CN114133848A - 锌铝镁合金钢板表面处理液及其制备方法和使用方法 - Google Patents
锌铝镁合金钢板表面处理液及其制备方法和使用方法 Download PDFInfo
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- CN114133848A CN114133848A CN202111439885.1A CN202111439885A CN114133848A CN 114133848 A CN114133848 A CN 114133848A CN 202111439885 A CN202111439885 A CN 202111439885A CN 114133848 A CN114133848 A CN 114133848A
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- aluminum
- zinc
- steel plate
- water
- magnesium alloy
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- -1 Zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 61
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 57
- 239000010959 steel Substances 0.000 title claims abstract description 57
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 39
- 238000004381 surface treatment Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 150000003754 zirconium Chemical class 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 14
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 239000004203 carnauba wax Substances 0.000 claims description 3
- 235000013869 carnauba wax Nutrition 0.000 claims description 3
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000007730 finishing process Methods 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229930182470 glycoside Natural products 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007850 degeneration Effects 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- 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
- C23C2/26—After-treatment
Abstract
本发明属于锌铝镁合金镀层钢板技术领域，具体涉及锌铝镁合金镀层钢板表面处理液及其制备方法和使用方法。本发明首先提供了一种锌铝镁合金镀层钢板表面处理液，所述处理液各成分含量以100重量份的水为基准计，硅烷偶联剂5～20重量份、碱性缓蚀剂0.5～10重量份、锆盐1～10重量份、水性润滑剂5～20重量份、水性有机乳液15～35重量份、表面活性剂0.1～2.0重量份。本发明中的钢板表面处理液适用于镀层成分0.5～6％Al、0.2～3.0％Mg的锌铝镁钢板，可使锌铝镁表面环保涂层致密均匀，阻碍了镀层与环境中水汽和氧的接触，显著提升了表面涂层的耐蚀性、耐黑变性、耐水性、耐指纹性、可涂装性、自润滑性，满足了用户冲压、涂装的使用要求。
Description
技术领域
本发明属于锌铝镁合金镀层钢板技术领域，具体涉及锌铝镁合金镀层钢板表面处理液及其制备方法和使用方法。
背景技术
锌铝镁合金镀层钢板具有十分优异的耐蚀性(漆膜下耐蚀性、平板耐蚀性和切口防护性)，还具有良好的成形性、焊接性及涂装性，替代热镀锌板、热镀铝锌板、热浸镀锌铝板的趋势日益明显。
现有热浸镀锌铝镁合金镀层钢板可分为“低铝”(WAl＜5％)、“中铝”(5％≤WAl＜13％) 和“高铝”(47％≤WAl≤57％)三种类型。随着Al和Mg含量的增多，镀层的耐蚀性升高，但成形性能和焊接性能下降。在家电、汽车应用领域，为保证锌铝镁合金镀层钢板满足用户的冲压成型要求，要求其具有良好的成形性，需采用低铝的成分体系。
锌铝镁合金镀层表面有大量的Al、Mg元素，在放置和储运过程中极易发生氧化，出现发黑现象，严重时出现黑色锈蚀现象。为提高锌铝镁合金镀层钢板的耐蚀性，并预防其发生黑变，需对锌铝镁合金镀层钢板表面进行钝化处理。但是，目前关于锌铝镁镀层钢板环保表面处理技术尚不成熟。
中国专利文献CN107418328A公开了一种锌铝镁镀层钢板的专用无铬耐指纹液，该专用无铬耐指纹液由下列质量分数的原料组分组成：硅烷偶联剂1～20份；水性丙烯酸树脂1～ 20份；水性聚氨酯树脂1～20份；金属化合物1～10份；润滑助剂1～10份；去离子水20～70份。硅烷偶联剂一般在一定的条件下(酸性、碱性或中性)水解，该专利文献中未规定条件，无法保证硅烷偶联剂作用的发挥和产品质量的稳定。
黑变是锌铝镁产品的特性，目前尚未见有优异耐黑变的环保表面涂层。因此，为实现锌铝镁合金镀层钢板产品在家电领域的应用，有必要开展具有耐黑变性能的锌铝镁合金镀层钢板及其制备方法的研究。
发明内容
本发明所要解决的技术问题是提供一种能使锌铝镁合金钢板具有优异的耐黑变性能的锌铝镁合金镀层钢板表面处理液及其制备方法和使用方法。
本发明为解决上述技术问题采用的技术方案是：首先提供了一种锌铝镁合金镀层钢板表面处理液，所述处理液各成分含量以100重量份的水为基准计，硅烷偶联剂5～20重量份、碱性缓蚀剂0.5～10重量份、锆盐1～10重量份、水性润滑剂5～20重量份、水性有机乳液 15～35重量份、表面活性剂0.1～2.0重量份。
进一步的是：硅烷偶联剂10～20重量份、碱性缓蚀剂1～8重量份、锆盐3～10重量份、水性润滑剂8～16重量份、水性有机乳液20～30重量份、表面活性剂0.5～2.0重量份。
进一步的是：所述硅烷偶联剂为N,N-二甲基-3-氨丙基三甲氧基硅烷、N,N-二乙基-3-氨丙基三甲氧基硅烷、3-氨丙基甲基二甲氧基硅烷、3-氨丙基甲基二乙氧基硅烷、3-氨丙基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基甲基二乙氧基硅烷或N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷中的至少一种。
进一步的是：所述碱性缓释剂为硅酸钠、硅酸钾、钼酸钠、钼酸钾、钼酸锂、钼酸铵、三聚磷酸钠、六偏磷酸钠、磷酸三钠、磷酸三钾、磷酸氢二钠、氟化钠、氟化钾、钨酸钠、钨酸钾、钨酸铵、偏钒酸铵、偏钒酸钾、偏钒酸钠中的至少一种。
进一步的是：所述锆盐为氟锆酸钠、氟锆酸钾、氟锆酸锂、氟锆酸钡、锆酸钠、锆酸钾、锆酸铵中的至少一种。
进一步的是：所述水性润滑剂为氟碳乳液、聚醚型改性硅氧烷、聚醚烷基硅油、环氧改性硅油、巴西棕榈蜡乳液、硬聚乙烯蜡乳液中的至少一种。
进一步的是：所述表面活性剂为十二烷基硫酸钠、聚乙二醇、烷基糖苷、椰油酸二乙醇酰胺、十二烷基苯磺酸钠中的至少一种。
进一步的是：所述水性有机乳液为水性丙烯酸树脂乳液、水性苯丙乳液、水性聚氨酯乳液、水性硅丙乳液、水性聚醚改性丙烯酸树脂乳液、水性环氧树脂乳液中的至少一种，且必须包含水洗聚氨酯乳液；其中，水性聚氨酯乳液与基准水相比，其质量百分比≥15％。即相当于水性有机乳液中必须有水洗聚氨酯乳液，其他的水性丙烯酸树脂乳液、水性苯丙乳液、水性硅丙乳液、水性聚醚改性丙烯酸树脂乳液、水性环氧树脂乳液，可以含有一种或者多种，也可以没有。
本发明还提供了一种上述锌铝镁合金钢板表面处理液的制备方法，包括以下步骤：将碱性缓蚀剂和锆盐溶于水中，然后加入硅烷偶联剂，再加入水性有机乳液，待水解完成后加入水性润滑剂，最后加入表面活性剂，搅拌10～60min放置即可。
本发明还提供了一种上述锌铝镁合金钢板表面处理液的使用方法，包括以下步骤：将锌铝镁合金钢板表面处理液以辊涂或喷淋方式涂敷在锌铝镁合金钢板表面，在80～150℃下固化5～60s即得耐黑变热浸镀锌铝镁涂层板；在涂敷锌铝镁合金钢板表面处理液前的锌铝镁合金钢板镀层成分中，按照重量比计，Al含量为0.5％～6％，Mg含量为0.2％～3.0％。
进一步的是：所述耐黑变热浸镀锌铝镁涂层板的涂层厚度为0.4～2.5μm。
进一步的是：涂层固化后进行光整，所述光整工艺中光整辊的表面粗糙度Ra为2.5～ 4.0μm，光整延伸率0.4～2.0％。采用上述光整工艺后得到的涂层板的表面粗糙度为0.6～2.0μm。
本发明的有益效果是：
本发明结合锌铝镁合金钢板表面镀层的组成特性，采用锆盐、碱性缓蚀剂和硅烷偶联剂与镀层中的Mg、Al反应使镀层和膜层紧密结合，采用聚氨酯(聚氨酯水性乳液的主要成分是聚氨酯树脂)等树脂构建膜层架构、硅烷偶联剂交联填充增强膜层致密性，采用表面活性剂增大膜层与水或水溶液的接触角，采用润滑剂增强涂层的润滑性。采用本发明钢板处理液使锌铝镁表面环保涂层致密均匀，阻碍了镀层与环境中水汽和氧的接触，显著提升了表面涂层的耐蚀性、耐黑变性、耐水性、耐指纹性、可涂装性、自润滑性，满足了用户冲压、涂装的使用要求。
本发明中的钢板表面处理液适用于镀层成分0.5～6％Al、0.2～3.0％Mg的锌铝镁钢板，这是由于镀层含量的不同，镀层表面的Al、Zn、Mg的含量不同，表面处理液呈碱性，其与镀层发生反应，若Al、Mg含量过高，则反应加速，不利于膜层的稳定性。
硅烷偶联剂在涂覆时发生水解反应，部分Si-O与Mg、Al、Zn发生键合作用，部分与有机树脂发生交联反应；以有机树脂为主要成分的水性有机乳液在固化时，有机树脂发生交联作用，与硅烷偶联剂形成一体的膜层，与镀层接触的位置，聚氨酯的氨基集团与Al、Mg反应结合；碱性缓蚀剂增强了表面处理液的碱性，促进了硅烷偶联剂的水解，加快了成膜反应，并与镀层Mg、Al反应沉淀成膜；锆盐密度较大，主要分布在接触界面，加快沉淀成膜，增强膜层与镀层的结合；部分锆盐和碱性缓蚀剂分布在膜层中间的缝隙中，提高膜层中部的致密性；水性润滑剂和表面活性剂共同作用，封闭了膜层表面的空隙，增大了膜层与水或水溶液的接触角，将水汽阻挡在膜层外部。正是由于膜层中不同成分的充分协同作用，其表-中- 界均十分的致密，阻碍了水和氧对镀层的腐蚀，从而提高了表面膜层的耐蚀性和耐黑变性。
具体实施方式
下面将通过具体的实施例对本发明的具体实施方式作进一步地阐述。
一、锌铝镁合金钢板表面处理液的制备方法和使用方法
1、锌铝镁合金钢板表面处理液的制备方法
按照表1中锌铝镁合金钢板表面处理液的各组分含量称取各组分，将碱性缓蚀剂和锆盐溶于水中，然后加入硅烷偶联剂，再加入水性有机乳液，待水解完成后加入水性润滑剂，最后加入表面活性剂，搅拌30min放置即可。
2、锌铝镁合金钢板表面处理液的使用方法
将制备得到的锌铝镁合金钢板表面处理液分别辊涂涂敷在1.5％Al-1.5％Mg-Zn的热镀锌铝镁合金镀层钢板上，在90℃下固化20s分别得到实施例1-12和对比例1-6的热镀锌铝镁板。
锌铝镁合金钢板表面处理液实施例1～12和对比例1～6各组分含量见表1。
表1实施例中绝缘涂层液的组分含量
实施例1～12和对比例1～6中，各组分的具体选择如下：
实施例1～6、对比例1～6中，硅烷偶联剂为N,N-二乙基-3-氨丙基三甲氧基硅烷、碱性缓蚀剂为钼酸钠、锆盐为氟锆酸钾、水性润滑剂为氟碳乳液、水性有机乳液为水性聚氨酯乳液和水性硅丙乳液，其中聚氨酯乳液的质量百分比为15％、表面活性剂为十二烷基苯磺酸钠。
实施例7中，与实施例1不同的是，硅烷偶联剂为3-氨丙基三乙氧基硅烷。
实施例8中，与实施例1不同的是，碱性缓蚀剂为偏钒酸钠。
实施例9中，与实施例1不同的是，锆盐为锆酸钾。
实施例10中，与实施例1不同的是，水性润滑剂为巴西棕榈蜡乳液。
实施例11中，与实施例1不同的是，水性有机乳液为水性聚氨酯乳液和水性苯丙乳液，其中聚氨酯乳液的质量百分比为20％。
实施例12中，与实施例1不同的是，表面活性剂为椰油酸二乙醇酰胺。
二、锌铝镁合金钢板表面处理液用于热镀锌铝镁板后的性能测试
通过本测试例来测定热镀锌铝镁合金钢板表面处理液的稳定性，其测试方法为：将配置好的处理液置于室内通风处，观察液体稳定储存(不出现颜色变化、沉淀、凝聚等不良现象) 的时间，结果见表2(目前处理液的保质期为90d)。
通过本测试例来测定热镀锌铝镁合金钢板表面涂层实施例1～12和对比例1～6涂层的耐蚀性、耐黑变性、耐指纹性、耐水性、涂装性。结果见表3。
其中，耐蚀性按照GB/T10125中规定的方法和条件进行腐蚀试验，然后按照GB12335-90 的规定对腐蚀结果进行评价(以96h、120h后的腐蚀面积占总面积的百分比表示)。其中，腐蚀面积越小越好(目前一般要求NSST/72h腐蚀面积≤5％)。
耐黑变性按照测试NSST/72h的盐雾试验前后的色差变化，若表面未见有明显色变，即色差值≤2，则耐黑变性良好。
耐指纹性按照试样表面涂抹凡士林前后色差值的变化判定：若前后色差的变化小于1，则为A级；若前后色差的变化大于1，小于2，则为B级；若前后色差的变化大于2小于4，则为C级；若前后色差的变化大于4，则为D级。目前涂层的耐指纹性一般为B级及以上。
耐水性是采用100℃去离子水滴于试样来测定：若试样完全无水迹，则为A级；有轻微水迹，则为B级；明显水迹，则为C级。目前涂层耐水性一般为A级或B级。
表2处理液稳定性的测定结果
| 处理液 | 稳定时间(d) | 处理液 | 稳定天数(d) |
| 实施例1 | ≥180 | 实施例10 | ≥180 |
| 实施例2 | ≥180 | 实施例11 | ≥180 |
| 实施例3 | ≥180 | 实施例12 | ≥180 |
| 实施例4 | ≥180 | 对比例1 | ≥180 |
| 实施例5 | ≥180 | 对比例2 | ＜2 |
| 实施例6 | ≥180 | 对比例3 | ≥180 |
| 实施例7 | ≥180 | 对比例4 | ≥180 |
| 实施例8 | ≥180 | 对比例5 | ≥180 |
| 实施例9 | ≥180 | 对比例6 | ≥180 |
表3耐黑变热浸镀锌铝镁涂层板
由实施例1～12和对比例1～6的结果对比可知，本发明提供的锌铝镁合金钢板表面处理液具有良好的稳定性，在涂敷固化后形成的热浸镀锌铝镁涂层板具有良好的耐蚀性、耐指纹性、耐水性等性能，尤其具有优异的耐黑变性。
Claims (10)
1.锌铝镁合金钢板表面处理液，其特征在于：各成分含量以100重量份的水为基准计，硅烷偶联剂5～20重量份、碱性缓蚀剂0.5～10重量份、锆盐1～10重量份、水性润滑剂5～20重量份、水性有机乳液15～35重量份、表面活性剂0.1～2.0重量份。
2.根据权利要求1所述的锌铝镁合金钢板表面处理液，其特征在于：硅烷偶联剂10～20重量份、碱性缓蚀剂1～8重量份、锆盐3～10重量份、水性润滑剂8～16重量份、水性有机乳液20～30重量份、表面活性剂0.5～2.0重量份。
3.根据权利要求1所述的锌铝镁合金钢板表面处理液，其特征在于：所述硅烷偶联剂为N,N-二甲基-3-氨丙基三甲氧基硅烷、N,N-二乙基-3-氨丙基三甲氧基硅烷、3-氨丙基甲基二甲氧基硅烷、3-氨丙基甲基二乙氧基硅烷、3-氨丙基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基甲基二乙氧基硅烷或N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷中的至少一种。
4.根据权利要求1所述的锌铝镁合金钢板表面处理液，其特征在于：所述碱性缓释剂为硅酸钠、硅酸钾、钼酸钠、钼酸钾、钼酸锂、钼酸铵、三聚磷酸钠、六偏磷酸钠、磷酸三钠、磷酸三钾、磷酸氢二钠、氟化钠、氟化钾、钨酸钠、钨酸钾、钨酸铵、偏钒酸铵、偏钒酸钾、偏钒酸钠中的至少一种；
所述锆盐为氟锆酸钠、氟锆酸钾、氟锆酸锂、氟锆酸钡、锆酸钠、锆酸钾、锆酸铵中的至少一种。
5.根据权利要求1所述的锌铝镁合金钢板表面处理液，其特征在于：所述水性润滑剂为氟碳乳液、聚醚型改性硅氧烷、聚醚烷基硅油、环氧改性硅油、巴西棕榈蜡乳液、硬聚乙烯蜡乳液中的至少一种；
所述表面活性剂为十二烷基硫酸钠、聚乙二醇、烷基糖苷、椰油酸二乙醇酰胺、十二烷基苯磺酸钠中的至少一种。
6.根据权利要求1～5任一项所述的锌铝镁合金钢板表面处理液，其特征在于：所述水性有机乳液为水性丙烯酸树脂乳液、水性苯丙乳液、水性聚氨酯乳液、水性硅丙乳液、水性聚醚改性丙烯酸树脂乳液、水性环氧树脂乳液中的至少一种，且必须包含水洗聚氨酯乳液；其中，水性聚氨酯乳液与基准水相比，其质量百分比≥15％。
7.权利要求1～6任一项所述的锌铝镁合金钢板表面处理液的制备方法，其特征在于：将碱性缓蚀剂和锆盐溶于水中，然后加入硅烷偶联剂，再加入水性有机乳液，待水解完成后加入水性润滑剂，最后加入表面活性剂，搅拌10～60min放置即可。
8.锌铝镁合金钢板表面处理液的使用方法，其特征在于：将权利要求1～6任一项所述的锌铝镁合金钢板表面处理液以辊涂或喷淋方式涂敷在锌铝镁合金钢板表面，在80～150℃下固化5～60s即得耐黑变热浸镀锌铝镁涂层板；在涂敷锌铝镁合金钢板表面处理液前的锌铝镁合金钢板镀层成分中，按照重量比计，Al含量为0.5％～6％，Mg含量为0.2％～3.0％。
9.根据权利要求8所述的锌铝镁合金钢板表面处理液的使用方法，其特征在于：所述耐黑变热浸镀锌铝镁涂层板的涂层厚度为0.4～2.5μm。
10.根据权利要求8或9所述的锌铝镁合金钢板表面处理液的使用方法，其特征在于：涂层固化后进行光整，所述光整工艺中光整辊的表面粗糙度Ra为2.5～4.0μm，光整延伸率0.4～2.0％。
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