TWI792932B - 表面處理鋼材 - Google Patents
表面處理鋼材 Download PDFInfo
- Publication number
- TWI792932B TWI792932B TW111107688A TW111107688A TWI792932B TW I792932 B TWI792932 B TW I792932B TW 111107688 A TW111107688 A TW 111107688A TW 111107688 A TW111107688 A TW 111107688A TW I792932 B TWI792932 B TW I792932B
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- Prior art keywords
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- film
- plating layer
- amorphous phase
- solution
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 88
- 239000010959 steel Substances 0.000 title claims abstract description 88
- 238000004381 surface treatment Methods 0.000 title description 21
- 238000007747 plating Methods 0.000 claims abstract description 105
- 239000011701 zinc Substances 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 5
- -1 that is Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract 5
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 90
- 239000010410 layer Substances 0.000 description 86
- 239000000243 solution Substances 0.000 description 77
- 230000007797 corrosion Effects 0.000 description 42
- 238000005260 corrosion Methods 0.000 description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- 239000012948 isocyanate Substances 0.000 description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 description 19
- 238000002156 mixing Methods 0.000 description 19
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 19
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 18
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 18
- 235000019838 diammonium phosphate Nutrition 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000010936 titanium Substances 0.000 description 15
- 239000003973 paint Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 150000003682 vanadium compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 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
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- BEWZPBWLGIPWFP-UHFFFAOYSA-N [V].P(=O)(=O)[Mo] Chemical compound [V].P(=O)(=O)[Mo] BEWZPBWLGIPWFP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 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
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Classifications
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- 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
-
- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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Abstract
本案的表面處理鋼材具有:鋼板、形成於前述鋼板上且含鋅的鍍敷層、及形成於前述鍍敷層上的皮膜;前述皮膜的厚度為100nm以上且1000nm以下;前述皮膜是由非晶質相A與非晶質相B所構成,所述非晶質相A含有下述元素作為構成元素:Si、C、O、P、Zn及V,還有選自Ti、Zr及Al所構成群組之1種或2種以上,且以EDS進行分析時,Zn與Si之峰值強度比即Zn/Si會是1.0以上,V與P之質量比即V/P會是0.050~1.000;所述非晶質相B含有Si、O、Zn,且以EDS進行分析時,Zn與Si之峰值強度比即Zn/Si會小於1.0;前述非晶質相A之Zn含量為10質量%以下;在厚度方向的剖面中,前述鍍敷層與前述非晶質相B之界面長度佔前述鍍敷層與前述皮膜之界面長度的30%以上。
Description
發明領域
本發明是有關於表面處理鋼材。
本案基於2021年3月4日在日本提出申請之特願2021-034369主張優先權,並在此援引其內容。
發明背景
以往,鋼板表面形成有以鋅為主體之鍍敷層的鍍敷鋼板(鋅系鍍敷鋼板)被使用在汽車或建材、家電製品等廣泛用途上。通常在鍍敷鋼板表面上會施予無鉻的化學轉化處理,藉此不實施塗油即可賦予進一步的耐蝕性。
該化學轉化處理所形成之化學轉化處理皮膜需要均勻披覆於表面,且其與鍍敷之附著性需要優異、耐蝕性亦需要優異。惟,鋅系鍍敷鋼板表面由於受到氧化皮膜所披覆,因此就算想要形成化學轉化處理皮膜,氧化皮膜也會成為阻礙而化學轉化處理皮膜之附著性會降低,有時會發生化學轉化處理皮膜附著性降低所導致之塗裝不良、塗裝不均,或者,導致化學轉化處理皮膜從鍍敷層剝離。
面對如此之課題,例如專利文獻1揭示:在含鋅之鍍敷鋼板上形成下述皮膜,該皮膜含有丙烯酸樹脂、鋯、釩、磷、鈷;皮膜剖面中自表面起至膜厚1/5厚度為止之區域中,丙烯酸樹脂之面積率為80~100面積%;自皮膜之膜厚中心起朝前述表面側至膜厚1/10厚度為止之區域、與自前述膜厚中心起朝前述鍍敷層側至膜厚1/10厚度為止之區域,此兩者所構成的區域中,丙烯酸樹脂之面積率為5~50面積%;藉此,便可獲得一種與接著劑之接著性良好且具有優異耐蝕性的皮膜。
專利文獻2則揭示一種表面處理鋼板,包含鋼板及樹脂系化學轉化處理皮膜;該樹脂系化學轉化處理皮膜以重量比50/1~1/1之範圍含有基質(matrix)樹脂、與分散於該基質樹脂中的難溶性鉻酸鹽的膠體粒子;關於該膠體,就分散於該基質樹脂中之粒子的平均粒徑而言為小於1μm。
專利文獻2記載,該表面處理鋼板之耐鉻溶出性、SST(240hr)、加工部耐蝕性、處理液穩定性優異。
專利文獻3揭示一種化學轉化處理鋼板,具備:具有Zn系鍍敷層的Zn系鍍敷鋼板、及配置於前述Zn系鍍敷層上的化學轉化處理皮膜,該Zn系鍍敷層含有Al:0.1~22.0質量%;前述化學轉化處理皮膜具有:配置於前述Zn系鍍敷層表面且含有V、Mo及P的第1化學轉化處理層、及配置於前述第1化學轉化處理層上且含有4A族金屬含氧酸鹽的第2化學轉化處理層;前述化學轉化處理皮膜中,5價V相對總V之比率為0.7以上。
專利文獻3揭示,該化學轉化處理鋼板是一種以Zn系鍍敷鋼板為母板的化學轉化處理鋼板,其即使將塗佈後的化學轉化處理液以低溫且短時間進行乾燥,也能加以製造,且耐蝕性及耐發黑性優異。
專利文獻4揭示一種表面處理鋼材,(1)在鋼材表面塗佈水系金屬表面處理劑並使其乾燥,藉此形成含有各成分的複合皮膜;所述水系金屬表面處理劑是由(2)有機矽化合物(W)、(3)選自氫氟酸鈦或氫氟酸鋯之至少1種氟化合物(X)、(4)磷酸(Y)、與(5)釩化合物(Z)所構成;所述有機矽化合物(W)之平均分子量為1000~10000,並且是將分子中含有1個胺基之矽烷偶合劑(A)、與分子中含有1個環氧丙基之矽烷偶合劑(B),以固體成分質量比[(A)/(B)]計0.5~1.7之比例調配而得,且其在分子內含有2個以上的官能基(a)與1個以上的親水性官能基(b);所述官能基(a)以式-SiR
1R
2R
3(式中,R
1、R
2及R
3相互獨立表示烷氧基或羥基,且至少1者表示烷氧基)來表示,所述親水性官能基(b)是選自羥基(不同於官能基(a)所能包含者)及胺基之至少1種;並且,在該複合皮膜之各成分中,(6)有機矽化合物(W)與氟化合物(X)之固體成分質量比[(X)/(W)]為0.02~0.07,(7)有機矽化合物(W)與磷酸(Y)之固體成分質量比[(Y)/(W)]為0.03~0.12,(8)有機矽化合物(W)與釩化合物(Z)之固體成分質量比[(Z)/(W)]為0.05~0.17,且(9)氟化合物(X)與釩化合物(Z)之固體成分質量比[(Z)/(X)]為1.3~6.0。
根據專利文獻4,揭示該表面處理鋼材就耐蝕性、耐熱性、耐指紋性、導電性、塗裝性及加工時之耐黑渣性而言是全部都滿足。
[先行技術文獻]
[專利文獻]
[專利文獻1]日本國特許第6191806號公報
[專利文獻2]國際公開第97/00337號
[專利文獻3]日本國特許第6272207號公報
[專利文獻4]日本國特許第4776458號公報
發明概要
發明所欲解決之課題
惟,隨著近年來品質要求的高度化,對於具有化學轉化處理皮膜等皮膜的表面處理鋼材,也開始需要更加優異的塗裝附著性及優異的耐蝕性。本案發明人等檢討之結果瞭解到,以專利文獻1~4而言,有時並無法回應這種近年來高度化之要求。
又,專利文獻1、2所揭示的這種含樹脂之化學轉化處理,其由於使用有機樹脂成分,故也會有以下課題:加工時之耐黑渣性有時會不足。金屬在施予壓製加工等加工時,壓製模具等會使金屬表面遭受強烈的滑動,從金屬材表面所披覆之皮膜會產生黑色渣滓性物質並固著、堆積,導致外觀受損;而所謂的加工時之耐黑渣性,則是指對抗前述情況的耐性。黑色渣滓性物質有時會因為化學轉化處理皮膜之有機樹脂成分而產生出來。
本發明是有鑑於上述課題而完成者。本發明之課題在於提供一種具有優異塗裝附著性及優異耐蝕性的表面處理鋼材。
用以解決課題之手段
本案發明人等對於具有鍍敷層及皮膜的表面處理鋼材,針對能夠兼具優異塗裝附著性及優異耐蝕性的皮膜構成進行了檢討。結果獲得的見解是:1)含有預定元素作為皮膜的構成元素,藉此能獲得優異耐蝕性;以及,2)在皮膜其與鍍敷層之界面的一部分或全部,形成異於其他部分之構成的層,藉此會提升皮膜的附著性並提升塗裝附著性。
本發明是有鑑於上述見解所完成者。本發明之要點如下所述。
[1]本發明之一態樣的表面處理鋼材具有:
鋼板、
形成於前述鋼板上且含鋅的鍍敷層、及
形成於前述鍍敷層上的皮膜;
前述皮膜的厚度為100nm以上且1000nm以下;
前述皮膜是由非晶質相A與非晶質相B所構成,
所述非晶質相A含有下述元素作為構成元素:Si、C、O、P、Zn及V,還有選自Ti、Zr及Al所構成群組之1種或2種以上,且以EDS進行分析時,Zn與Si之峰值強度比即Zn/Si會是1.0以上,V與P之質量比即V/P會是0.050~1.000;
所述非晶質相B含有Si、O、Zn,且以EDS進行分析時,Zn與Si之峰值強度比即Zn/Si會小於1.0;
前述非晶質相A之Zn含量為10質量%以下;
在厚度方向的剖面中,前述鍍敷層與前述非晶質相B之界面長度佔前述鍍敷層與前述皮膜之界面長度的30%以上。
[2]上述[1]所記載的表面處理鋼材,其中,前述鍍敷層之化學組成以質量%計亦可由下述所構成:Al:0.1%以上且小於25.0%、Mg:0%以上且小於12.5%、Sn:0%以上且20%以下、Bi:0%以上且小於5.0%、In:0%以上且小於2.0%、Ca:0%以上且3.0%以下、Y:0%以上且0.5%以下、La:0%以上且小於0.5%、Ce:0%以上且小於0.5%、Si:0%以上且小於2.5%、Cr:0%以上且小於0.25%、Ti:0%以上且小於0.25%、Ni:0%以上且小於0.25%、Co:0%以上且小於0.25%、V:0%以上且小於0.25%、Nb:0%以上且小於0.25%、Cu:0%以上且小於0.25%、Mn:0%以上且小於0.25%、Fe:0%以上且5.0%以下、Sr:0%以上且小於0.5%、Sb:0%以上且小於0.5%、Pb:0%以上且小於0.5%、B:0%以上且小於0.5%、及剩餘部分:Zn及不純物。
發明效果
根據本發明之上述態樣,便能提供一種具有優異塗裝附著性及優異耐蝕性的表面處理鋼材。
用以實施發明之形態
以下,針對本發明一實施形態之表面處理鋼材(本實施形態之表面處理鋼材)進行說明。
如圖1所示,本實施形態之表面處理鋼材1具有:鋼板11、形成於鋼板11上且含鋅的鍍敷層12、及形成於鍍敷層12上的皮膜13。
又,皮膜13具備:具有預定構成元素的非晶質相A131、及有別於非晶質相A131的非晶質相B132。
在圖1中,鍍敷層12及皮膜13僅形成於鋼板11之單面,不過亦可形成於雙面。又,鍍敷層12形成在鋼板上(表面)之至少一部分即可,不過亦可形成在整面。又,皮膜13形成在鍍敷層12上(表面)之至少一部分即可,不過亦可形成在整面。
以下,分別針對鋼板11、鍍敷層12、皮膜13進行說明。
<鋼板>
本實施形態之表面處理鋼材1是透過鍍敷層12及皮膜13來獲得優異塗裝附著性及耐蝕性。因此,針對鋼板11並無特別限定。鋼板11依據所應用之製品、所需強度或板厚等來決定即可,例如可使用JIS G3113:2018或JIS G3131:2018所記載之熱軋鋼板、JIS G3135:2018或JIS G3141:2017所記載之冷軋鋼板。
<鍍敷層>
本實施形態之表面處理鋼材1所具備的鍍敷層12是一種形成在鋼板11之表面上且含鋅的鋅系鍍敷層。
鍍敷層12只要是鋅系鍍敷層,則對於化學組成並無限定。惟,化學組成以質量%計由下述所構成:Al:0.1%以上且小於25.0%、Mg:0%以上且小於12.5%、Sn:0%以上且20%以下、Bi:0%以上且小於5.0%、In:0%以上且小於2.0%、Ca:0%以上且3.0%以下、Y:0%以上且0.5%以下、La:0%以上且小於0.5%、Ce:0%以上且小於0.5%、Si:0%以上且小於2.5%、Cr:0%以上且小於0.25%、Ti:0%以上且小於0.25%、Ni:0%以上且小於0.25%、Co:0%以上且小於0.25%、V:0%以上且小於0.25%、Nb:0%以上且小於0.25%、Cu:0%以上且小於0.25%、Mn:0%以上且小於0.25%、Fe:0%以上且5.0%以下、Sr:0%以上且小於0.5%、Sb:0%以上且小於0.5%、Pb:0%以上且小於0.5%、B:0%以上且小於0.5%、及剩餘部分:Zn及不純物,藉此能獲得更為顯著的提升耐蝕性效果,因而適宜。
針對鍍敷層12適宜的化學組成之理由進行說明。以下,包夾「~」所表示之數值範圍基本上包含其兩端之數值作為下限值、上限值。不過,當在數值記載小於或大於時,則不含該數值作為下限值或上限值。
又,只要無特別申明,鍍敷層之化學組成相關的%為質量%。
[Al:0.1%以上且小於25.0%]
Al是在鋅系鍍敷層中用以提升耐蝕性很有效的元素。若要充分獲得上述效果時,Al含量宜設為0.1%以上。
另一方面,Al含量若為25.0%以上,則鍍敷層之切斷端面的耐蝕性會降低。因此,Al含量宜小於25.0%。
鍍敷層12亦可含Al且剩餘部分由Zn及不純物所構成。不過亦可視需要而進一步含有以下元素。此時,Zn含量仍宜為50%以上。
[Mg:0%以上且小於12.5%]
Mg是具有提高鍍敷層之耐蝕性效果的元素。若要充分獲得上述效果時,Mg含量宜設為大於1.0%。
另一方面,Mg含量若為12.5%以上,則提升耐蝕性之效果會達飽和之外,有時鍍敷層之加工性會降低。又,會產生鍍敷浴之浮渣生成量大增等製造上的問題。因此,Mg含量宜設為小於12.5%。
[Sn:0%以上且20%以下]
[Bi:0%以上且小於5.0%]
[In:0%以上且小於2.0%]
此等元素是有助於提升耐蝕性、犧牲防蝕性的元素。因此,亦可含有任1種以上。若想獲得上述效果,則宜將含量分別設為0.05%以上。
此等之中,Sn是低熔點金屬且能在不損及鍍敷浴之性質狀態下而輕易被含有,因而適宜。
另一方面,若Sn含量大於20%、Bi含量為5.0%以上、或者In含量為2.0%以上,則耐蝕性會降低。因此,宜分別將Sn含量設為20%以下、Bi含量設為小於5.0%、In含量設為小於2.0%。
[Ca:0%以上且3.0%以下]
Ca能降低作業時易於形成的浮渣形成量,而是有助於提升鍍敷製造性的元素。因此,亦可含有Ca。若想獲得此效果,Ca含量宜設為0.1%以上。
另一方面,Ca含量若高,則鍍敷層之平面部的耐蝕性本身會傾向於劣化,有時溶接部周圍之耐蝕性也會劣化。因此,Ca含量宜為3.0%以下。
[Y:0%以上且0.5%以下]
[La:0%以上且小於0.5%]
[Ce:0%以上且小於0.5%]
Y、La、Ce是有助於提升耐蝕性的元素。若想獲得此效果,宜分別含有0.05%以上的此等之中1種以上。
另一方面,此等元素含量達過量時,鍍敷浴之黏性會增高,鍍敷浴之建浴本身多半會變得困難,恐無法製造出鍍敷性質狀態良好的鋼材。因此,Y含量宜設為0.5%以下,La含量宜設為小於0.5%,Ce含量宜設為小於0.5%。
[Si:0%以上且小於2.5%]
Si是有助於提升耐蝕性的元素。又,在鋼板上形成鍍敷層時,Si會抑制鋼板表面與鍍敷層之間所形成之合金層形成得過厚,其也是一種具有提高鋼板與鍍敷層之附著性效果的元素。若想獲得此等效果,Si含量宜設為0.1%以上。Si含量較宜為0.2%以上。
另一方面,Si含量若達2.5%以上,則在鍍敷層中會析出過量的Si,不僅耐蝕性會降低,鍍敷層之加工性還會降低。據此,Si含量宜設為小於2.5%。Si含量較宜為1.5%以下。
[Cr:0%以上且小於0.25%]
[Ti:0%以上且小於0.25%]
[Ni:0%以上且小於0.25%]
[Co:0%以上且小於0.25%]
[V:0%以上且小於0.25%]
[Nb:0%以上且小於0.25%]
[Cu:0%以上且小於0.25%]
[Mn:0%以上且小於0.25%]
此等元素是有助於提升耐蝕性的元素。若想獲得此效果,則此等元素之1種以上的含量宜設為0.05%以上。
另一方面,此等元素含量達過量時,鍍敷浴之黏性會增高,鍍敷浴之建浴本身多半會變得困難,恐無法製造出鍍敷性質狀態良好的鋼材。因此,各元素之含量宜分別設為小於0.25%。
[Fe:0%以上且5.0%以下]
Fe在製造鍍敷層時會以不純物形式混入鍍敷層。有時雖含有至5.0%左右,不過若為此範圍,則對於本實施形態之表面處理鋼材之效果所帶來不良影響的程度低。因此,Fe含量宜設為5.0%以下。
[Sr:0%以上且小於0.5%]
[Sb:0%以上且小於0.5%]
[Pb:0%以上且小於0.5%]
若在鍍敷層中含有Sr、Sb、Pb,則鍍敷層外觀會變化且會形成鋅花,而可確認到金屬光澤的提升。若想獲得此效果,Sr、Sb、Pb之1種以上的含量宜設為0.05%以上。
另一方面,此等元素含量達過量時,鍍敷浴之黏性會增高,鍍敷浴之建浴本身多半會變得困難,恐無法製造出鍍敷性質狀態良好的鋼材。因此,各元素之含量宜分別設為小於0.5%。
[B:0%以上且小於0.5%]
B是如下的元素:若含於鍍敷層中,其便會與Zn、Al、Mg等產生化合而形成各種金屬間化合物。該金屬間化合物具有改善LME之效果。若想獲得此效果,B含量宜設為0.05%以上。B含量較宜為0.1%以上。
另一方面,B含量達過量,則鍍敷熔點會顯著增高,鍍敷作業性會變差且恐無法獲得鍍敷性質狀態良好的表面處理鋼材。因此,B含量宜設為小於0.5%。
鍍敷層12之附著量雖未限定,不過為了提升耐蝕性,至少每一面宜為10g/m
2以上。另一方面,每一面附著量即使大於200g/m
2,耐蝕性也會達飽和,此外還會不利於經濟層面。因此,附著量宜為200g/m
2以下。
<皮膜>
如圖1所示,本實施形態之表面處理鋼材1所具備的皮膜13具有:非晶質相A131與非晶質相B132。非晶質相B132主要形成在皮膜13其與鍍敷層12之界面側的一部分,且有助於提升皮膜13之附著性。
[非晶質相A]
本實施形態之表面處理鋼材1所具備的皮膜13是將下述處理液以預定條件塗佈於含鋅之鍍敷層上並使其乾燥,藉此獲得者;所述處理液含有:矽烷偶合劑等的Si化合物、磷酸鹽等的P化合物、V化合物,還有選自閥金屬(Valve metal)即Ti、Zr及Al所構成群組之1種以上的化合物。非晶質相A131是佔據皮膜13主要部分的層體,就構成元素而言,含有:來自矽烷偶合劑的Si、C及O,來自P化合物的P,來自V化合物的V,選自閥金屬即Ti、Zr及Al所構成群組之1種以上,還有從鍍敷層溶出的Zn。
Si、C及O(主要以矽化合物形式存在)是構成皮膜13之基質的元素。
V及P(主要以化合物形式存在)是抑制劑;不含此等時,便無法獲得充分的耐蝕性。
又,在本實施形態之表面處理鋼材1中,非晶質相A131含有P及V,此外還必須將V與P以質量%計之含量比即V/P設為0.050~1.000。
V/P若小於0.050,便無法獲得P與V之加成效果,不僅無法獲得充分的耐蝕性,塗裝附著性也會降低。又,V/P若大於1.000,則自皮膜13溶出的溶出量會變多,塗裝附著性會降低。
又,Ti、Zr、及/或Al(閥金屬)是一種氧化物很穩定的元素,若含於皮膜中,便能使皮膜13表面變得鈍態而提升耐蝕性。皮膜13不含此等元素時,便無法獲得充分的耐蝕性。
又,如後所述,閥金屬亦有助於形成非晶質相B。因此,不含閥金屬時,便無法獲得充分的塗裝附著性。
又,如後所述,在本實施形態之表面處理鋼材1中,於皮膜13其與鍍敷層12之界面附近形成具有Si-O-Zn鍵結的層體(非晶質相B)而提高了皮膜13之附著性;所述Si-O-Zn鍵結是從鍍敷層12溶出的Zn與皮膜13中的Si產生氫鍵而得者。
惟,Zn會與抑制劑反應形成磷酸鋅並沉澱。因此,從鍍敷層溶出的Zn溶出量會過量,在非晶質相A中,若Zn含量大於10質量%,則皮膜13中作為抑制劑存在的P就會減少而耐蝕性會降低。因此,非晶質相A131之Zn含量設為10質量%以下。
[非晶質相B]
非晶質相B132是一種具有Si-O-Zn鍵結的層體,所述Si-O-Zn鍵結是由下述反應所產生之共價鍵而形成:在形成皮膜13時,從鍍敷層12溶出的Zn、與用以形成皮膜之處理液所含矽烷偶合劑之Si進行脫水縮合反應而產生共價鍵。因此,非晶質相B132含有Si、O及Zn。另一方面,非晶質相B132雖富含Si-O-Zn鍵結,不過,未與Si鍵結的Zn則會優先與非晶質相A131中的P產生離子鍵結,故其Zn與Si之峰值強度比即Zn/Si會變得相較Zn/Si為1.0以上之非晶質相A還低(Zn/Si會小於1.0)。關於生成該非晶質相B之理由雖不明,不過可認為是一種以閥金屬作為催化劑的矽烷偶合劑之脫水縮合反應。
非晶質相B132存在於皮膜13之界面且是皮膜13與鍍敷層12的界面,藉此提升皮膜13之附著性。因此,在本實施形態之表面處理鋼材1中,是使非晶質相B132形成在皮膜13其與鍍敷層12之界面側。非晶質相B132可間斷形成亦可連續形成。若想充分獲得提升附著性之效果,則在厚度方向的剖面觀察時,鍍敷層12與非晶質相B132之界面長度必須佔鍍敷層12與皮膜13之界面長度的30%以上。亦即,鍍敷層12與非晶質相A131之界面長度佔鍍敷層12與皮膜13之界面長度的70%以下。在鍍敷層12與皮膜13之界面長度中,鍍敷層12與非晶質相B132之界面長度的比例亦可為100%,不過從非均相反應場之觀點來看亦可為70%以下。
非晶質相B的存在會提升附著性,其理由雖不明,不過可認為是因為非晶質相B所具有的Si-O-Zn鍵結是透過鍍敷層表面之Zn(鋅)、與用以形成皮膜之處理液所含矽烷偶合劑發生脫水縮合反應所形成者。
還可認為,鍍敷層12與非晶質相B132之界面長度佔鍍敷層12與皮膜13之界面長度的比例也會受到鍍敷表面氧化膜之厚度的影響。
關於鑑別皮膜13中的非晶質相A與非晶質相B、以及非晶質相A與非晶質相B所含構成元素之含量、峰值強度比、質量比,是可以使用EDS(Energy dispersive X-ray spectroscopy)來測定。
具體而言,使用聚焦離子束裝置(RB)FB2000A(日立製作所製)或與此等同之裝置,透過FIB-μ取樣法,從測定對象位置製作出用於TEM觀察的薄膜樣品。樣品之最外表面進行W蒸鍍來加以保護。篩網(mesh)是使用Cu網。
對於所獲得的樣品,使用場發射型穿透電子顯微鏡HF-2000(日立製作所製),並將加速電壓設為200kV,以5萬倍之視野來觀察組織,同時使用附屬之EDS分析裝置delta plus level 2 (Kevex製),將加速電壓設為200kV來進行元素分析。
關於Si、C、O、P、V、Zn、Ti、Zr、Al,是透過半定量法(semiquantitative method)來進行定量評價。求出測定位置之元素含量,同時也算出元素之峰值強度比、質量比(以質量%計的含量比)。
測定結果,Zn與Si之峰值強度比Zn/Si為1.0以上且以TEM電子線繞射而判斷為非晶質之部分,判別為非晶質相A;Zn與Si之峰值強度比Zn/Si小於1.0且以TEM電子線繞射而判斷為非晶質之部分,判別為非晶質相B。
又,在非晶質相A、非晶質相B各自中,若Si、C、O、P、Zn、V、Ti、Zr、Al含量分別為0.5質量%以上,則判斷為含有對象元素(0.5質量%以上之元素)。
在測定時,選擇比測定點尺寸還厚的相,並對於該各相之中央部進行點分析。又,針對認為是非晶質相A與非晶質相B的相,分別測定3點以上,並採用其平均值當作該相中的含量。
又,鍍敷層與非晶質相B之界面長度佔鍍敷層與皮膜之界面長度(比例)是透過下述來求出:使用上述場發射型穿透電子顯微鏡,就界面長度而言為10μm以上之範圍,觀察鍍敷層與皮膜之界面,其中,測定鍍敷層與非晶質相B之界面長度,藉此求出。(透過[鍍敷層與非晶質相B之界面長度]/[鍍敷層與皮膜之界面長度]×100來算出。)
[皮膜厚度]
皮膜13(包含非晶質相A131及非晶質相B132)之厚度設為100nm以上且1000nm以下。
皮膜13之厚度小於100nm時,耐蝕性、塗裝附著性會劣化。另一方面,皮膜13之厚度大於1000nm時,耐蝕性雖良好,但從皮膜13溶出的抑制劑成分溶出量會變多,而塗裝附著性會降低。
皮膜厚度是以電磁膜厚計來測定。具體而言,使用電磁膜厚計測定任意10點,並以其平均值作為皮膜厚度。
接著,針對本實施形態之表面處理鋼材適宜的製造方法進行說明。
本實施形態之表面處理鋼材無關製造方法,只要具有上述特徴就能獲得其效果,不過,若為以下所示製造方法則可穩定製造,因而適宜。
亦即,本實施形態之表面處理鋼材可透過含有以下步驟的製造方法來製造。
(I)鍍敷步驟:將鋼材(鋼板)浸漬於含Zn之鍍敷浴,或者透過在含Zn之水溶液、熔融鹽中進行電鍍,藉此在表面形成鍍敷層;
(II)塗佈步驟:在具有鍍敷層之鋼材上,塗佈表面處理金屬劑(處理液);及
(III)加熱步驟:將塗佈了表面處理金屬劑的鋼材予以加熱而形成皮膜,該皮膜含有:Si、C、O、P、Zn及V,還有選自Ti、Al及Zr所構成群組之1種以上。
針對各個步驟說明適宜的條件。
[鍍敷步驟]
關於鍍敷步驟,並不特別限定。進行一般方法以獲得充分的鍍敷附著性即可。
又,關於供應至鍍敷步驟的鋼材其製造方法亦不限定。
例如,可為JIS G3302:2019所規定之鍍鋅鋼板的製造方法,亦可為JIS G3323:2019、JIS G3313:2017所規定之鍍敷鋼板的製造方法。
鍍敷浴之組成亦因應所欲獲得鍍敷層之組成來調整即可。
在鍍敷冷卻步驟後且至塗佈步驟之間,避免表面過度氧化、附油等,宜控管在未有藥劑沾附之鍍敷表面狀態。
[塗佈步驟]
在塗佈步驟中,對於具有含Zn鍍敷層的鋼板等鋼材塗佈表面處理金屬劑,該表面處理金屬劑含有Si化合物、P化合物、V化合物,還有Ti、Zr及/或Al之化合物。Si化合物、P化合物、V化合物,還有Ti化合物、Zr化合物及/或Al化合物是添加作為皮膜的構成元素。又,P化合物亦具有下述效果:透過蝕刻反應而使鍍敷層之Zn溶出;透過其與閥金屬之組合,會有助於生成非晶質相B。
在塗佈步驟中,關於表面處理金屬劑之塗佈方法並不限定。例如可使用輥塗佈機、桿塗佈機、噴塗(spray)等來進行塗佈。
透過沾料輥(pick up roll)與塗佈輥(application roll)的旋轉速度、周速比(peripheral speed ratio)來改變塗佈量,藉此可使皮膜厚度變化。
在本實施形態中,為了形成非晶質相B,表面處理金屬劑所含Si化合物宜設為在分子中含有異氰酸酯基、胺基或環氧基等的矽烷偶合劑,其中,較佳為異氰酸酯基。
表面處理金屬劑中的Si化合物濃度宜為5~20質量%。
在本實施形態中,表面處理金屬劑所含P化合物雖不特別限定,不過可例示:磷酸、磷酸銨鹽、磷酸鉀鹽、磷酸鈉鹽等。其中,較佳為磷酸。使用磷酸時可獲得較優異的耐蝕性。表面處理金屬劑中的P化合物濃度宜為1~5質量%。
又,表面處理金屬劑所含V化合物可例示:五氧化釩V
2O
5、偏釩酸HVO
3、偏釩酸銨、偏釩酸鈉、三氯氧化釩VOCl
3、三氧化釩V
2O
3、二氧化釩VO
2、硫酸氧釩VOSO
4、乙醯丙酮氧釩VO(OC(=CH
2)CH
2COCH
3)
2、乙醯丙酮釩V(OC(=CH
2)CH
2COCH
3)
3、三氯化釩VCl
3、磷釩鉬酸等。又,亦可使用下述成分:透過含有選自羥基、羰基、羧基、1~3級胺基、醯胺基、磷酸基及膦酸基所構成群組之至少1種官能基的有機化合物,將5價釩化合物還原成4價~2價後的成分。表面處理金屬劑中的V化合物之濃度宜為0.0001~4.0質量%。
又,關於Ti化合物、Zr化合物、Al化合物則可例示:硝酸鈦、硝酸鋯、硝酸鋁等。
[加熱步驟]
在加熱步驟中,將塗佈了表面處理金屬劑的鋼材予以加熱並使其乾燥、燒黏而形成皮膜。關於加熱溫度(使其乾燥之溫度),最高到達溫度宜為60~200℃,較宜為80~150℃。最高到達溫度若小於60℃,則表面處理金屬劑之溶劑未完全揮發,因而不佳。另一方面,最高到達溫度若大於200℃,則加熱所帶來的溶劑乾燥效果會達飽和且不經濟,因而不佳。
在加熱步驟中,表面處理金屬劑之加熱方法並不限定。例如可使用IH、熱風爐等進行加熱並使其乾燥。
又,在室溫下塗佈表面處理金屬劑(處理液)(塗佈完成時)起至達到最高到達溫度為止之時間若長,則從鍍敷層溶出的Zn溶出量就會變多,因此,塗佈表面處理金屬劑(處理液)起至達到最高到達溫度為止之時間宜設為10.0秒以下,較宜設為4.0秒以下。
達到最高到達溫度後的表面處理鋼材則冷卻至室溫附近為止。關於冷卻條件並不特別限定,不過可考慮氣體冷卻、使用液體的水霧冷卻或淹沒冷卻。
[實施例]
準備熔融鍍鋅鋼板,作為用以在表面形成皮膜的鍍敷鋼板;該熔融鍍鋅鋼板是JIS G3302:2019所規定的鍍鋅鋼板且其鍍敷附著量以Z08來標記。
使用輥塗佈機,且如表1所示,對於該鍍敷鋼板塗佈以下種類的處理液A~S之任一者。
(處理液A)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩75mg與磷酸氫二銨3g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液B)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩70mg與磷酸氫二銨2g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液C)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩70mg與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液D)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩100mg與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液E)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液F)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩1.7g與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液G)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩9.0g與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液H)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液I)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液J)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g而獲得之水溶液。
(處理液K)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鋯1g而獲得之水溶液。
(處理液L)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鋁1g而獲得之水溶液。
(處理液M)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鈦與硝酸鋯分別0.5g而獲得之水溶液。
(處理液N)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鈦與硝酸鋁分別0.5g而獲得之水溶液。
(處理液O)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鋯與硝酸鋁分別0.5g而獲得之水溶液。
(處理液P)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩84mg與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液Q)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩1.6g與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液R)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達10%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩1.3g與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
(處理液S)
透過1:1混合乙醇與0.05%氨水而得之溶液,來將3-異氰酸酯丙基三乙氧基矽烷調整至以質量比計達3%及將氧化矽溶膠(日產化學製ST-NXS)調整至以質量比計達7%,並將其放置3小時後,所得之溶液作為基液,在該溶液100mL中溶解乙醯丙酮氧釩170mg與磷酸氫二銨1g,同時溶解硝酸鈦1g而獲得之水溶液。
對於鋼板,在室溫(20℃)塗佈上述表面處理金屬劑後,視需要而放置,之後再以塗佈完成起至達到最高到達溫度為止之時間為表1所示數值之方式,透過熱風乾燥爐加熱至最高到達溫度。平均加熱速度是包含放置時間在內而計算出塗佈完成起至達到最高到達溫度為止之平均加熱速度。
之後自然冷卻至室溫為止。
藉此獲得表面處理鋼材No.1~30。
對於所獲得之表面處理鋼材,透過上述方法(Zn/Si及是否為非晶質)來鑑別非晶質相A及非晶質相B,同時求出:皮膜的厚度、非晶質相A及非晶質相B之元素分析、鍍敷層與前述非晶質相B之界面長度佔鍍敷層與皮膜之界面長度的比例。
結果列示於表2。
又,針對所獲得之表面處理鋼材,透過以下方法來評價耐蝕性及塗裝附著性。
[耐蝕性]
製作平板試驗片,對於各試驗片進行根據JIS Z 2371:2015的鹽水噴霧試驗,並評價120小時後表面產生白鏽之狀況(試驗片面積中產生白鏽之面積的比例)。
產生白鏽面積率若為5%以下,則判斷為耐蝕性優異。
[塗裝附著性]
製作出平板試驗片,以乾燥後之膜厚達20μm之方式塗佈白色塗料(Amilac#1000)。將該試驗片浸漬於沸騰水30分鐘後,透過依契遜(Erichsen)鼓脹裝置進行鼓脹至高度7mm為止,再實施膠帶剝離試驗來確認塗膜殘存率。
塗膜殘存面積率若為80%以上,則判斷為塗裝附著性優異。
從表1~表2可知,就No.4~6、8、9、14~18、20~23、25、28、29而言,其等含有預定量的Si、C、O、P、Zn、V,還有預定量的選自Ti、Zr及Al所構成群組之1種或2種以上,且與非晶質相B之界面長度比例為30%以上,其等獲得優異的耐蝕性及塗裝附著性。
相對於此,就比較例No.1~3、7、10~13、19、24、26、27、30而言,其等不滿足1個以上的本發明要件,其等耐蝕性、塗裝附著性之任一者或兩者差。
產業上之可利用性
依照本發明,便可提供一種具有優異塗裝附著性及優異耐蝕性的表面處理鋼材。該表面處理鋼材在產業上之可利用性高。
1:表面處理鋼材
11:鋼板
12:鍍敷層
13:皮膜
131:非晶質相A
132:非晶質相B
圖1是顯示本實施形態之表面處理鋼材其剖面之一例的圖。
1:表面處理鋼材
11:鋼板
12:鍍敷層
13:皮膜
131:非晶質相A
132:非晶質相B
Claims (2)
- 一種表面處理鋼材,其特徵在於具有: 鋼板、 形成於前述鋼板上且含鋅的鍍敷層、及 形成於前述鍍敷層上的皮膜; 前述皮膜的厚度為100nm以上且1000nm以下; 前述皮膜是由非晶質相A與非晶質相B所構成, 所述非晶質相A含有下述元素作為構成元素:Si、C、O、P、Zn及V,還有選自Ti、Zr及Al所構成群組之1種或2種以上,且以EDS進行分析時,Zn與Si之峰值強度比即Zn/Si會是1.0以上,V與P之質量比即V/P會是0.050~1.000; 所述非晶質相B含有Si、O、Zn,且以EDS進行分析時,Zn與Si之峰值強度比即Zn/Si會小於1.0; 前述非晶質相A之Zn含量為10質量%以下; 在厚度方向的剖面中,前述鍍敷層與前述非晶質相B之界面長度佔前述鍍敷層與前述皮膜之界面長度的30%以上。
- 如請求項1之表面處理鋼材,其中,前述鍍敷層之化學組成以質量%計是由下述所構成: Al:0.1%以上且小於25.0%、 Mg:0%以上且小於12.5%、 Sn:0%以上且20%以下、 Bi:0%以上且小於5.0%、 In:0%以上且小於2.0%、 Ca:0%以上且3.0%以下、 Y:0%以上且0.5%以下、 La:0%以上且小於0.5%、 Ce:0%以上且小於0.5%、 Si:0%以上且小於2.5%、 Cr:0%以上且小於0.25%、 Ti:0%以上且小於0.25%、 Ni:0%以上且小於0.25%、 Co:0%以上且小於0.25%、 V:0%以上且小於0.25%、 Nb:0%以上且小於0.25%、 Cu:0%以上且小於0.25%、 Mn:0%以上且小於0.25%、 Fe:0%以上且5.0%以下、 Sr:0%以上且小於0.5%、 Sb:0%以上且小於0.5%、 Pb:0%以上且小於0.5%、 B:0%以上且小於0.5%、及 剩餘部分:Zn及不純物。
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TW111107688A TWI792932B (zh) | 2021-03-04 | 2022-03-03 | 表面處理鋼材 |
Country Status (11)
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US (1) | US20240043981A1 (zh) |
EP (1) | EP4303340A1 (zh) |
JP (1) | JP7376843B2 (zh) |
KR (1) | KR20230141860A (zh) |
CN (1) | CN117015631B (zh) |
AU (1) | AU2022230506A1 (zh) |
BR (1) | BR112023017302A2 (zh) |
CA (1) | CA3209039A1 (zh) |
MX (1) | MX2023010121A (zh) |
TW (1) | TWI792932B (zh) |
WO (1) | WO2022186380A1 (zh) |
Citations (2)
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JP2009242815A (ja) * | 2008-03-28 | 2009-10-22 | Jfe Steel Corp | 表面処理鋼板およびその製造方法 |
TW201638389A (zh) * | 2015-02-03 | 2016-11-01 | Nippon Steel & Sumitomo Metal Corp | 燃料槽用鋼板 |
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JPS6191806U (zh) | 1984-11-22 | 1986-06-14 | ||
JPH0529123Y2 (zh) | 1985-10-25 | 1993-07-27 | ||
US5525431A (en) * | 1989-12-12 | 1996-06-11 | Nippon Steel Corporation | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
WO1997000337A1 (fr) | 1995-06-15 | 1997-01-03 | Nippon Steel Corporation | Feuille d'acier a surface traitee pourvue d'un revetement de resine a conversion chimique et procede de fabrication de ladite feuille |
JP2000309880A (ja) * | 1999-04-23 | 2000-11-07 | Sumitomo Metal Ind Ltd | 高耐食性表面処理鋼板 |
JP2000313966A (ja) * | 1999-04-27 | 2000-11-14 | Sumitomo Metal Ind Ltd | 塗装後耐食性に優れる表面処理鋼板 |
JP4002534B2 (ja) * | 2003-02-03 | 2007-11-07 | 新日本製鐵株式会社 | 塗膜密着性と鮮映性に優れ環境負荷の小さい高耐食性塗装鋼板 |
JP4470515B2 (ja) * | 2004-02-16 | 2010-06-02 | Jfeスチール株式会社 | 耐白錆性と外観が優れた表面処理鋼板 |
JP4776458B2 (ja) | 2005-07-22 | 2011-09-21 | 新日本製鐵株式会社 | 耐食性、耐熱性、耐指紋性、導電性、塗装性および加工時の耐黒カス性に優れたクロメートフリー表面処理金属材 |
JP5398310B2 (ja) * | 2009-03-09 | 2014-01-29 | 日新製鋼株式会社 | 塗装鋼板および外装部材 |
MY171037A (en) * | 2011-08-24 | 2019-09-23 | Nippon Steel Corp | Painted plated-steel |
BR112016010299B1 (pt) * | 2013-11-14 | 2021-11-09 | Nisshin Steel Co., Ltd | Solução de tratamento de conversão química e chapa de aço quimicamente convertida |
WO2016203703A1 (ja) * | 2015-06-15 | 2016-12-22 | Jfeスチール株式会社 | 表面処理亜鉛系めっき鋼板およびその製造方法 |
KR102043572B1 (ko) * | 2015-07-15 | 2019-11-11 | 닛폰세이테츠 가부시키가이샤 | 수계 처리제, 아연 도금 강재 또는 아연 합금 도금 강재 및 도장 아연 도금 강재 또는 도장 아연 합금 도금 강재 |
MX2018007963A (es) | 2016-03-09 | 2018-11-09 | Nippon Steel & Sumitomo Metal Corp | Lamina de acero con superficie tratada y metodo para producir la lamina de acero con superficie tratada. |
CN113631743B (zh) * | 2019-03-19 | 2022-08-26 | 日本制铁株式会社 | 表面处理金属材料 |
TWM590795U (zh) | 2019-08-22 | 2020-02-11 | 映興電子股份有限公司 | 連接器結構 |
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2022
- 2022-03-03 TW TW111107688A patent/TWI792932B/zh active
- 2022-03-04 WO PCT/JP2022/009421 patent/WO2022186380A1/ja active Application Filing
- 2022-03-04 JP JP2023503971A patent/JP7376843B2/ja active Active
- 2022-03-04 BR BR112023017302A patent/BR112023017302A2/pt unknown
- 2022-03-04 AU AU2022230506A patent/AU2022230506A1/en active Pending
- 2022-03-04 US US18/278,429 patent/US20240043981A1/en active Pending
- 2022-03-04 EP EP22763430.0A patent/EP4303340A1/en active Pending
- 2022-03-04 MX MX2023010121A patent/MX2023010121A/es unknown
- 2022-03-04 CA CA3209039A patent/CA3209039A1/en active Pending
- 2022-03-04 CN CN202280018115.6A patent/CN117015631B/zh active Active
- 2022-03-04 KR KR1020237030364A patent/KR20230141860A/ko unknown
Patent Citations (2)
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JP2009242815A (ja) * | 2008-03-28 | 2009-10-22 | Jfe Steel Corp | 表面処理鋼板およびその製造方法 |
TW201638389A (zh) * | 2015-02-03 | 2016-11-01 | Nippon Steel & Sumitomo Metal Corp | 燃料槽用鋼板 |
Also Published As
Publication number | Publication date |
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JP7376843B2 (ja) | 2023-11-09 |
US20240043981A1 (en) | 2024-02-08 |
AU2022230506A1 (en) | 2023-09-28 |
JPWO2022186380A1 (zh) | 2022-09-09 |
KR20230141860A (ko) | 2023-10-10 |
EP4303340A1 (en) | 2024-01-10 |
CN117015631B (zh) | 2024-04-02 |
CN117015631A (zh) | 2023-11-07 |
WO2022186380A1 (ja) | 2022-09-09 |
TW202239990A (zh) | 2022-10-16 |
MX2023010121A (es) | 2023-09-11 |
BR112023017302A2 (pt) | 2023-09-26 |
CA3209039A1 (en) | 2022-09-09 |
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