CN115323364A - 一种高温锌锰系磷化液的制备方法及应用 - Google Patents
一种高温锌锰系磷化液的制备方法及应用 Download PDFInfo
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- CN115323364A CN115323364A CN202111031702.2A CN202111031702A CN115323364A CN 115323364 A CN115323364 A CN 115323364A CN 202111031702 A CN202111031702 A CN 202111031702A CN 115323364 A CN115323364 A CN 115323364A
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- phosphating solution
- acid
- manganese phosphating
- zinc
- temperature zinc
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 88
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 44
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 239000011787 zinc oxide Substances 0.000 claims abstract description 28
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 21
- 235000015393 sodium molybdate Nutrition 0.000 claims description 21
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 16
- 239000011975 tartaric acid Substances 0.000 claims description 16
- 235000002906 tartaric acid Nutrition 0.000 claims description 16
- 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 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 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
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 239000000467 phytic acid Substances 0.000 claims description 2
- 229940068041 phytic acid Drugs 0.000 claims description 2
- 235000002949 phytic acid Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 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
- 239000001384 succinic acid Substances 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005034 decoration Methods 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- -1 sodium fluoroborate Chemical compound 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also 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
- C23C22/07—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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- 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
- C23C22/36—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 containing also phosphates
- C23C22/364—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 containing also phosphates containing also manganese cations
- C23C22/365—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 containing also phosphates containing also manganese cations containing also zinc and nickel cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
本发明公开了一种高温锌锰系磷化液，其制备原料包括马日夫盐25～33％、氧化锌5～9％、硝酸2～6％、磷酸16～25％、硝酸镍0.4～0.8％、促进剂0.1～0.3％、助膜剂0.3～0.6％、络合剂0.2～0.8％、去离子水余量，所制备的磷化液形成的磷化膜表面致密、结晶均匀、防腐蚀性能强，在汽车零部件的前处理、钢铁制件的表面处理、装饰工艺涂装底层等方面具有广泛的应用前景。
Description
技术领域
本发明涉及的是金属表面处理技术领域(C23C22/22)，具体涉及一种高温锌锰系磷化液的制备方法及应用。
背景技术
随着汽车行业的发展，汽车配件的需求日益广泛，汽车内部众多金属零件中间体需要达到长期防锈，保护等作用。磷化是金属材料防腐蚀的重要方法之一，其可以在基体金属表面形成磷酸盐化学转化膜，给基体金属提供保护、防止金属腐蚀。而锌锰系磷化液可以用于金属表面处理，在金属表面生成结晶磷化膜，提高金属的抗磨性能和防锈效果。
中国专利(CN201010122354.5)涉及了一种薄层耐磨磷化液及其配制方法，使用马日夫盐、水、磷酸及碳酸锰来调整溶液的酸度，直到总酸度与游离酸度之比为6∶1～7∶1，即得到薄层耐磨磷化剂。但是在配制过程中需要不断的调整溶液的酸度，工艺复杂。专利(CN201711034294.X)涉及了一种锌锰系磷化液及其制备方法，使用该锌锰系磷化液能形成防腐效果明显提高的磷化膜。但所采用的促进剂为亚硝酸钠，有一定的危险性。
为了解决现有技术所存在的技术问题，本发明提供了一种操作便捷、处理速度快、抗腐蚀效果好的高温锌锰系磷化剂及使用方法。
发明内容
为了解决上述问题，本发明的第一方面提供了一种高温锌锰系磷化液，以质量分数计，其制备原料包括马日夫盐25～33％、氧化锌5～9％、硝酸2～6％、磷酸16～25％、硝酸镍0.3～0.8％、促进剂0.1～0.3％、助膜剂0.3～0.6％、络合剂0.2～0.8％、去离子水余量。
作为一种优选的技术方案，所述马日夫盐的纯度大于等于98％。
进一步地，本发明所使用的马日夫盐的质量分数优选为30％。
作为一种优选的技术方案，本发明所使用的氧化锌的质量分数优选为8％。
作为一种优选的技术方案，所述硝酸为质量分数为65-70％的工业硝酸稀硝酸。
进一步地，所述硝酸优选为质量分数为68％的工业硝酸稀硝酸。
进一步地，本发明所使用的硝酸的质量分数优选为4％。
作为一种优选的技术方案，所述磷酸为质量分数为83～86％的工业磷酸。
进一步地，所述磷酸优选为质量分数为85％的工业磷酸。
进一步地，本发明所使用的磷酸的质量分数优选为20％。
作为一种优选的技术方案，本发明所使用的硝酸镍的质量分数优选为0.5％。
作为一种优选的技术方案，所述促进剂选自硝酸盐、亚硝酸盐、氯酸盐、有机氮化物、钼酸盐中的一种或多种。
进一步地，本发明所使用的促进剂的质量分数优选为0.2％。
进一步地，所述促进剂选自钼酸盐中的一种。
进一步地，所述钼酸盐选自钼酸钠、钼酸钾和钼酸铵中的一种或多种。
作为一种优选的技术方案，所述络合剂选自柠檬酸、柠檬酸铵、柠檬酸钠、酒石酸、磺基水杨酸、乙二胺四乙酸、丁二酸、甘油磷酸脂中的一种或多种。
进一步地，本发明所使用的络合剂的质量分数优选为0.5％。
作为一种优选的技术方案，所述助膜剂选自六偏磷酸钠、1-羟基亚乙基-1,1-二膦酸、氟硼酸钠、植酸中的一种或多种。
进一步地，本发明所使用的助膜剂的质量分数优选为0.5％。
作为一种优选的技术方案，所述促进剂和助膜剂的质量分数比为(2～3)：1。
本发明的第二方面提供了一种如上所述的高温锌锰系磷化液的制备方法，该方法包括以下步骤：
(1)依次准备，以质量分数计，马日夫盐25～33％、氧化锌5～9％、硝酸2～6％、磷酸16～25％、硝酸镍0.3～0.8％、促进剂0.1～0.3％、助膜剂0.3～0.6％、络合剂0.2～0.8％、去离子水余量，备用；
(2)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(3)在溶液A中加入马日夫盐、硝酸镍、促进剂、助膜剂、络合剂和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液。
本发明的第三方面提供了一种如上所述的高温锌锰系磷化液的应用，所述高温锌锰系磷化液的使用温度为80～90℃，待加工的物品浸泡到所述高温锌锰系磷化液中，浸泡时间为10～15min。
有益效果：
(1)本发明的高温锌锰系磷化剂由马日夫盐、氧化锌、硝酸、磷酸、硝酸镍、氟硼酸钠、酒石酸、钼酸钠和去离子水组成，所述高温锌锰系磷化剂能够使铁制品表面获得磷化保护膜层，所形成的磷化膜防腐蚀能力强，结合力好，在汽车零部件的前处理、钢铁制件的表面处理、装饰工艺涂装底层等方面具有广泛的应用前景。
(2)本发明通过加入马日夫盐，可以使高温锌锰系磷化剂所形成的磷化膜具有较好的硬度和耐腐蚀性；马日夫盐的分子式为Mn(H2PO4)2·2H2O，当马日夫盐的纯度大于98％时，所能提供的游离酸、总酸和锰离子较多，能够更好的与体系中的氧化锌、硝酸镍相互作用，使形成的磷化膜结晶粗细均匀、表面粗糙度小，耐腐蚀性增加。
(3)本发明中，加入氟硼酸钠作为助膜剂、钼酸钠作为促进剂，可以提高磷化膜的成膜速度，减少磷化渣；特别是氟硼酸钠和钼酸钠的质量分数比例为(2～3)：1时，磷化膜的形成速度与体系中反应速度达到一定的平衡，使反应平稳、高温锌锰系磷化溶液稳定、使用寿命长、沉渣少。
(4)本发明加入酒石酸作为络合剂，络合磷化膜中的金属离子，形成大分子；特别是体系中酒石酸的质量分数在0.2～0.8％时，可以更好的稳定溶液的总酸度和游离酸度，使形成的磷化膜更加致密，结晶均匀，提高磷化膜的耐蚀性。
(5)通过将氧化锌、磷酸、硝酸、马日夫盐三种组分，按照马日夫盐20～33％、氧化锌5～9％、硝酸2～6％、磷酸16～25％的比例去搭配，再配合钼酸钠、氟硼酸钠、硝酸镍、酒石酸等助剂，能够更好的制备出高温锌锰系磷化剂，制备过程简单且在使用磷化剂时操作简单，成膜速度快、膜层致密均匀。
具体实施方式
氧化锌
氧化锌是一种无机物，化学式为ZnO，难溶于水，可溶于酸、浓氢氧化碱、氨水和铵盐溶液，不溶于水、乙醇。与磷酸反应生成磷酸二氢锌，氧化锌含量低时，成膜困难；含量过高时，会使膜层变厚，空隙率增大。
硝酸
硝酸是一种具有强氧化性、腐蚀性的强酸，化学式为HNO3，强氧化性的硝酸能防止磷化液老化；在高温中，硝酸根可用为促进剂使用；硝酸与磷酸共同溶解氧化锌等金属氧化物，可以减少磷酸的用量，防止磷酸过量而水解析出磷酸盐结晶，起稳定作用。
磷酸
磷酸是一种常见的无机酸，是中强酸，化学式为H3PO4，不易挥发，不易分解，几乎没有氧化性。磷酸主要是提供游离酸促进与氧化锌反应，但是需要控制磷酸的量，含量太高的话磷化膜的形成速度跟不上溶解速度，形成不了磷化膜；含量太低生成磷化膜速度慢，在规定时间内厚度达不到要求。
硝酸镍
硝酸镍的化学式为Ni(NO3)2·6H2O，有氧化性，易溶于水，溶于乙醇、氨水，其中镍离子可以参与磷化反应，加速成膜，并且使膜层细化，增强磷化膜的防锈和耐蚀性。
下面通过实施例对本发明进行具体描述。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。
另外，如果没有其它说明，所用原料都是市售得到的。
实施例1
实施例1提供了一种高温锌锰系磷化液，其包括以下按照质量分数的原料：马日夫盐30％、氧化锌8％、硝酸4％、磷酸20％、硝酸镍0.5％、氟硼酸钠0.5％、酒石酸0.5％、钼酸钠0.2％、去离子水余量；
其中：马日夫盐纯度98％；硝酸为68％工业硝酸稀硝酸；磷酸为85％工业磷酸；氟硼酸钠和钼酸钠的质量分数比为2.5：1；
制备方法：
(1)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(2)在溶液A中加入马日夫盐、硝酸镍、氟硼酸钠、酒石酸、钼酸钠和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液；
使用方法：在90℃下，将待加工的金属浸泡到所述高温锌锰系磷化液中，浸泡时间为12min。
实施例2
实施例2提供了一种高温锌锰系磷化液，其包括以下按照质量分数的原料：马日夫盐25％、氧化锌5％、硝酸2％、磷酸16％、硝酸镍0.3％、氟硼酸钠0.3％、酒石酸0.2％、钼酸钠0.1％、去离子水余量；
其中：马日夫盐纯度98％；硝酸为68％工业硝酸稀硝酸；磷酸为85％工业磷酸；氟硼酸钠和钼酸钠的质量分数比为3：1；
制备方法：
(1)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(2)在溶液A中加入马日夫盐、硝酸镍、氟硼酸钠、酒石酸、钼酸钠和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液；
使用方法：在80℃下，将待加工的金属浸泡到所述高温锌锰系磷化液中，浸泡时间为10min。
实施例3
实施例3提供了一种高温锌锰系磷化液，其包括以下按照质量分数的原料：马日夫盐33％、氧化锌9％、硝酸6％、磷酸25％、硝酸镍0.8％、氟硼酸钠0.6％、酒石酸0.8％、钼酸钠0.3％、去离子水余量；
其中：马日夫盐纯度99％；硝酸为68％工业硝酸稀硝酸；磷酸为85％工业磷酸；氟硼酸钠和钼酸钠的质量分数比为2：1；
制备方法：
(1)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(2)在溶液A中加入马日夫盐、硝酸镍、氟硼酸钠、酒石酸、钼酸钠和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液；
使用方法：在85℃下，将待加工的金属浸泡到所述高温锌锰系磷化液中，浸泡时间为15min。
对比例1
对比例1提供了一种高温锌锰系磷化液，其包括以下按照质量分数的原料：马日夫盐30％、氧化锌8％、硝酸4％、磷酸20％、硝酸镍0.5％、氟硼酸钠1.0％、酒石酸0.5％、钼酸钠0.2％、去离子水余量；
其中：马日夫盐纯度98％；硝酸为68％工业硝酸稀硝酸；磷酸为85％工业磷酸；氟硼酸钠和钼酸钠的质量分数比为5：1；
制备方法：
(1)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(2)在溶液A中加入马日夫盐、硝酸镍、氟硼酸钠、酒石酸、钼酸钠和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液；
使用方法：在90℃下，将待加工的金属浸泡到所述高温锌锰系磷化液中，浸泡时间为12min。
对比例2
对比例2提供了一种高温锌锰系磷化液，其包括以下按照质量分数的原料：马日夫盐30％、氧化锌8％、硝酸4％、磷酸20％、硝酸镍0.5％、氟硼酸钠0.5％、酒石酸1.5％、钼酸钠0.2％、去离子水余量；
其中：马日夫盐纯度98％；硝酸为68％工业硝酸稀硝酸；磷酸为85％工业磷酸；氟硼酸钠和钼酸钠的质量分数比为2.5：1；
制备方法：
(1)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(2)在溶液A中加入马日夫盐、硝酸镍、氟硼酸钠、酒石酸、钼酸钠和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液；
使用方法：在90℃下，将待加工的金属浸泡到所述高温锌锰系磷化液中，浸泡时间为12min。
性能测试
对使用实施例1～3和对比例1～2所述锌锰系磷化液处理后生成的磷化膜，进行耐中性盐雾试验对比，耐中性盐雾试验48h后，实施例1～3的磷化膜表面未产生任何锈蚀；对比例1的磷化膜表面出现轻微锈蚀；对比例2的磷化膜表面产生大量锈蚀。
Claims (10)
1.一种高温锌锰系磷化液，其特征在于，以质量分数计，其制备原料包括马日夫盐25～33％、氧化锌5～9％、硝酸2～6％、磷酸16～25％、硝酸镍0.3～0.8％、促进剂0.1～0.3％、助膜剂0.3～0.6％、络合剂0.2～0.8％、去离子水余量。
2.根据权利要求1所述的一种高温锌锰系磷化液，其特征在于，所述马日夫盐的纯度大于等于98％。
3.根据权利要求1所述的一种高温锌锰系磷化液，其特征在于，所述促进剂选自硝酸盐、亚硝酸盐、氯酸盐、有机氮化物、钼酸盐中的一种或多种。
4.根据权利要求1所述的一种高温锌锰系磷化液，其特征在于，所述促进剂选自钼酸盐中的一种。
5.根据权利要求4所述的一种高温锌锰系磷化液，其特征在于，所述钼酸盐选自钼酸钠、钼酸钾、钼酸铵中的一种或多种。
6.根据权利要求1所述的一种高温锌锰系磷化液，其特征在于，所述络合剂选自柠檬酸、柠檬酸铵、柠檬酸钠、酒石酸、磺基水杨酸、乙二胺四乙酸、丁二酸、甘油磷酸脂中的一种或多种。
7.根据权利要求1所述的一种高温锌锰系磷化液，其特征在于，所述助膜剂选自六偏磷酸钠、1-羟基亚乙基-1,1-二膦酸、氟硼酸钠、植酸中的一种或多种。
8.根据权利要求1所述的一种高温锌锰系磷化液，其特征在于，所述促进剂和助膜剂的质量分数比为(2～3)：1。
9.根据权利要求1～7任一项所述的高温锌锰系磷化液的制备方法，其特征在于，它包括如下步骤：
(1)依次准备，以质量分数计，马日夫盐25～33％、氧化锌5～9％、硝酸2～6％、磷酸16～25％、硝酸镍0.3～0.8％、促进剂0.1～0.3％、助膜剂0.3～0.6％、络合剂0.2～0.8％、去离子水余量，备用；
(2)将氧化锌、磷酸、硝酸混合在一起，完全溶解得到溶液A；
(3)在溶液A中加入马日夫盐、硝酸镍、促进剂、助膜剂、络合剂和去离子水，混合后搅拌均匀即得到高温锌锰系磷化液。
10.根据权利要求1～7任一项所述的高温锌锰系磷化液的应用，其特征在于，所述高温锌锰系磷化液的使用温度为80～90℃，待加工的物品浸泡到所述高温锌锰系磷化液中，浸泡时间为10～15min。
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