板并不限于下述的实施例。
＜基底钢板＞
在以下，首先制造具有以下的表1中所述的化学组成的钢水。之后，使用制造的各个钢水，通过连续铸造法而制造板坯。对所得到的板坯进行热轧，制造热轧钢板。接着，对热轧钢板进行酸洗，然后实施冷轧，制造冷轧钢板，制作具有表1中记载的化学组成的钢#1～#8的钢板。如表1所示，各钢种的钢板的板厚均为1.6mm。
[表1]
＜热浸镀锌系层＞
对钢#1～#8的钢板进行热浸镀锌处理，之后，实施合金化处理。在合金化处理中的最高温度均为530℃，加热约30秒之后，冷却至室温，制造合金化热浸镀锌钢板(GA)。此外，使用钢#1，进行热浸镀锌处理而不进行合金化处理，制造热浸镀锌钢板(GI)。
进而，对于钢#1，使用熔融Zn－55％Al、熔融Zn－6％Al－3％Mg、熔融Zn－11％Al－3％Mg－0.2％Si的3种镀覆浴，进行各种热浸镀锌，制造热浸镀锌系钢板A1～A3。
A1：熔融Zn－55％Al
A2：熔融Zn－6％Al－3％Mg
A3：熔融Zn－11％Al－3％Mg－0.2％Si
此外，对于钢#1，进行电镀锌处理，制造电镀锌钢板(EG)。
其中，在上述的热浸镀锌系钢板中，热浸镀锌系层的附着量设为50g/m2。
需要说明的是，对于上述热浸镀锌钢板的镀覆覆膜中的Al浓度通过以下的方法求出。即、从各热浸镀锌系钢板采取样品。在10％HCl水溶液中溶解所采取的样品的热浸镀锌系层，通过ICP发射光谱分析法进行热浸镀锌系层的组成分析。基于所得到的分析结果，求出每单面的Al浓度(质量％)。将所得到的结果总结示出于以下的表3。
＜表面处理层＞
接着，为了形成成为在表2中所示的组成以及附着量的覆膜，使用水混合氧化物以及试剂。粉末状态的氧化物分散于添加有树脂的水中，用球磨机将粉末粉碎至在树脂成分酸溶液中分散的程度，然后使用。用棒涂涂布所得到的处理液，在最高到达温度100℃下保持8秒钟的条件下使用烘箱进行干燥，从而制造热压用镀覆钢板。对于处理液的附着量，以表面处理层中的氧化物的金属换算的每单面的附着量成为表2中所示的数值的方式，利用液的稀释以及棒涂的档位来调整。
表2中的各成分(符号)如以下所述。
(i)氧化物等：Ti氧化物、Si氧化物
TPA：二氧化钛粉末(IoLiTec GmbH制)、粒径10～30nm(目录值)
TPB：二氧化钛粉末(Tayca Corporation TITANIX JA－1)、粒径180nm(目录值)
TZ：二氧化钛溶胶(Tayca Corporation二氧化钛溶胶TKS－203)、粒径6nm(目录值)
SZ：二氧化硅溶胶(日产化学工业株式会社Snowtex ST－C)、粒径10～20nm(目录值)
MP：氧化锰(Mn3O4)粉末(IOX Co.,Ltd.制)、平均粒径25nm(目录值)
需要说明的是，上述5种氧化物为在相同温度下的标准生成自由能(ΔG0)比ZnO的标准生成自由能(ΔG0 Zn)小、并且比Al2O3的标准生成自由能(ΔG0 Al)大的物质。
(ii)碱土：碱土金属的氧化物
Mg：氧化Mg(高纯度化学株式会社氧化镁)
Ca：氧化Ca(高纯度化学株式会社氧化钙)
Sr：氧化Sr(高纯度化学株式会社氧化锶)
(iii)树脂
A：氨基甲酸酯系树脂乳液(第一工业制药株式会社Superflex(注册商标)E－2000)
B：氨基甲酸酯系树脂乳液(第一工业制药株式会社Superflex(注册商标)150)
C：聚酯树脂乳液(东洋纺株式会社Vylonal(注册商标)MD1480)
(iv)交联剂
M：三聚氰胺树脂(Mitsui Cytec Ltd.Cymel(注册商标)325)
Z：碳酸锆铵(Kishida Chemical Co.,Ltd.碳酸锆铵溶液)
S：硅烷偶联剂(日美商事株式会社Sila-Ace S510)
(v)颜料
PZ：亚磷酸锌(东邦颜料株式会社NP－530)(含P化合物)
Al：氧化铝溶胶(日产化学株式会社AS－200)(含Al化合物)
V：钒酸钾(一般试剂)(含V化合物)
Cr：氧化Cr(VI)(一般试剂)(含Cr化合物)
Cu：氧化铜(II)(一般试剂)(含Cu化合物)
[表2]
[表3]
＜热压工序＞
表面处理层的形成工序后，对于各试验编号的钢板，用炉加热的加热方式进行热压加热，实施热压。在炉加热中，将炉内气氛设为910℃、将空燃比设为1.1，钢板温度达到900℃后快速地从炉内取出。
热压加热后，冷却至钢板温度为700℃为止。冷却后，利用具备水冷夹套的平板模具，夹持钢板，制造热压钢材(钢板)。即便在热压时冷却速度慢的部分，在作为马氏体相变开始点的360℃左右为止，以50℃/秒以上的冷却速度进行冷却、淬火。
＜评价方法＞
[氧化锌量的定量]
作为基于化学分析的氧化锌层的定量方法，使用用5％碘－甲醇溶液溶解镀覆层，将产生的残査溶解于盐酸中，进行定量的方法，用重铬酸铵水溶液溶解表面的氧化膜进行定量的方法的任一种。其中，对于进行溶解的溶液，可以使用各自的空白溶液，用ICP法等发射光谱分析等进行定量。
此外，作为基于物理分析的氧化锌层的定量方法，用X射线衍射求出源自ZnO的峰强度即可。此时，若预先氧化锌量使用已知的标准样品，制作表示氧化锌量与源自ZnO的峰强度的关系的标准曲线，则可以根据来自特定衍射面的峰强度，对生成的氧化锌量进行定量。
在本实施例中，用使用Co管球的X射线衍射装置，根据ZnO的[100]面的衍射峰强度基于以下的式(1)而算出生成氧化锌量。
生成氧化锌量＝XZ－XZ0···式(1)
其中，在上述式(1)中，XZ为热压加热后的ZnO[100]面的衍射峰强度，XZ0为热压加热前的ZnO[100]面的衍射峰强度。将所得到的生成氧化锌量与作为比较例而实施的无表面处理层的GA以及锌系镀覆钢板进行比较，将生成氧化锌量几乎没有的情况设为A、将生成氧化锌量少的情况设为B、将生成氧化锌量多的情况设为C。
[耐腐蚀性试验]
用聚酯带对评价试验片的端面以及背面进行遮蔽，实施90个循环的下述循环条件的循环腐蚀试验。
○循环条件
将盐水喷雾(SST、5％NaCl、35℃气氛)2小时→干燥(60℃)2小时→湿润(50℃、98％RH)4小时作为1个循环来实施。
之后，去除聚酯带之后，用柠檬酸铵溶液溶解·去除腐蚀生成物。将评价面划分为8等分，在各分区，用尖头千分尺测定腐蚀部的板厚，根据与实施了遮蔽的健全部的差，求出各分区中由腐蚀导致的板厚减少。所得到的各分区的板厚减少值之中，算出上位3点的平均值，作为各试验片的腐蚀深度。
表3中的“耐腐蚀性”栏的“G”意味着产生超过0.5mm的腐蚀深度。“F”意味产生0.4mm～不足0.5mm的腐蚀深度。“E”意味着产生0.3mm～不足0.4mm的腐蚀深度。“D”意味着产生0.2mm～不足0.3mm的腐蚀深度。“C”意味着产生0.15mm～不足0.2mm的腐蚀深度。“B”意味着产生0.10mm～不足0.15mm的腐蚀深度。“A”意味着产生0.10mm以下的腐蚀深度。在所述耐腐蚀性试验中，为“F”、“E”、“D”、“C”、“B”或“A”时，判断为耐腐蚀性优异。
[耐凝结性试验]
作为将向模具的凝结性定量化的指标，使用上述的平板模具，测定通过热压而得到的钢板表面的覆膜密合性，从而进行定量化。
具体而言，对于所得到的钢板的表面，使用Nichiban Co.,Ltd.制的聚酯带，进行热压成形后的表层覆膜的剥离试验。此时，将剥离带的剥离量作为基底的透过度情况，使用Minolta Co.,Ltd.制的色彩色差计CR－300，作为亮度指数进行评价。评价方法将亮度指数L*的N＝3平均值(L*ave)为55以下的情况设为“C”，表层覆膜的剥离大，对模具的耐凝结性差。此外，将L*ave超过55且60以下时设为“B”、将L*ave超过60时设为“A”。对于“A”、“B”，判断为抑制表层覆膜的剥离、对模具的耐凝结性优异。
[表4]
[表5]
[表6]
[表7]
[表8]
[表9]
如上述表3所明确的那样，对于本发明所述的热浸镀锌系钢板，可知不仅表现出抑制热压后的表层的锌氧化物的过度生成，优异的耐腐蚀性，而且具有优异的耐模具凝结性。
以上，对于本发明的适宜实施方式进行了详细地说明，但本发明并不限于所述例子。具有本发明所述的技术领域中通常的知识的技术人员，在本发明记载的技术的思想的范围内，可以想到各种变更例或修正例是明确的，对此，可知自然也处于本发明的技术的范围。
Claims (12)
1.一种热压用热浸镀锌系钢板，其具备：
作为基材的基底钢板、
在所述基底钢板上设置的热浸镀锌系层、和
至少在单面的所述热浸镀锌系层上形成的表面处理层，
所述表面处理层含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的粒状的氧化物，所述粒状的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能ΔG0比氧化锌的标准生成自由能ΔG0 Zn小、并且比氧化铝的标准生成自由能ΔG0 Al大，进而，以每单面的含量计按照以下所示的范围含有含磷化合物或含钒化合物，所述表面处理层还含有树脂，所述树脂不包含直链硅树脂，
所述粒状的氧化物的粒径为3nm以上且100nm以下，
含磷化合物：以P换算计0.0017g/m2以上且0.003g/m2以下，
含钒化合物：以V换算计0.0024g/m2以上且0.01g/m2以下。
2.根据权利要求1所述的热压用热浸镀锌系钢板，其中，所述表面处理层还以每单面的含量计按照以下所示的范围含有：含铜化合物、含铝化合物或含铬化合物的至少任一者，
含铜化合物：以Cu换算计0.0g/m2以上且0.02g/m2以下，
含铝化合物：以Al换算计0.0g/m2以上且0.005g/m2以下，
含铬化合物：以Cr换算计0.0g/m2以上且0.01g/m2以下。
3.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述基底钢板具有如下化学组成：以质量％计含有
C：0.05～0.4％，
Si：0.5％以下，
Mn：0.5～2.5％，
P：0.03％以下，
S：0.01％以下，
酸可溶Al：0.1％以下，
N：0.01％以下，
B：0～0.005％，
Ti：0～0.1％，
Cr：0～0.5％，
Nb：0～0.1％，
Ni：0～1.0％，
Mo：0～0.5％，
余量为Fe以及杂质。
4.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述基底钢板具有如下化学组成：以质量％计含有
C：0.05～0.4％，
Si：0.5％以下，
Mn：0.5～2.5％，
P：0.03％以下，
S：0.01％以下，
酸可溶Al：0.1％以下，
N：0.01％以下，
B：0～0.005％，
Ti：0～0.1％，
Cr：超过0％且为0.5％以下，
Nb：0～0.1％，
Ni：0～1.0％，
Mo：0～0.5％，
余量为Fe以及杂质，
并且，满足Mn+Cr：0.5～3.0％的关系。
5.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述粒状的氧化物为金属氧化物。
6.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述粒状的氧化物为钛的氧化物。
7.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述粒状的氧化物的粒径为5nm以上且30nm以下。
8.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述粒状的氧化物的含量以金属换算计每单面为0.2g/m2以上且0.8g/m2以下。
9.根据权利要求1或2所述的热压用热浸镀锌系钢板，其中，所述表面处理层还含有以金属换算计每单面为0.05g/m2以上且0.35g/m2以下的碱土金属的氧化物，所述碱土金属的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能ΔG0比氧化铝的标准生成自由能ΔG0 Al小。
10.根据权利要求9所述的热压用热浸镀锌系钢板，其中，所述碱土金属的氧化物为钙的氧化物或镁的氧化物。
11.根据权利要求9或10所述的热压用热浸镀锌系钢板，其中，所述碱土金属的氧化物的含量以金属换算计每单面为0.05g/m2以上且0.2g/m2以下。
12.一种热压用热浸镀锌系钢板，其具备：
作为基材的基底钢板、
在所述基底钢板上设置的热浸镀锌系层、和
至少在单面的所述热浸镀锌系层上形成的表面处理层，
所述表面处理层含有以金属换算计每单面为0.1g/m2以上且1.2g/m2以下的粒状的氧化物，所述粒状的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能ΔG0比氧化锌的标准生成自由能ΔG0 Zn小、并且比氧化铝的标准生成自由能ΔG0 Al大，进而，含有以金属换算计每单面为0.05g/m2以上且0.35g/m2以下的碱土金属的氧化物，所述碱土金属的氧化物在900～1300K的温度区域中在同一温度下的氧化物的标准生成自由能ΔG0比氧化铝的标准生成自由能ΔG0 Al小，进而，以每单面的含量计按照以下所示的范围含有含磷化合物或含钒化合物，所述表面处理层还含有树脂，所述树脂不包含直链硅树脂，
所述粒状的氧化物的粒径为3nm以上且100nm以下，
含磷化合物：以P换算计0.0017g/m2以上且0.003g/m2以下，
含钒化合物：以V换算计0.0024g/m2以上且0.01g/m2以下。
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| EP3263742B1 (en) | 2023-12-13 |
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