CN115287642B - 一种水性富锌漆用锌/铝粉析氢抑制钝化剂及其制备方法 - Google Patents
一种水性富锌漆用锌/铝粉析氢抑制钝化剂及其制备方法 Download PDFInfo
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- CN115287642B CN115287642B CN202210914321.7A CN202210914321A CN115287642B CN 115287642 B CN115287642 B CN 115287642B CN 202210914321 A CN202210914321 A CN 202210914321A CN 115287642 B CN115287642 B CN 115287642B
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- agent
- zinc
- passivating agent
- water
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 79
- 239000011701 zinc Substances 0.000 title claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003973 paint Substances 0.000 title claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 239000000080 wetting agent Substances 0.000 claims abstract description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005282 brightening Methods 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 13
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- -1 ethylenediamine-tetramethyl phosphonic acid Chemical compound 0.000 claims description 12
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical group COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 claims description 6
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 claims description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 claims description 6
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 241001122767 Theaceae Species 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical group [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 6
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims description 6
- 229940074393 chlorogenic acid Drugs 0.000 claims description 6
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 claims description 6
- 235000001368 chlorogenic acid Nutrition 0.000 claims description 6
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 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 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 238000002161 passivation Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 239000007921 spray Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
- 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
- C23C22/46—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 oxalates
-
- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- 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
- C23C22/34—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 fluorides or complex fluorides
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc 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
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
本发明提供一种水性富锌漆用锌/铝粉析氢抑制钝化剂及其制备方法。所述钝化剂由A和B两种组分构成，两种组分分开存放，使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中；所述A组分由以下质量配比的原料制得：6.0g无机主钝化剂、3.5g有机辅助钝化剂、0.5g氧化剂、5.0g缓蚀剂、1.0g润湿剂以及6.0g改性硅溶胶；所述B组分由以下质量配比的原料制得：75.0g二丙二醇甲醚、3.0g光亮剂、2.0g稀土钝化剂以及17.0g成膜促进剂。该钝化剂可有效抑制锌/铝粉在水性漆中的析氢行为，该钝化剂的钝化过程对水性富锌漆的自身性能无影响。
Description
技术领域
本发明涉及涂料技术领域，具体涉及一种水性富锌漆用锌/铝粉析氢抑制钝化剂及其制备方法。
背景技术
近年来，随着世界各国对总有机挥发物(VOCs)污染的日益重视及环保法规在VOC排放标准方面的逐步严格，油性漆的使用越来越受到限制，以水为主要溶剂的水性漆占据着越来越重要的市场地位。为提升水性漆的腐蚀防护性能，通常辅助以牺牲阳极的阴极保护技术，将标准电极电位约为0.4V的锌粉添加到漆液中，同时添加一定量的铝粉以提升涂层的光泽度。当材料受到腐蚀时，Zn会优先失去电子，金属铁因而得到保护。但锌粉活性高，在水性漆中极易与水发生析氢反应(方程式1所示)，从而使漆液防腐性能下降，且大量H2析出会导致较大的安全风险，这严重阻碍了水性富锌漆的快速发展应用。
Zn+2H2O→Zn(OH)2+H2 (1)
众所周知，金属钝化是一种金属表面处理技术，是指将金属表面由活化状态转变为钝化状态，产生一层致密的保护膜，从而降低金属溶解的一个过程。为解决上述问题，传统含铬化合物钝化技术被应用于锌粉钝化处理，经钝化处理的锌粉反应活性低，可直接添加到水性漆中。然而，随着国家环保要求的逐步严格，含铬化合物钝化已被禁止使用，开发新型无铬锌/铝粉析氢抑制钝化剂已是当务之急，也是促进水性富锌漆快速发展应用的关键。
发明内容
针对上述技术难题，本发明提供了一种水性富锌漆用锌/铝粉析氢抑制无铬钝化剂及其制备方法。
一种水性富锌漆用锌/铝粉析氢抑制钝化剂，所述钝化剂由A和B两种组分构成，两种组分分开存放，使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中；
所述A组分由以下质量配比的原料制得：6.0g无机主钝化剂、3.5g有机辅助钝化剂、0.5g氧化剂、5.0g缓蚀剂、1.0g润湿剂以及6.0g改性硅溶胶；
所述B组分由以下质量配比的原料制得：75.0g二丙二醇甲醚、3.0g光亮剂、2.0g稀土钝化剂以及17.0g成膜促进剂。
在其中一实施例中，无机主钝化剂选自草酸氧钒、硫酸氧钛、氟硅酸铵中的一种、两种或者两种以上。
在其中一实施例中，有机辅助钝化剂选自绿原酸、乙二胺-四甲基膦酸、茶多酚中的一种、两种或者两种以上。
在其中一实施例中，氧化剂选自硝酸钾、过硫酸铵中的一种，缓蚀剂选自三乙醇胺硼酸酯、咪唑啉和咪唑-4-甲基亚胺基硫脲中的一种、两种或者两种以上
在其中一实施例中，润湿剂选自聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚醚改性有机硅润湿剂WET-628的一种或两种。
在其中一实施例中，光亮剂为茴香醛或水杨醛。
在其中一实施例中，稀土钝化剂为硫酸铈、硝酸钴或者硝酸钇，成膜促进剂选自环氧树脂128，硬脂酸和γ-氨丙基三乙氧基硅烷中的一种、两种或者两种以上。
在其中一实施例中，改性硅溶胶的制备方法为：
a.将1.0g平均粒径约为45nm的金属氧化物加入到50mL去离子水中，加入0.2g分散剂，先剧烈搅拌均匀，再超声振荡30min得到分散均匀的金属氧化物浆料；所述金属氧化物可以为二氧化钛或二氧化锆；
b.将0.5g两性金属盐粉末加入到20mL去离子水中，搅拌直至完全溶解，再将上述制备的金属氧化物浆料缓慢加入，充分搅拌混合均匀；所述两性金属盐为硫酸锌或偏铝酸钠；
c.将步骤b所制备的混合液缓慢加入到盛装有50g 30％酸性硅溶胶的圆底烧瓶中，边滴加边搅拌，滴加完毕后，在100℃下回流反应至少1h后，减压蒸馏出部分去离子水将反应液体积浓缩至50mL，停止加热，待反应液冷却至室温后再用2mol/L的硫酸溶液将其pH值调节至4.0以下，取出，存储备用。
在其中一实施例中，所述分散剂为十六烷基三甲基溴化铵、三聚磷酸钠或者脂肪醇聚氧乙烯醚。
一种水性富锌漆用锌/铝粉析氢抑制钝化剂的制备方法，包括如下步骤：
(1)改性硅溶胶的制备
a.将1.0g平均粒径约为45nm的金属氧化物加入到50mL去离子水中，加入0.2g分散剂，先剧烈搅拌均匀，再超声振荡30min得到分散均匀的金属氧化物浆料；所述金属氧化物可以为二氧化钛或二氧化锆；所述分散剂为十六烷基三甲基溴化铵、三聚磷酸钠或者脂肪醇聚氧乙烯醚；
b.b.将0.5g两性金属盐粉末加入到20mL去离子水中，搅拌直至完全溶解，再将上述制备的金属氧化物浆料缓慢加入，充分搅拌混合均匀；所述两性金属盐为硫酸锌或偏铝酸钠；
c.将步骤b所制备的混合液缓慢加入到盛装有50g 30％酸性硅溶胶的圆底烧瓶中，边滴加边搅拌，滴加完毕后，在100℃下回流反应至少1h后，减压蒸馏出部分去离子水将反应液体积浓缩至50mL，停止加热，待反应液冷却至室温后再用2mol/L的硫酸溶液将其pH值调节至4.0以下，取出，存储备用。
(2)组分A的制备
在装有冷凝回流装置的圆底烧瓶中，先加入78.0g纯化水，然后依次加入6.0g无机主钝化剂，3.5g有机辅助钝化剂，0.5g氧化剂，5.0g缓蚀剂，1.0g润湿剂，每加入一种组分经搅拌加热溶解后再加入下一组分，直至全部成份添加溶解完毕后，再加入6.0g上述合成的改性硅溶胶，继续搅拌混合均匀即制得100.0g组分A；
其中，无机主钝化剂选自草酸氧钒、硫酸氧钛、氟硅酸铵中的一种、两种或者两种以上，有机辅助钝化剂选自绿原酸、乙二胺-四甲基膦酸、茶多酚中的一种、两种或者两种以上，氧化剂选自硝酸钾、过硫酸铵中的一种，缓蚀剂选自三乙醇胺硼酸酯、咪唑啉和咪唑-4-甲基亚胺基硫脲中的一种、两种或者两种以上，润湿剂选自聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚醚改性有机硅润湿剂WET-628的一种或两种；
(3)组分B的制备
在装有冷凝回流装置的100mL圆底烧瓶中，先加入75.0g二丙二醇甲醚，加热至80℃，然后依次加入3.0g光亮剂，2.0g稀土钝化剂，17.0g成膜促进剂，每加入一种组分后先加热搅拌至溶解，然后再加入下一种组分，直至全部组分添加并溶解完毕为止，可制得100.0g组分B；
其中，光亮剂为茴香醛或水杨醛，稀土钝化剂为硫酸铈、硝酸钴或者硝酸钇，成膜促进剂选自环氧树脂128，硬脂酸和γ-氨丙基三乙氧基硅烷中的一种、两种或者两种以上；
(4)使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中，室温下均匀分散一定时间即可。
本发明采用有机-无机杂化钝化技术，成功开发了一种高效的水性富锌漆用锌/铝粉析氢抑制钝化剂，该钝化剂可有效抑制锌/铝粉在水性漆中的析氢行为，经钝化后的锌/铝粉在0.1mol/L的盐酸溶液中24h的析氢量少于0.5mL，采用钝化锌/铝粉配制的水性富锌漆可稳定存放半年以上，且该钝化剂的钝化过程对水性富锌漆的自身性能无影响。
附图说明
图1为锌/铝粉析氢性能测试装置图。
图2为不同条件下制备的水性富锌漆涂层盐雾试验照片。
图3为采用钝化和未钝化锌粉所制备富锌漆涂层的交流阻抗谱图：(a)Nyquist图，(b)Bode图。
图4为采用钝化和未钝化锌粉所制备富锌漆涂层的Tafel极化曲线图。
具体实施方式
以下结合实施例对本发明做进一步描述，但不局限于此。在实例中，“份数”指重量份，除非另有说明。
本发明提供一种水性富锌漆用锌/铝粉析氢抑制钝化剂，所述钝化剂由A和B两种组分构成，两种组分分开存放，使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中，室温下均匀分散一定时间即可。
所述A组分由以下质量配比的原料制得：6.0g无机主钝化剂、3.5g有机辅助钝化剂、0.5g氧化剂、5.0g缓蚀剂、1.0g润湿剂以及6.0g改性硅溶胶。
其中，无机主钝化剂选自草酸氧钒、硫酸氧钛、氟硅酸铵中的一种、两种或者两种以上，有机辅助钝化剂选自绿原酸、乙二胺-四甲基膦酸、茶多酚中的一种、两种或者两种以上，氧化剂选自硝酸钾、过硫酸铵中的一种，缓蚀剂选自三乙醇胺硼酸酯、咪唑啉和咪唑-4-甲基亚胺基硫脲中的一种、两种或者两种以上，润湿剂选自聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚醚改性有机硅润湿剂WET-628的一种、两种或者两种以上。
所述B组分由以下质量配比的原料制得：75.0g二丙二醇甲醚、3.0g光亮剂、2.0g稀土钝化剂以及17.0g成膜促进剂。
其中，光亮剂为茴香醛或水杨醛，稀土钝化剂为硫酸铈、硝酸钴或者硝酸钇，成膜促进剂选自环氧树脂128，硬脂酸和γ-氨丙基三乙氧基硅烷中的一种、两种或者两种以上。
所述钝化剂的制备方法包括如下步骤：
(1)改性硅溶胶的制备
a.将1.0g平均粒径约为45nm的金属氧化物加入到50mL去离子水中，加入0.2g分散剂，先剧烈搅拌均匀，再超声振荡30min得到分散均匀的金属氧化物浆料。
所述金属氧化物可以为二氧化钛或二氧化锆；所述分散剂为十六烷基三甲基溴化铵、三聚磷酸钠或者脂肪醇聚氧乙烯醚。
b.将0.5g两性金属盐粉末加入到20mL去离子水中，搅拌直至完全溶解，再将上述制备的金属氧化物浆料缓慢加入，充分搅拌混合均匀；所述两性金属盐为硫酸锌或偏铝酸钠；c.将步骤b所制备的混合液缓慢加入到盛装有50g 30％酸性硅溶胶的圆底烧瓶中，边滴加边搅拌，滴加完毕后，在100℃下回流反应至少1h后，减压蒸馏出部分去离子水将反应液体积浓缩至50mL，停止加热，待反应液冷却至室温后再用2mol/L的硫酸溶液将其pH值调节至4.0以下，取出，存储备用。
(2)组分A的制备
在装有冷凝回流装置的圆底烧瓶中，先加入78.0g纯化水，然后依次加入6.0g无机主钝化剂，3.5g有机辅助钝化剂，0.5g氧化剂，5.0g缓蚀剂，1.0g润湿剂，每加入一种组分经搅拌加热溶解后再加入下一组分，直至全部成份添加溶解完毕后，再加入6.0g上述合成的改性硅溶胶，继续搅拌混合均匀即制得100.0g组分A。
其中，无机主钝化剂选自草酸氧钒、硫酸氧钛、氟硅酸铵中的一种、两种或者两种以上，有机辅助钝化剂选自绿原酸、乙二胺-四甲基膦酸、茶多酚中的一种、两种或者两种以上，氧化剂选自硝酸钾、过硫酸铵中的一种，缓蚀剂选自三乙醇胺硼酸酯、咪唑啉和咪唑-4-甲基亚胺基硫脲中的一种、两种或者两种以上，润湿剂选自聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚醚改性有机硅润湿剂WET-628的一种或者两种。
(3)组分B的制备
在装有冷凝回流装置的100mL圆底烧瓶中，先加入75.0g二丙二醇甲醚，加热至80℃，然后依次加入3.0g光亮剂，2.0g稀土钝化剂，17.0g成膜促进剂，每加入一种组分后先加热搅拌至溶解，然后再加入下一种组分，直至全部组分添加并溶解完毕为止，可制得100.0g组分B。
其中，光亮剂为茴香醛或水杨醛，稀土钝化剂为硫酸铈、硝酸钴或者硝酸钇，成膜促进剂选自环氧树脂128，硬脂酸和γ-氨丙基三乙氧基硅烷中的一种、两种或者两种以上。
(4)本发明所提供的锌/铝粉钝化剂由A和B两种组分构成，两种组分分开存放，使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中，室温下均匀分散一定时间即可。
析氢抑制性能测试方法
(1)锌/铝粉析氢装置测试
取上述配制的组分A20.0g和组分B2.0g混合均匀，然后加入二丙二醇甲醚78.0g搅拌混合均匀即可得到稀释后的钝化液，将一定量的锌/铝粉加入混合液中，室温下搅拌10min，过滤，纯化水清洗，真空干燥即可完成锌/铝粉的钝化。锌粉钝化效果采取如下方法进行测试，并与空白锌粉进行对照。
采用如图1所示的测试装置，将具有刻度的试管装满水，倒置并调整液面刻度至50mL，用150mL锥形瓶装锌粉5.0g，加入0.2mol/L的盐酸水溶液70mL，将锥形瓶置于磁力搅拌器上，开启磁力搅拌，设定加热温度为50℃，每隔5min观察倒置试管中液面高度并记录析氢量，总时长为30min，同时做空白试验。
(2)盐雾试验
取100g锌粉加入到58mL二丙二醇二甲醚中，搅拌10min，加入钝化组分B1.0g，搅拌10min，再加入涂料功能助剂并与锌浆混合均匀，最后加入成膜树脂69g和钝化剂组分A10.0g，启动涂料研磨分散机，研磨4h后即可制得钝化锌粉水性富锌漆。
向上述制备的漆液中加入纯化水15mL，搅拌均匀，放置一定时间后通过喷漆装置喷涂在经过预处理的碳钢片表面，300℃高温固化即可，采用同样的方法制备空白涂层碳钢片。将上述制备的涂层钢片表面制造划痕，然后将其置于盐雾试验机中进行盐雾试验。
(3)电化学测试
选取经过钝化处理和未经过钝化处理的富锌漆涂层碳钢片样品，并在涂层表面制备十字交叉划痕，将样品采用东华DH7000型电化学工作站测定其耐腐蚀性能，电解质溶液为3.5％的中性氯化钠溶液，处理系统采用三电极体系，饱和甘汞电极为参比电极，4cm2的铂片为辅助电极，碳钢片样品为工作电极。工作电极仅保留1cm2的待测工作面，其余部分用环氧树脂封装。交流阻抗谱测试交流正弦激励信号幅值为5mV，频率范围为1×(10-2～105)Hz，从开路电位开始测试。Tafel极化曲线测试扫描速度为0.5mV/s，扫描范围为相对于开路电位-0.25V～0.25V。
实验结果与讨论
1.锌/铝粉析氢实验结果
锌/铝粉析氢实验测试结果如表1所示，经过钝化处理的锌粉，其30min析氢量仅为1.5mL，相较未钝化锌粉减少了17.8mL，这说明锌粉的钝化处理有效抑制了锌粉在0.2mol/L盐酸水溶液中的析氢行为，表明钝化锌粉可安全添加到水性漆中。
表1析氢量测试结果明细表
2.盐雾试验结果
表2涂层碳钢片盐雾试验结果明细表
水性富锌漆涂层钢片盐雾试验结果如表2和图2所示，所有样品均可耐受13天(312h)以上的盐雾试验。首先，1～4号样品第5天、第13天盐雾试验结果及最终耐盐雾时间与空白样品一致，这表明锌粉的钝化过程对涂层的盐雾性能无明显影响。其次，钝化过程对锌粉的析氢反应有明显的抑制效果，如采用钝化的锌粉配制的水性富锌漆，在漆液中加水放置30天后依然可耐受13天以上的盐雾试验，且其最终耐盐雾试验时间可达491h，与空白样的盐雾性能基本相当。最后，通过对钝化剂组分A和B进行热储试验验证结果发现，钝化剂组分A和B分别热储14天后所配制漆液的最终耐盐雾性能依然可达589h，这说明经过热储后钝化剂的钝化效果与新制备溶液无较大差异，钝化剂的物理化学性质稳定，可长时间储存。
为进一步验证钝化锌/铝粉在水中的长期析氢抑制性能，将钝化好的锌浆中加入20％以上的水，室温放置5d后在50℃下热储14天，然后考察其析氢抑制性能。结果发现钝化锌浆加水热储14天后无析氢现象发生，且采用该锌浆配制的水性富锌漆的最终平均耐盐雾时间可长达1018h，相较空白样其耐盐雾性能并未明显下降，再次验证了本发明所述锌/铝粉钝化技术的显著效果，经钝化处理的锌/铝粉具有长期析氢抑制性能。
钝化锌粉和未钝化锌粉所制备的富锌漆涂层的电化学测试实验结果如图3和图4所示。由电化学阻抗谱Nyquist图和Bode图可以看出，采用钝化锌粉所制备的涂层和未钝化锌粉所制备的涂层的交流阻抗模值|Z|分别为5830Ω和5923Ω，两者的腐蚀电流密度分别为6.96×10-6mA/cm2和6.30×10-6mA/cm2，两者的耐腐蚀能力差别不大，这再一次说明锌/铝粉的钝化过程对水性富锌漆涂层的防腐蚀性能无影响。
对本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及形变，而所有的这些改变以及形变都应该属于本发明权利要求的保护范围之内。
Claims (5)
1.一种水性富锌漆用锌/铝粉析氢抑制钝化剂，其特征在于，所述钝化剂由A和B两种组分构成，两种组分分开存放，使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中；
组分A由以下质量配比的原料制得：6.0g无机主钝化剂、3.5g有机辅助钝化剂、0.5g氧化剂、5.0g缓蚀剂、1.0g润湿剂以及6.0g改性硅溶胶，
所述无机主钝化剂为草酸氧钒、硫酸氧钛、氟硅酸铵中的一种或者两种以上，
所述有机辅助钝化剂为绿原酸、乙二胺-四甲基膦酸、茶多酚中的一种或者两种以上，
所述氧化剂为硝酸钾、过硫酸铵中的一种，所述缓蚀剂为三乙醇胺硼酸酯、咪唑啉和咪唑-4-甲基亚胺基硫脲中的一种或者两种以上，
所述改性硅溶胶的制备方法为，
a.将1.0g平均粒径45nm的金属氧化物加入到50mL去离子水中，加入0.2g分散剂，先剧烈搅拌均匀，再超声振荡30min得到分散均匀的金属氧化物浆料；所述金属氧化物为二氧化钛或二氧化锆；
b.将0.5g两性金属盐粉末加入到20mL去离子水中，搅拌直至完全溶解，再缓慢加入步骤a所制备的金属氧化物浆料，搅拌混合均匀；所述两性金属盐为硫酸锌或偏铝酸钠；
c.将步骤b所制备的混合液缓慢加入到盛装有50g 30％酸性硅溶胶的圆底烧瓶中，边滴加边搅拌，滴加完毕后，在100℃下回流反应至少1h后，减压蒸馏出部分去离子水将反应液体积浓缩至50mL，停止加热，待反应液冷却至室温后再用2mol/L的硫酸溶液将其pH值调节至4.0以下，取出，存储备用；
组分B由以下质量配比的原料制得：75.0g二丙二醇甲醚、3.0g光亮剂、2.0g稀土钝化剂以及17.0g成膜促进剂，
所述稀土钝化剂为硫酸铈、硝酸钴或者硝酸钇，所述成膜促进剂为环氧树脂128、硬脂酸和γ-氨丙基三乙氧基硅烷中的一种或者两种以上。
2.根据权利要求1所述的水性富锌漆用锌/铝粉析氢抑制钝化剂，其特征在于，所述润湿剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚醚改性有机硅润湿剂WET-628的一种或两种。
3.根据权利要求1所述的水性富锌漆用锌/铝粉析氢抑制钝化剂，其特征在于，所述光亮剂为茴香醛或水杨醛。
4.根据权利要求1所述水性富锌漆用锌/铝粉析氢抑制钝化剂，其特征在于，所述分散剂为十六烷基三甲基溴化铵、三聚磷酸钠或者脂肪醇聚氧乙烯醚。
5.一种水性富锌漆用锌/铝粉析氢抑制钝化剂的制备方法，包括如下步骤：
(1)改性硅溶胶的制备
a.将1.0g平均粒径45nm的金属氧化物加入到50mL去离子水中，加入0.2g分散剂，先剧烈搅拌均匀，再超声振荡30min得到分散均匀的金属氧化物浆料；所述金属氧化物为二氧化钛或二氧化锆；所述分散剂为十六烷基三甲基溴化铵、三聚磷酸钠或者脂肪醇聚氧乙烯醚；
b.将0.5g两性金属盐粉末加入到20mL去离子水中，搅拌直至完全溶解，再将上述制备的金属氧化物浆料缓慢加入，充分搅拌混合均匀；所述两性金属盐为硫酸锌或偏铝酸钠；
c.将步骤b所制备的混合液缓慢加入到盛装有50g 30％酸性硅溶胶的圆底烧瓶中，边滴加边搅拌，滴加完毕后，在100℃下回流反应至少1h后，减压蒸馏出部分去离子水将反应液体积浓缩至50mL，停止加热，待反应液冷却至室温后再用2mol/L的硫酸溶液将其pH值调节至4.0以下，取出，存储备用；
(2)组分A的制备
在装有冷凝回流装置的圆底烧瓶中，先加入78.0g纯化水，然后依次加入6.0g无机主钝化剂，3.5g有机辅助钝化剂，0.5g氧化剂，5.0g缓蚀剂，1.0g润湿剂，每加入一种组分经搅拌加热溶解后再加入下一组分，直至全部成分添加溶解完毕后，再加入6.0g上述改性硅溶胶，继续搅拌混合均匀即制得100.0g组分A；
其中，无机主钝化剂为草酸氧钒、硫酸氧钛、氟硅酸铵中的一种或者两种以上，所述有机辅助钝化剂为绿原酸、乙二胺-四甲基膦酸、茶多酚中的一种或者两种以上，所述氧化剂为硝酸钾、过硫酸铵中的一种，所述缓蚀剂为三乙醇胺硼酸酯、咪唑啉和咪唑-4-甲基亚胺基硫脲中的一种或者两种以上，所述润湿剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚醚改性有机硅润湿剂WET-628中的一种或两种；
(3)组分B的制备
在装有冷凝回流装置的100mL圆底烧瓶中，先加入75.0g二丙二醇甲醚，加热至80℃，然后依次加入3.0g光亮剂，2.0g稀土钝化剂，17.0g成膜促进剂，每加入一种组分后先加热搅拌至溶解，然后再加入下一种组分，直至全部组分添加并溶解完毕为止，制得100.0g组分B；
其中，光亮剂为茴香醛或水杨醛，稀土钝化剂为硫酸铈、硝酸钴或者硝酸钇，成膜促进剂为环氧树脂128，硬脂酸和γ-氨丙基三乙氧基硅烷中的一种或者两种以上；
(4)使用时将A和B两种组分按照10:1的质量比同时加入到水性漆中，室温下均匀分散。
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