CN117015631B - 表面处理钢材 - Google Patents
表面处理钢材 Download PDFInfo
- Publication number
- CN117015631B CN117015631B CN202280018115.6A CN202280018115A CN117015631B CN 117015631 B CN117015631 B CN 117015631B CN 202280018115 A CN202280018115 A CN 202280018115A CN 117015631 B CN117015631 B CN 117015631B
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- China
- Prior art keywords
- less
- plating layer
- amorphous phase
- film
- coating
- 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.)
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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
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000007747 plating Methods 0.000 claims abstract description 99
- 239000011701 zinc Substances 0.000 claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 66
- 239000011248 coating agent Substances 0.000 claims description 64
- 239000000126 substance Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 5
- 239000010408 film Substances 0.000 description 85
- 239000010410 layer Substances 0.000 description 73
- 230000007797 corrosion Effects 0.000 description 46
- 238000005260 corrosion Methods 0.000 description 46
- 239000000243 solution Substances 0.000 description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 238000011282 treatment Methods 0.000 description 36
- 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 29
- 239000002184 metal Substances 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 27
- 239000007788 liquid Substances 0.000 description 21
- 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 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- 239000012948 isocyanate Substances 0.000 description 19
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 19
- 239000007864 aqueous solution Substances 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
- 239000011247 coating layer Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 238000007739 conversion coating Methods 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 238000012360 testing method Methods 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
- 239000012530 fluid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000001035 drying 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
- 239000003112 inhibitor Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003682 vanadium compounds Chemical class 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
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 238000012545 processing Methods 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
- 230000001133 acceleration Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011651 chromium Substances 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
- 238000010828 elution Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 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 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- JZDMNWBZPLJKBT-UHFFFAOYSA-N F.[Zr] Chemical compound F.[Zr] JZDMNWBZPLJKBT-UHFFFAOYSA-N 0.000 description 1
- BKXZLZVGNZNKGG-UHFFFAOYSA-N P(=O)(=O)[V] Chemical compound P(=O)(=O)[V] BKXZLZVGNZNKGG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003368 amide group Chemical group 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
- 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
- 239000013043 chemical agent 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
- 229910052804 chromium Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution 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
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007602 hot air drying 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
- 239000002932 luster Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 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
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint 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
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 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
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 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
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
-
- 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
- C23C2/26—After-treatment
-
- 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
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Abstract
本发明的表面处理钢材具有:钢板;形成在上述钢板上且含锌的镀覆层;以及形成在上述镀覆层上的皮膜,所述皮膜的厚度为100nm以上且1000nm以下,上述皮膜包含非晶质相A和非晶质相B,所述非晶质相A作为构成元素含有Si、C、O、P、Zn及V、以及选自Ti、Zr及Al中的1种或2种以上,进行利用EDS的分析时,作为Zn与Si的峰强度比的Zn/Si为1.0以上、作为V与P的质量比的V/P为0.050~1.000,所述非晶质相B含有Si、O、Zn,进行利用EDS的分析时,作为Zn与Si的峰强度比的Zn/Si小于1.0,上述非晶质相A的Zn含量为10质量%以下,在厚度方向的截面中,上述镀覆层与上述非晶质相B的界面长度占上述镀覆层与上述皮膜的界面长度为30%以上。
Description
技术领域
本发明涉及表面处理钢材。
本申请基于2021年03月04日在日本提出申请的日本特愿2021-034369号主张优先权,在此援引其内容。
背景技术
一直以来,在钢板的表面形成有以锌为主体的镀覆层的镀覆钢板(锌系镀覆钢板)在汽车或者建筑材料、家电制品等范围宽广的用途中使用。通常,为了在不涂油的情况下对镀覆钢板的表面赋予进一步的耐腐蚀性,实施无铬的化学转化处理。
通过该化学转化处理形成的化学转化处理皮膜要求均匀地将表面覆盖、且与镀覆的密合性优异,耐腐蚀性也优异。但是,锌系镀覆钢板的表面由于被氧化皮膜覆盖,因此即便是要形成化学转化处理皮膜,也有氧化皮膜变为障碍、化学转化处理皮膜的密合性低、发生因化学转化处理皮膜的密合性降低所导致的涂饰不良-涂饰不均、或者化学转化处理皮膜从镀覆层上剥离的情况。
对于这种课题,例如专利文献1中公开了通过在含锌的镀覆钢板上形成皮膜,可获得与粘接剂的粘接性良好、具有优异耐腐蚀性的皮膜,所述皮膜包含丙烯酸树脂、锆、钒、磷以及钴,在皮膜的截面中从表面至膜厚1/5厚度的区域中、丙烯酸树脂的面积率为80~100面积%,在皮膜的由从膜厚中心至上述表面侧的膜厚1/10厚度的区域和从上述膜厚中心至上述镀覆层侧的膜厚1/10厚度的区域形成的区域中、丙烯酸树脂的面积率为5~50面积%。
专利文献2中公开了一种表面处理钢板,其为包含钢板以及树脂系化学转化处理皮膜的表面处理钢板,该树脂系化学转化处理皮膜以重量比50/1~1/1的范围具有基体树脂和分散在该基体树脂中的难溶性铬酸盐的胶体粒子,该胶体作为分散在该基体树脂中的粒子的平均粒径小于1μm。
专利文献2中记载了该表面处理钢板的耐铬溶出性、SST(240hr)、加工部耐腐蚀性、处理液稳定性优异。
专利文献3中公开了一种化学转化处理钢板,其具有:有包含Al:0.1~22.0质量%的Zn系镀覆层的Zn系镀覆钢板;和配置在上述Zn系镀覆层上的化学转化处理皮膜,上述化学转化处理皮膜具有:配置在上述Zn系镀覆层表面上且包含V、Mo及P的第一化学转化处理层;和配置在上述第一化学转化处理层上且包含4A族金属含氧酸盐的第二化学转化处理层,上述化学转化处理皮膜中的5价V与全部V的比例为0.7以上。
专利文献3中公开了该化学转化处理钢板是以Zn系镀覆钢板为原板的化学转化处理钢板,即便是在低温且短时间内对所涂布的化学转化处理液进行干燥也可制造,耐腐蚀性及耐黑变性优异。
专利文献4中公开了一种表面处理钢材,其在(1)钢材表面上涂布一种水系金属表面处理剂进行干燥来形成含有各成分的复合皮膜,其中,所述水系金属表面处理剂包含
(2)以固体成分质量比[(A)/(B)]计为0.5~1.7的比例配合分子中含有1个氨基的硅烷偶联剂(A)和分子中含有1个缩水甘油基的硅烷偶联剂(B)所获得的分子内含有2个以上式-SiR1R2R3(式中,R1、R2以及R3彼此独立地表示烷氧基或羟基,至少1个表示烷氧基)所示官能团(a)及1个以上选自羟基(与官能团(a)可以包含的基团不同者)和氨基中的至少1种亲水性官能团(b)且平均分子量为1000~10000的有机硅化合物(W);
(3)选自氢氟酸钛或氢氟酸锆中的至少1种氟化合物(X);
(4)磷酸(Y);以及(5)钒化合物(Z),
并且,
在该复合皮膜的各成分中,
(6)有机硅化合物(W)与氟化合物(X)的固体成分质量比[(X)/(W)]为0.02~0.07,
(7)有机硅化合物(W)与磷酸(Y)的固体成分质量比[(Y)/(W)]为0.03~0.12,
(8)有机硅化合物(W)与钒化合物(Z)的固体成分质量比[(Z)/(W)]为0.05~0.17,且
(9)氟化合物(X)与钒化合物(Z)的固体成分质量比[(Z)/(X)]为1.3~6.0。
根据专利文献4,公开了该表面处理钢材满足耐腐蚀性、耐热性、耐指纹性、导电性、涂饰性以及加工时的抗黑渣性全部。
现有技术文献
专利文献
专利文献1:日本专利第6191806号公报
专利文献2:国际公开第97/00337号
专利文献3:日本专利第6272207号公报
专利文献4:日本专利第4776458号公报
发明内容
发明要解决的课题
但是,由于近年的品质要求的高度化,开始要求具有化学转化处理皮膜等皮膜的表面处理钢材具有优异的涂饰密合性以及优异的耐腐蚀性。本发明人们进行研究的结果发现,专利文献1~4中仍有时无法应对这种近年有所高度化的要求。
另外,专利文献1、2中公开的包含树脂的化学转化处理还具有以下课题:由于使用有机树脂成分,因此仍具有加工时的抗黑渣性变得不充分的情况。加工时的抗黑渣性是指对于金属在实施了压制加工等加工时、金属表面因压制模具等受到强烈的滑动而由被覆在金属材表面上的皮膜产生黑渣性物质并进行固定、堆积而有损外观的耐受性。黑渣性物质有时是因化学转化处理皮膜的有机树脂成分所导致发生的。
本发明鉴于上述课题而完成。本发明的课题在于提供具有优异涂饰密合性以及优异耐腐蚀性的表面处理钢材。
用于解决课题的手段
本发明人们对于在具有镀覆层以及皮膜的表面处理钢材中用于兼顾优异涂饰密合性以及优异耐腐蚀性的皮膜的构成进行了研究。结果发现,1)作为皮膜的构成元素,通过含有规定的元素而获得优异的耐腐蚀性;以及2)通过在皮膜的与镀覆层的界面的一部分或全部上形成不同于其它部分的构成的层,皮膜的密合性提高、涂饰密合性提高。
本发明鉴于上述发现而完成。本发明的主旨如下所述。
[1]本发明一个方式的表面处理钢材具有:
钢板;
形成在上述钢板上且含锌的镀覆层;以及
形成在上述镀覆层上的皮膜,
上述皮膜的厚度为100nm以上且1000nm以下,
上述皮膜包含非晶质相A和非晶质相B,所述非晶质相A作为构成元素含有Si、C、O、P、Zn及V、以及选自Ti、Zr以及Al中的1种或2种以上,进行利用EDS的分析时,作为Zn与Si的峰强度比的Zn/Si为1.0以上、作为V与P的质量比的V/P为0.050~1.000,所述非晶质相B含有Si、O、Zn,进行利用EDS的分析时,作为Zn与Si的峰强度比的Zn/Si小于1.0,
所述非晶质相A的Zn含量为10质量%以下,在厚度方向的截面中,所述镀覆层与所述非晶质相B的界面长度占所述镀覆层与所述皮膜的界面长度为30%以上。
[2]上述[1]所述的表面处理钢材,所述镀覆层的化学组成以质量%计可以包含Al:0.1%以上且小于25.0%、Mg:0%以上且小于12.5%、Sn:0%以上且20%以下、Bi:0%以上且小于5.0%、In:0%以上且小于2.0%、Ca:0%以上且3.0%以下、Y:0%以上且0.5%以下、La:0%以上且小于0.5%、Ce:0%以上且小于0.5%、Si:0%以上且小于2.5%、Cr:0%以上且小于0.25%、Ti:0%以上且小于0.25%、Ni:0%以上且小于0.25%、Co:0%以上且小于0.25%、V:0%以上且小于0.25%、Nb:0%以上且小于0.25%、Cu:0%以上且小于0.25%、Mn:0%以上且小于0.25%、Fe:0%以上且5.0%以下、Sr:0%以上且小于0.5%、Sb:0%以上且小于0.5%、Pb:0%以上且小于0.5%、B:0%以上且小于0.5%、以及剩余部分:Zn及杂质。
发明效果
根据本发明的上述方式,可以提供具有优异涂饰密合性以及优异耐腐蚀性的表面处理钢材。
附图说明
图1为表示本实施方式的表面处理钢材的截面之一例的图。
具体实施方式
以下说明本发明一个实施方式的表面处理钢材(本实施方式的表面处理钢材)。
本实施方式的表面处理钢材1如图1所示具有钢板11、形成于钢板11上且含锌的镀覆层12、以及形成于镀覆层12上的皮膜13。
另外,皮膜13具有含有规定构成元素的非晶质相A131和不同于非晶质相A131的非晶质相B132。
图1中,镀覆层12以及皮膜13仅形成在钢板11的单面上,但也可以形成在两面上。另外,镀覆层12只要形成在钢板上(表面)的至少一部分上即可,也可以形成在整个面上。另外,皮膜13只要形成在镀覆层12上(表面)的至少一部分上即可,也可以形成在整个面上。
以下分别说明钢板11、镀覆层12、皮膜13。
<钢板>
本实施方式的表面处理钢材1通过镀覆层12以及皮膜13可获得优异的涂饰密合性以及耐腐蚀性。因此,对于钢板11并无特别限定。钢板11只要由所应用的制品或所要求的强度或板厚等决定即可,例如可以使用JIS G3113:2018或JIS G3131:2018中记载的热轧钢板或者JIS G3135:2018或JIS G3141:2017中记载的冷轧钢板。
<镀覆层>
本实施方式的表面处理钢材1具备的镀覆层12是形成在钢板11的表面上且含锌的锌系镀覆层。
镀覆层12只要是锌系镀覆层,则化学组成并无限定。但是化学组成以质量%计包含Al:0.1%以上且小于25.0%、Mg:0%以上且小于12.5%、Sn:0%以上且20%以下、Bi:0%以上且小于5.0%、In:0%以上且小于2.0%、Ca:0%以上且3.0%以下、Y:0%以上且0.5%以下、La:0%以上且小于0.5%、Ce:0%以上且小于0.5%、Si:0%以上且小于2.5%、Cr:0%以上且小于0.25%、Ti:0%以上且小于0.25%、Ni:0%以上且小于0.25%、Co:0%以上且小于0.25%、V:0%以上且小于0.25%、Nb:0%以上且小于0.25%、Cu:0%以上且小于0.25%、Mn:0%以上且小于0.25%、Fe:0%以上且5.0%以下、Sr:0%以上且小于0.5%、Sb:0%以上且小于0.5%、Pb:0%以上且小于0.5%、B:0%以上且小于0.5%、以及剩余部分:Zn及杂质,获得更为显著的耐腐蚀性提高的效果,因此优选。
对镀覆层12的优选化学组成的理由进行说明。以下,以夹着“~”进行显示的数值范围作为下限值、上限值包含其两端数值作为基本。其中,小于或者超过数值进行记载时,作为下限值或上限值不包含该数值。
另外,只要无特别限定,则关于镀覆层的化学组成的%为质量%。
[Al:0.1%以上且小于25.0%]
Al是在锌系镀覆层中对于提高耐腐蚀性有效的元素。充分地获得上述效果时,优选使Al含量为0.1%以上。
而当Al含量为25.0%以上时,镀覆层的切断端面的耐腐蚀性会降低。因此Al含量优选小于25.0%。
镀覆层12可以含Al,剩余部分包含Zn及杂质。但是,还可根据需要进一步包含以下元素。此时,Zn含量优选为50%以上。
[Mg:0%以上且小于12.5%]
Mg是具有提高镀覆层的耐腐蚀性效果的元素。充分地获得上述效果时,优选使Mg含量超过1.0%。
而当Mg含量为12.5%以上时,不仅耐腐蚀性提高的效果饱和,有时镀覆层的加工性也会降低。另外,会发生镀覆浴的渣滓产生量增大等制造上的问题。因而,优选使Mg含量小于12.5%。
[Sn:0%以上且20%以下]
[Bi:0%以上且小于5.0%]
[In:0%以上且小于2.0%]
这些元素是有助于提高耐腐蚀性、牺牲防蚀性的元素。因此,均可含有1种以上。获得上述效果时,优选使各自的含量为0.05%以上。
其中,Sn由于是低熔点金属、不会损害镀覆浴的性状、可以容易地含有,因此优选。
而当Sn含量超过20%、Bi含量为5.0%以上、或In含量为2.0%以上时,耐腐蚀性降低。因此优选分别使Sn含量为20%以下、Bi含量小于5.0%、In含量小于2.0%。
[Ca:0%以上且3.0%以下]
Ca是有助于减少在操作时容易形成的渣滓的形成量、提高镀覆制造性的元素。因此还可以含有Ca。获得此效果时,优选使Ca含量为0.1%以上。
而当Ca含量多时,具有镀覆层的平面部的耐腐蚀性其自身发生劣化的倾向,焊接部周围的耐腐蚀性有时也会劣化。因此,Ca含量优选为3.0%以下。
[Y:0%以上且0.5%以下]
[La:0%以上且小于0.5%]
[Ce:0%以上且小于0.5%]
Y、La、Ce是有助于提高耐腐蚀性的元素。获得此效果时,优选使它们中的1种以上分别含有0.05%以上。
而这些元素的含量变得过剩时,镀覆浴的粘性上升,镀覆浴的建浴其自身多会变难,有可能无法制造镀覆性状良好的钢材。因此优选使Y含量为0.5%以下、使La含量小于0.5%、使Ce含量小于0.5%。
[Si:0%以上且小于2.5%]
Si是有助于提高耐腐蚀性的元素。另外,Si还是在钢板上形成镀覆层时具有抑制形成于钢板表面与镀覆层之间的合金层过厚地形成、提高钢板与镀覆层的密合性的效果的元素。获得这些效果时,优选使Si含量为0.1%以上。Si含量更优选为0.2%以上。
而当Si含量变为2.5%以上时,过剩的Si析出至镀覆层中,不仅耐腐蚀性降低,而且镀覆层的加工性降低。因此优选使Si含量小于2.5%。Si含量更优选为1.5%以下。
[Cr:0%以上且小于0.25%]
[Ti:0%以上且小于0.25%]
[Ni:0%以上且小于0.25%]
[Co:0%以上且小于0.25%]
[V:0%以上且小于0.25%]
[Nb:0%以上且小于0.25%]
[Cu:0%以上且小于0.25%]
[Mn:0%以上且小于0.25%]
这些元素是有助于提高耐腐蚀性的元素。获得此效果时,优选使这些元素的1种以上的含量为0.05%以上。
而这些元素的含量变得过剩时,镀覆浴的粘性上升,镀覆浴的建浴其自身多会变难,有可能无法制造镀覆性状良好的钢材。因此优选使各元素的含量分别小于0.25%。
[Fe:0%以上且5.0%以下]
Fe是在制造镀覆层时作为杂质混入到镀覆层中的。有时使其含有达到5.0%左右,若为此范围,则对本实施方式的表面处理钢材效果的不良影响小。因此,优选使Fe含量为5.0%以下。
[Sr:0%以上且小于0.5%]
[Sb:0%以上且小于0.5%]
[Pb:0%以上且小于0.5%]
Sr、Sb、Pb含有在镀覆层中时,可确认镀覆层的外观发生变化、形成锌花、金属光泽提高。获得此效果时,优选使Sr、Sb、Pb的1种以上的含量为0.05%以上。
而这些元素的含量变得过剩时,镀覆浴的粘性上升,镀覆浴的建浴其自身多会变难,有可能无法制造镀覆性状良好的钢材。因此优选使各元素的含量分别小于0.5%。
[B:0%以上且小于0.5%]
B含有在镀覆层中时,是与Zn、Al、Mg等化合来制作各种金属间化合物的元素。该金属间化合物具有改善LME的效果。获得此效果时,优选使B含量为0.05%以上。B含量更优选为0.1%以上。
而B含量变得过剩时,会担心镀覆的熔点明显上升、镀覆操作性恶化、无法获得镀覆性状良好的表面处理钢材。因此优选使B含量小于0.5%。
镀覆层12的附着量并无限定,为了提高耐腐蚀性,优选至少每个单面为10g/m2以上。而即便每个单面附着量超过200g/m2,不仅耐腐蚀性饱和,而且在经济上也会变得不利。因此,优选附着量为200g/m2以下。
<皮膜>
本实施方式的表面处理钢材1具备的皮膜13如图1所示,具有非晶质相A131和非晶质相B132。非晶质相B132主要形成在皮膜13的与镀覆层12的界面侧的一部分上,有助于提高皮膜13的密合性。
[非晶质相A]
本实施方式的表面处理钢材1具备的皮膜13通过在规定条件下将含有硅烷偶联剂等Si化合物、磷酸盐等P化合物、V化合物、以及选自作为阀金属(valve metal)的Ti、Zr以及Al中的1种以上化合物的处理液涂布在含锌的镀覆层上并将其干燥来获得。非晶质相A131是占据皮膜13的主要部分的层,作为构成元素,包含来自于硅烷偶联剂的Si、C及O,来自于P化合物的P,来自于V化合物的V,选自作为阀金属的Ti、Zr及Al中的1种以上,以及自镀覆层溶出的Zn。
Si、C以及O(主要作为硅化合物存在)是构成皮膜13的基质的元素。
V以及P(主要作为化合物存在)是缓蚀剂,不含它们时则无法获得充分的耐腐蚀性。
另外,本实施方式的表面处理钢材1中,不仅需要非晶质相A131含有P及V,还需要使V与P的以质量%计的含量比V/P为0.050~1.000。
V/P小于0.050时,无法获得P与V的协同效果,不仅不会获得充分的耐腐蚀性,涂饰密合性也会降低。另外,V/P超过1.000时,自皮膜13的溶出量会增多、涂饰密合性会降低。
另外,Ti、Zr及/或Al(阀金属)是氧化物稳定的元素,含有在皮膜中时,会使皮膜13的表面钝化、提高耐腐蚀性。皮膜13不含这些元素时,无法获得充分的耐腐蚀性。
另外,如后所述,阀金属还有助于非晶质相B的形成。因此,当不含阀金属时,无法获得充分的涂饰密合性。
另外,如后所述,本实施方式的表面处理钢材1中,在皮膜13与镀覆层12的界面附近形成自镀覆层12溶出的Zn与皮膜13中的Si进行氢键合而获得的具有Si-O-Zn键的层(非晶质相B),提高皮膜13的密合性。
但是,Zn与缓蚀剂进行反应、形成磷酸锌,进行沉淀。因此Zn自镀覆层的溶出量过剩,在非晶质相A中当Zn的含量超过10质量%时,作为皮膜13中的缓蚀剂存在的P减少、耐腐蚀性降低。因此非晶质相A131的Zn含量为10质量%以下。
[非晶质相B]
非晶质相B132是在形成皮膜13时,自镀覆层12溶出的Zn与用于形成皮膜的处理液所含硅烷偶联剂的Si通过脱水缩合反应得到的共价键而形成的具有Si-O-Zn键的层。因此,非晶质相B132包含Si、O以及Zn。而非晶质相B132虽然多含Si-O-Zn键,但不与Si键合的Zn由于优先地与非晶质相A131中的P形成离子键,因而作为Zn与Si的峰强度比的Zn/Si小于Zn/Si为1.0以上的非晶质相A(Zn/Si变得小于1.0)。对于该非晶质相B产生的理由虽不清楚,但认为对于硅烷偶联剂的脱水缩合反应而言,阀金属变成催化剂。
非晶质相B132通过存在于皮膜13的皮膜13与镀覆层12的界面上,皮膜13的密合性提高。因此,本实施方式的表面处理钢材1中,在皮膜13的与镀覆层12的界面侧上形成非晶质相B132。非晶质相B132可以断续地形成,也可以连续地形成。充分地获得密合性提高效果时,在厚度方向的截面上进行观察时,需要镀覆层12与非晶质相B132的界面长度占镀覆层12与皮膜13的界面长度为30%以上。即,镀覆层12与非晶质相A131的界面长度占镀覆层12与皮膜13的界面长度为70%以下。镀覆层12与皮膜13的界面长度中的镀覆层12与非晶质相B132的界面长度比例还可以为100%,从不均匀反应场的观点出发,还可以为70%以下。
因非晶质相B存在而密合性提高的理由虽不清楚,但认为其原因在于,非晶质相B具有的Si-O-Zn键是通过镀覆层表面的Zn(锌)与用于形成皮膜的处理液所含硅烷偶联剂的脱水缩合反应而产生的。
另外认为,镀覆层12与非晶质相B132的界面长度占镀覆层12与皮膜13的界面长度的比例对镀覆表面的氧化膜厚度也产生影响。
皮膜13中的非晶质相A及非晶质相B的鉴定以及非晶质相A及非晶质相B所含构成元素的含量、峰强度比、质量比可以使用EDS(Energy dispersive X-ray spectroscopy,能量色散型X射线分光法)测定。
具体地说,使用会聚离子束装置(RB)FB2000A(日立制作所制)或与其同等的装置,利用FIB-μ采样法由测定对象位置制作TEM观察用的薄膜试样。为了保护,试样的最表面进行W蒸镀。筛网使用Cu筛网。
对于所得的试样,使用场发射透射式电子显微镜HF-2000(日立制作所制)使加速电压为200kV、以5万倍的视场观察组织,同时使用附带的EDS分析装置delta plus level 2(Kevex制)使加速电压为200kV进行元素分析。
对于Si、C、O、P、V、Zn、Ti、Zr、Al,利用半定量法进行定量评价。在求算测定位置的元素的含量的同时,还算出元素的峰强度比、质量比(以质量%计的含量比)。
测定的结果为,将Zn与Si的峰强度比Zn/Si为1.0以上且通过TEM的电子束衍射被判断为非晶质的部分判断为非晶质相A,将Zn与Si的峰强度比Zn/Si小于1.0且通过TEM的电子束衍射被判断为非晶质的部分判断为非晶质相B。
另外,在非晶质相A、非晶质相B中,若Si、C、O、P、Zn、V、Ti、Zr、Al的含量分别为0.5质量%以上,则判断为含有对象的元素(0.5质量%以上的元素)。
在测定时,选择比测定点尺寸更厚的相,对该各相的中央部进行点分析。另外,对于认为是非晶质相A、非晶质相B的相分别测定3点以上,采用其平均值作为该相中的含量。
另外,镀覆层与非晶质相B的界面长度占镀覆层与皮膜的界面长度(比例)使用上述场发射透射式电子显微镜,作为界面长度以10μm以上的范围观察镀覆层与皮膜的界面,其中,测定镀覆层与非晶质相B的界面长度,从而求得。(通过[镀覆层与非晶质相B的界面长度]/[镀覆层与皮膜的界面长度]×100算出。)
[皮膜厚度]
皮膜13(包含非晶质相A131以及非晶质相B132)的厚度为100nm以上且1000nm以下。
皮膜13的厚度小于100nm时,耐腐蚀性或涂饰密合性会发生劣化。而皮膜13的厚度超过1000nm时,虽然耐腐蚀性是良好的,但缓蚀剂成分自皮膜13的溶出量变多、涂饰密合性降低。
皮膜厚度利用电磁膜厚计进行测定。具体地说,使用电磁膜厚计测定任意10点,将其平均值作为皮膜厚度。
接着,对本实施方式的表面处理钢材的优选制造方法进行说明。
本实施方式的表面处理钢材与制造方法无关,只要具有上述特征则可以获得该效果,若为以下所示的制造方法,则可以稳定地制造,因此优选。
即,本实施方式的表面处理钢材可以利用包含以下工序的制造方法进行制造。
(I)通过将钢材(钢板)浸渍于含Zn的镀覆浴中或者在含Zn的水溶液或熔融盐中的电镀,在表面上形成镀覆层的镀覆工序;
(II)在具有镀覆层的钢材上涂布表面处理金属剂(处理液)的涂布工序;以及
(III)对涂布有表面处理金属剂的钢材进行加热,形成包含Si、C、O、P、Zn及V、以及选自Ti、Al及Zr中的1种以上的皮膜的加热工序。
对各个工序说明优选的条件。
[镀覆工序]
镀覆工序并无特别限定。只要是按照获得充分镀覆密合性的方式利用通常的方法进行即可。
另外,对于供至镀覆工序的钢材的制造方法也无限定。
例如,可以是JIS G3302:2019规定的镀锌钢板的制造方法,还可以是JIS G3323:2019或JIS G3313:2017规定的镀覆钢板的制造方法。
镀覆浴的组成只要是根据想要获得的镀覆层的组成进行调整即可。
镀覆冷却工序后,优选:在直至涂布工序之前的期间,管理成避免过剩的表面氧化、油附着等、不会排斥药剂的镀覆表面状态。
[涂布工序]
在涂布工序中,在具有含Zn的镀覆层的钢板等钢材上涂布包含Si化合物、P化合物、V化合物、以及Ti、Zr及/或Al的化合物的表面处理金属剂。Si化合物、P化合物、V化合物、以及Ti化合物、Zr化合物及/或Al化合物为了成为皮膜的构成元素而含有。另外,P化合物还具有使镀覆层的Zn通过蚀刻反应而溶出的效果,通过与阀金属的组合,有助于非晶质相B的生成。
在涂布工序中,表面处理金属剂的涂布方法并无限定。例如可以使用辊涂机、棒涂机、喷雾等进行涂布。
通过捡拾辊与涂抹辊的旋转速度或圆周速度比来改变涂布量,可以改变皮膜厚度。
本实施方式中,表面处理金属剂中所含的Si化合物为了形成非晶质相B,优选成为在分子中含有异氰酸酯基、氨基或环氧基等的硅烷偶联剂,其中更优选异氰酸酯基。
表面处理金属剂中的Si化合物的浓度优选为5~20质量%。
本实施方式中,表面处理金属剂包含的P化合物并无别限定,可以示例磷酸、磷酸铵盐、磷酸钾盐、磷酸钠盐等。其中,更优选磷酸。使用磷酸时,可以获得更为优异的耐腐蚀性。表面处理金属剂中的P化合物的浓度优选为1~5质量%。
另外,表面处理金属剂包含的V化合物可以示例五氧化钒V2O5、偏钒酸HVO3、偏钒酸铵、偏钒酸钠、三氯氧钒VOCl3、三氧化钒V2O3、二氧化钒VO2、硫酸氧钒VOSO4、乙酰丙酮氧钒VO(OC(=CH2)CH2COCH3)2、乙酰丙酮钒V(OC(=CH2)CH2COCH3)3、三氯化钒VCl3、磷钒钼酸等。另外,还可以使用通过具有选自羟基、羰基、羧基、伯~叔氨基、酰胺基、磷酸基以及膦酸基中的至少1种官能团的有机化合物,将5价的钒化合物还原成4价~2价者。表面处理金属剂中的V化合物的浓度优选为0.0001~4.0质量%。
另外,作为Ti化合物、Zr化合物、Al化合物,可示例硝酸钛、硝酸锆、硝酸铝等。
[加热工序]
加热工序中,对涂布有表面处理金属剂的钢材进行加热使其干燥,进行烘烤来形成皮膜。对于加热温度(使其干燥的温度)优选最高到达温度为60~200℃、更优选为80~150℃。最高到达温度小于60℃时,由于表面处理金属剂的溶剂不会完全地挥发,因此不优选。而最高到达温度超过200℃时,由加热带来的溶剂干燥效果饱和、不经济,因此不优选。
加热工序中,表面处理金属剂的加热方法并无限定。例如可以使用IH、热风炉等进行加热使其干燥。
另外,从室温下的表面处理金属剂(处理液)涂布(涂布结束时)至到达最高到达温度为止的时间很长时,由于自镀覆层的Zn溶出量增多,因此从表面处理金属剂(处理液)涂布至到达最高到达温度为止的时间优选为10.0秒钟以下、更优选为4.0秒钟以下。
到达最高到达温度之后的表面处理钢材冷却至室温附近。冷却条件并无特别限定,考虑到气体冷却或者使用了液体的喷雾冷却或液没冷却。
实施例
作为用于在表面形成皮膜的镀覆钢板,准备作为JIS G3302:2019中规定的镀锌钢板、镀覆附着量用Z08标记的熔融镀锌钢板。
对于该镀覆钢板,如表1所示的那样,使用辊涂机涂布以下种类的处理液A~S中的任一者。
(处理液A)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒75mg和磷酸氢二铵3g的同时,溶解了硝酸钛1g的水溶液。
(处理液B)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒70mg和磷酸氢二铵2g的同时,溶解了硝酸钛1g的水溶液。
(处理液C)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒70mg和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液D)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒100mg和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液E)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液F)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒1.7g和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液G)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒9.0g和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液H)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液I)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg的同时,溶解了硝酸钛1g的水溶液。
(处理液J)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的水溶液。
(处理液K)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,溶解了硝酸锆1g的水溶液。
(处理液L)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,溶解了硝酸铝1g的水溶液。
(处理液M)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,分别溶解了硝酸钛和硝酸锆0.5g的水溶液。
(处理液N)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,分别溶解了硝酸钛和硝酸铝0.5g的水溶液。
(处理液O)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,分别溶解了硝酸锆和硝酸铝0.5g的水溶液。
(处理液P)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒84mg和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液Q)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒1.6g和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液R)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到10%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒1.3g和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
(处理液S)
将用按照3-异氰酸酯丙基三乙氧基硅烷以质量比计达到3%且二氧化硅溶胶(日产化学制ST-NXS)以质量比计达到7%的方式以1:1混合有乙醇和0.05%氨水的溶液进行调整并放置了3小时的溶液作为基础液,在该溶液100mL中溶解乙酰丙酮氧钒170mg和磷酸氢二铵1g的同时,溶解了硝酸钛1g的水溶液。
在室温(20℃)下在钢板上涂布上述表面处理金属剂之后,根据需要进行放置,然后按照从涂布结束至到达最高到达温度的时间成为表1所示值的方式使用热风干燥炉加热至最高到达温度。平均加热速度是还包括了放置时间算出的从涂布结束至到达最高到达温度的平均加热速度。
之后放冷至室温。
由此,获得表面处理钢材No.1~30。
表1
利用上述方法(Zn/Si以及是否是非晶质)对所得的表面处理钢材进行非晶质相A以及非晶质相B的鉴定,同时求算皮膜的厚度、非晶质相A及非晶质相B的元素分析、镀覆层与上述非晶质相B的界面长度占镀覆层与皮膜的界面长度的比例。
将结果示于表2中。
另外,利用以下的方法对所得表面处理钢材评价耐腐蚀性及涂饰密合性。
[耐腐蚀性]
制作平板试验片,对各试验片进行基于JIS Z 2371:2015的盐水喷雾试验,评价120小时后的表面的白锈发生状况(试验片的面积中产生了白锈的面积的比例)。
若白锈产生面积率为5%以下,则判断为耐腐蚀性优异。
[涂饰密合性]
制作平板试验片,按照干燥后的膜厚达到20μm的方式涂布白色涂料(Amirac#1000)。将该试验片浸渍在沸水中30分钟后,使用Erichsen拉伸装置拉伸至7mm高度,实施带剥离试验,确认涂膜残留率。
涂膜的残留面积率若为80%以上,则判断为涂饰密合性优异。
由表1~表2可知,含有规定量的Si、C、O、P、Zn、V以及选自Ti、Zr及Al中的1种或2种以上,与非晶质相B的界面的长度比例为30%以上的No.4~6、8、9、14~18、20~23、25、28、29中,获得了优异的耐腐蚀性及涂饰密合性。
而未满足一个以上本发明要件的比较例No.1~3、7、10~13、19、24、26、27、30中,耐腐蚀性、涂饰密合性中的任一者或两者均差。
产业上的可利用性
根据本发明,可以提供具有优异涂饰密合性以及优异耐腐蚀性的表面处理钢材。该表面处理钢材的产业上的可利用性高。
符号说明
1表面处理钢材
11钢板
12镀覆层
13皮膜
131非晶质相A
132非晶质相B
Claims (2)
1.一种表面处理钢材,其具有:
钢板;
形成在所述钢板上且含锌的镀覆层;以及
形成在所述镀覆层上的皮膜;
所述皮膜的厚度为100nm以上且1000nm以下,
所述皮膜包含非晶质相A和非晶质相B,所述非晶质相A作为构成元素含有Si、C、O、P、Zn及V、以及选自Ti、Zr及Al中的1种或2种以上,进行利用EDS的分析时,作为Zn与Si的峰强度比的Zn/Si为1.0以上、作为V与P的质量比的V/P为0.050~1.000,所述非晶质相B含有Si、O、Zn,进行利用EDS的分析时,作为Zn与Si的峰强度比的Zn/Si小于1.0,
所述非晶质相A的Zn含量为10质量%以下,
在厚度方向的截面中,所述镀覆层与所述非晶质相B的界面长度占所述镀覆层与所述皮膜的界面长度为30%以上。
2.根据权利要求1所述的表面处理钢材,所述镀覆层的化学组成以质量%计包含
Al:0.1%以上且小于25.0%、
Mg:0%以上且小于12.5%、
Sn:0%以上且20%以下、
Bi:0%以上且小于5.0%、
In:0%以上且小于2.0%、
Ca:0%以上且3.0%以下、
Y:0%以上且0.5%以下、
La:0%以上且小于0.5%、
Ce:0%以上且小于0.5%、
Si:0%以上且小于2.5%、
Cr:0%以上且小于0.25%、
Ti:0%以上且小于0.25%、Ni:0%以上且小于0.25%、Co:0%以上且小于0.25%、V:0%以上且小于0.25%、Nb:0%以上且小于0.25%、Cu:0%以上且小于0.25%、Mn:0%以上且小于0.25%、Fe:0%以上且5.0%以下、Sr:0%以上且小于0.5%、Sb:0%以上且小于0.5%、Pb:0%以上且小于0.5%、B:0%以上且小于0.5%、以及剩余部分:Zn及杂质。
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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 |
JP2004292943A (ja) * | 2003-02-03 | 2004-10-21 | Nippon Steel Corp | 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 |
JP2005226142A (ja) * | 2004-02-16 | 2005-08-25 | Jfe Steel Kk | 耐白錆性と外観が優れた表面処理鋼板 |
JP2010208067A (ja) * | 2009-03-09 | 2010-09-24 | Nisshin Steel Co Ltd | 塗装鋼板および外装部材 |
WO2013027837A1 (ja) * | 2011-08-24 | 2013-02-28 | 新日鐵住金株式会社 | 塗装めっき鋼材 |
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TWI792932B (zh) | 2023-02-11 |
MX2023010121A (es) | 2023-09-11 |
JP7376843B2 (ja) | 2023-11-09 |
KR20230141860A (ko) | 2023-10-10 |
WO2022186380A1 (ja) | 2022-09-09 |
CA3209039A1 (en) | 2022-09-09 |
AU2022230506A1 (en) | 2023-09-28 |
CN117015631A (zh) | 2023-11-07 |
JPWO2022186380A1 (zh) | 2022-09-09 |
EP4303340A1 (en) | 2024-01-10 |
TW202239990A (zh) | 2022-10-16 |
BR112023017302A2 (pt) | 2023-09-26 |
US20240043981A1 (en) | 2024-02-08 |
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