CN108456884B - 一种镁合金无铬转化膜均匀化的前处理方法 - Google Patents
一种镁合金无铬转化膜均匀化的前处理方法 Download PDFInfo
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- CN108456884B CN108456884B CN201710093762.4A CN201710093762A CN108456884B CN 108456884 B CN108456884 B CN 108456884B CN 201710093762 A CN201710093762 A CN 201710093762A CN 108456884 B CN108456884 B CN 108456884B
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- 238000000265 homogenisation Methods 0.000 title claims abstract description 76
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- 238000011282 treatment Methods 0.000 claims abstract description 36
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 238000002203 pretreatment Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 20
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 238000012805 post-processing Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000007739 conversion coating Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000004519 grease Substances 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 43
- 229910019142 PO4 Inorganic materials 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 21
- 238000013329 compounding Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 4
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical group OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- QCCJRRYXJSOBIM-UHFFFAOYSA-N CC[NH+](CC)CC.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F Chemical compound CC[NH+](CC)CC.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QCCJRRYXJSOBIM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004512 die casting Methods 0.000 description 8
- 239000004115 Sodium Silicate Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012876 topography Methods 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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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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- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
本发明涉及镁合金表面处理领域,具体地说是一种镁合金无铬转化膜均匀化的前处理方法。该前处理主要包括前置处理,均匀化处理以及均匀化后处理三步。前置处理可以去除基体表面存在的油脂和污物,并在镁合金α基体相上形成一层薄的保护膜;均匀化处理工序可以使基体表面存在较大尺寸的第二相优先发生溶解,随后的均匀化后处理过程可以去除表面残留的盐类晶粒和氧化皮,并起到一定活化的作用。经过本发明方法处理后的样品在转化膜溶液中基体表面形核更均匀,晶粒分布更紧密,提高膜层整体的耐腐蚀性能,解决了镁合金表面由于第二相的影响导致其初期成膜不均匀的问题。
Description
技术领域
本发明涉及镁合金表面处理领域,具体地说是一种镁合金无铬转化膜均匀化的前处理方法。
背景技术
镁合金化学转化膜具有成本低、工艺简单等优点,适合于工业化应用。但转化膜的形成过程对基体自身状态要求较高,比如:腐蚀坑、氧化皮,尤其是镁合金表面存在的第二相会导致合金微观结构不均匀,影响膜的初始沉积和生长,最终影响膜层质量。然而,镁合金在冶炼过程中都需要添加一些合金元素以提高其力学性能,第二相的存在不可避免,导致转化膜的均匀性较差。若想提高转化膜的质量,需要采用适宜的前处理工艺,使其获得一个均匀的成膜表面。因此,选择最佳的前处理工艺就显得格外重要。
目前,已经报道了几种转化膜前处理工艺,如钼酸盐前处理溶液(公开号CN105463415A),酸洗液中添加磷酸钠及高锰酸钾的前处理溶液(公开号CN101148762),还有采用氯化锡敏化、氯化铅活化的工艺(公开号CN105803431A)等等。这些前处理工艺的原理基本都是在基体表面形成较多的活性点,以促进后期磷酸盐更均匀的形核。
然而,经过这些方法前处理后的合金表面依然存在第二相,其缺点就在于:(1)对于第二相尺寸较大的镁合金,第二相导致的微观结构不均匀仍然存在,成膜效果往往较差;(2)上述提到的前处理方法往往只适用于单一的一种或几种牌号镁合金,一旦更换另一种牌号镁合金作为基体时,其活化效果就会明显下降,即通用性差。因此,迫切需要发展一种可以减小第二相对成膜不良影响且适用性广的镁合金前处理方法。
发明内容:
针对上述问题,本发明的目的在于提供一种镁合金无铬转化膜均匀化的前处理方法,经过该方法处理后的样品在转化膜溶液中基体表面形核更均匀,晶粒分布更紧密,提高膜层整体的耐腐蚀性能,解决了镁合金表面由于第二相的影响导致其初期成膜不均匀的问题。
为了实现上述目的,本发明的技术方案是:
一种镁合金无铬转化膜均匀化的前处理方法,溶解镁合金表面存在的尺寸较大的第二相,获得化学成分和微观结构均匀的表面,有利于后续转化膜的均匀形核和生长,提高转化膜的耐蚀性,具体步骤如下:
(1)前置处理:将镁合金浸泡在碱性溶液中,控制其温度为30~90℃,浸泡时间为2~20min,去除表面残留的油脂和污物,并在镁合金α基体相上形成一层薄的保护膜;
(2)均匀化处理:经前置处理后的镁合金浸泡在均匀化处理液中,常温操作,浸泡时间为30s~5min,溶解基体表面存在的尺寸较大的第二相;
(3)均匀化后处理:经均匀化处理后的镁合金浸泡在酸性溶液中,常温操作,处理时间为10s~2min,去除表面残留的盐类晶粒及较薄的氧化皮,并对样品表面起到活化作用;
(4)前处理后的镁合金放在无铬转化膜溶液中进行成膜处理。
所述的镁合金无铬转化膜均匀化的前处理方法,前置处理溶液的成分包括30~120g/l氢氧化物,10~50g/l氟化物,2~30g/l碳酸盐中的一种或两种以上复配的碱性水溶液,pH值11~14。
所述的镁合金无铬转化膜均匀化的前处理方法,前处理溶液中,氢氧化物选自氢氧化钠、氢氧化钾中的一种或其复配;氟化物选自氟化钾、氟化钠、氟化氢铵中的一种或其复配;碳酸盐选自碳酸钠、碳酸钾、碳酸氢钠中的一种或其复配。
所述的镁合金无铬转化膜均匀化的前处理方法,均匀化处理液由20~120g/l铵盐、2~30g/l硅酸盐中的一种或其复配,并含有10~120mg/l缓蚀剂,余量为水,pH值3~6。
所述的镁合金无铬转化膜均匀化的前处理方法,均匀化处理液中,铵盐为磷酸铵、磷酸氢二铵、磷酸二氢铵中的一种或两种以上复配;硅酸盐为硅酸钠、硅酸钾中的一种或两者复配;缓蚀剂为硫酸羟胺、盐酸羟胺、偏钒酸铵、钒酸铵中的一种或两种以上复配。
所述的镁合金无铬转化膜均匀化的前处理方法,均匀化后处理液由1~10wt%的酸、50~300mg/l的表面活性剂和余量的水组成,pH值1~4。
所述的镁合金无铬转化膜均匀化的前处理方法,均匀化后处理液中,酸性溶液成分为磷酸、硝酸、柠檬酸、硫酸、盐酸中的一种或两种以上复配;表面活性剂为十二烷基磺酸钠、全氟辛基磺酸四乙胺、乙二胺四乙酸二钠中的一种或两种以上复配。
所述的镁合金无铬转化膜均匀化的前处理方法,前置处理、均匀化处理、均匀化后处理每步操作之后,均需要进行水洗。
所述的镁合金无铬转化膜均匀化的前处理方法,无铬转化膜溶液是工业应用的磷酸盐溶液,经过表面前处理后的样品进行磷酸盐转化膜的制备,形成磷酸盐转化膜,其厚度为3~8μm。
本发明的设计思想是:
本发明有效的镁合金转化膜前处理方法,首先在前置处理步骤中除去镁合金表面存在的油污,并使α镁基体上形成一层薄的氧化膜,使α镁基体被保护;然后采用均匀化处理工序,使镁合金表面存在的第二相优先发生溶解;最后采用均匀化后处理工序去除表面残留的盐类晶粒及较薄的氧化皮,并形成活化点,利于膜的沉积。第二相溶解后的镁合金表面微观结构更加均匀,表面活性剂的活化效果以及其通用性上都会明显提升,使得成膜物质形核均匀,晶核呈紧密排布,从根本上解决了成膜过程中镁合金表面由于第二相影响导致的成膜初期不均匀问题,最终可以得到致密性更好的耐腐蚀膜层。
本发明具有如下优点及有益效果是:
1.本发明的均匀化前处理工序不含对人体和环境有害的物质,属于绿色环保型工艺。
2.本发明操作工艺简单,易于控制,工艺稳定。
3.本发明可以去除镁合金表面第二相,获得微观结构和化学成分均匀的表面状态,避免第二相对后续成膜的不利影响。
4.本发明适用性广,可结合现有成熟的表面处理方法,得到的膜层更加均匀、致密、耐蚀。
附图说明
图1-图2.传统前处理与新型前处理后WE43镁合金表面形貌对比图:图1传统前处理;图2新型前处理。
图3-图4.传统与新型前处理工艺制备的磷酸盐转化膜在3.5wt%氯化钠溶液中浸泡150h后的腐蚀形貌对比图:图3传统工艺;图4新型工艺。
具体实施方式:
在具体实施过程中,本发明对镁合金磷酸盐转化膜前处理进行优化,该前处理主要包括前置处理,均匀化处理以及均匀化后处理三步:
(1)前置处理:用碱性溶液除去样品表面存留的油污,并在镁合金α基体相上形成一层薄的保护膜,温度30~90℃,时间2~20min。
(2)均匀化处理:经前置处理后的镁合金浸泡在均匀化处理液中,溶解基体表面存在的尺寸较大的第二相,常温操作,时间30s~5min。
(3)均匀化后处理:经均匀化处理后的镁合金浸泡在酸性溶液中,去除表面残留的盐类晶粒和较薄的氧化皮,并对样品表面起到活化作用,常温操作,时间10s~2min。
其中,前置处理可以去除基体表面存在的油脂和污物,并在镁合金α基体相上形成一层薄的保护膜,均匀化处理工序可以使基体表面存在较大尺寸的第二相优先发生溶解,随后的均匀化后处理过程可以去除表面残留的盐类晶粒和氧化皮,并起到一定活化的作用。
下面,通过实施例和附图对本发明的技术方案作进一步的具体说明。
实施例1
本实施例中,样品为压铸WE43镁合金,其具体步骤如下:
(1)前置处理:前置处理溶液为氢氧化钠50g/l,氟化钠20g/l,碳酸钠20g/l的水溶液,温度为60℃,浸泡5min;
(2)均匀化处理:均匀化处理溶液为磷酸铵20g/l,硅酸钠10g/l,硫酸羟胺20mg/l的水溶液,常温浸泡1min;
(3)均匀化后处理:均匀化后处理溶液为1wt%盐酸,50mg/l十二烷基磺酸钠的水溶液,室温浸泡30s。按此方法前处理后样品表面存在的第二相完全溶解,其形貌见图2;
(4)成膜:前处理后的样品浸泡在专利ZL201010125808.4(公开号CN102191493A)所述磷酸盐溶液中进行膜层的制备,形成磷酸盐转化膜,其厚度为6μm,且该膜层均匀、致密、耐腐蚀。
实施例2
本实施例中,样品为压铸GW93镁合金,其具体步骤如下:
(1)前置处理:前置处理溶液为氢氧化钾40g/l,氟化钾10g/l,碳酸钾25g/l的水溶液,温度为50℃,浸泡8min;
(2)均匀化处理:均匀化处理溶液为磷酸二氢铵50g/l,硅酸钠5g/l,盐酸羟胺40mg/l的水溶液,常温浸泡2min;
(3)均匀化后处理:均匀化后处理溶液为3wt%柠檬酸与100mg/l全氟辛基磺酸四乙胺的水溶液,室温浸泡30s。
(4)成膜:前处理后的样品浸泡在专利ZL02132772.6所述磷酸盐溶液中进行膜层的制备,形成磷酸盐转化膜,其厚度为4μm,且该膜层均匀、致密、耐腐蚀。
实施例3
本实施例中,样品为压铸EW75镁合金,其具体步骤如下:
(1)前置处理:前置处理溶液为氢氧化钠100g/l,氟化钠40g/l,碳酸钠20g/l的水溶液,温度为80℃,浸泡5min;
(2)均匀化处理:均匀化处理溶液为磷酸氢二铵25g/l,硅酸钠20g/l,偏钒酸铵100mg/l的水溶液,常温浸泡2min;
(3)均匀化后处理:均匀化后处理溶液为5wt%硝酸与150mg/l乙二胺四乙酸二钠的水溶液,室温浸泡60s。
(4)成膜:前处理后的样品浸泡在专利ZL201010125808.4所述磷酸盐溶液中进行膜层的制备,形成磷酸盐转化膜,其厚度为5μm,且该膜层均匀、致密、耐腐蚀。
实施例4
本实施例中,样品为压铸WE54镁合金,其具体步骤如下:
(1)前置处理:前置处理溶液为氢氧化钠70g/l的水溶液,温度为60℃,浸泡10min;
(2)均匀化处理:均匀化处理溶液为磷酸氢二铵60g/l,钒酸铵20mg/l的水溶液,常温浸泡3min;
(3)均匀化后处理:均匀化后处理溶液为10wt%盐酸与300mg/l十二烷基磺酸钠的水溶液,室温浸泡1min。
(4)成膜:前处理后的样品浸泡在专利ZL02132772.6所述磷酸盐溶液中进行膜层的制备,形成磷酸盐转化膜,其厚度为4.5μm,且该膜层均匀、致密、耐腐蚀。
实施例5
本实施例中,样品为压铸WE43镁合金,具体步骤如下:
(1)前置处理:前置处理溶液为氢氧化钾30g/l,氟化钾10g/l的水溶液,温度为70℃,浸泡20min;
(2)均匀化处理:均匀化处理溶液为硅酸钾30g/l,硫酸羟胺120mg/l的水溶液,常温浸泡5min;
(3)均匀化后处理:均匀化后处理溶液为8wt%柠檬酸与80mg/l乙二胺四乙酸二钠的水溶液,室温浸泡2min。
(4)成膜:前处理后的样品浸泡在专利ZL02132772.6所述磷酸盐溶液中进行膜层的制备,形成磷酸盐转化膜,其厚度为6μm,且该膜层均匀、致密、耐腐蚀。
对比例1
对比例1中,样品为压铸WE43镁合金,具体步骤如下:
(1)脱脂:碳酸钠20g/l,磷酸钠20g/l,硅酸钠20g/l的复配液,温度为60℃,浸泡5min;
(2)酸洗:氢氟酸与水比例1:1的氢氟酸水溶液,常温浸泡1min。
传统前处理后样品表面形貌见图1,第二相仍然存在。
(3)成膜:前处理后的样品浸泡在专利ZL201010125808.4所述磷酸盐溶液中进行膜层的制备。
对比例2
对比例2中,样品为压铸EW75镁合金,其具体步骤如下:
(1)脱脂:碳酸钠40g/l,磷酸钠40g/l,硅酸钠40g/l的复配液,温度为60℃,浸泡3min;
(2)酸洗:1wt%硝酸水溶液,常温浸泡1min。
(3)成膜:前处理后的样品浸泡在专利ZL201010125808.4所述磷酸盐溶液中进行膜层的制备。
对比例3
对比例3中,样品为压铸GW93镁合金,其具体步骤如下:
(1)脱脂:氢氧化钠50g/l,磷酸钠50g/l的复配液,温度为50℃,浸泡10min;
(2)酸洗:5wt%盐酸水溶液,常温浸泡2min。
(3)成膜:前处理后的样品浸泡在专利ZL02132772.6所述磷酸盐溶液中进行膜层的制备。
1.宏观形貌
按照上述实施例1~5以及对比例1所制得的膜层均呈现灰白色,颜色均匀,手感光滑,无挂灰现象,宏观形貌基本无差异,膜层厚度均为3~8微米厚,膜层状态良好。对比例2~3所制得膜层表面状态不均匀,部分位置有金属光泽,膜层状态较差。这也证明了传统前处理工艺在制备不同基体材料的化学转化膜时通用性较差。
2.耐蚀性测试
根据ASTM全浸实验标准,将按照实施例1~5及对比例1方法所制备的镁合金转化膜试样完全浸泡在3.5wt%NaCl溶液中,腐蚀介质体积与试样工作面积之比大于20ml/cm2,pH=7,温度控制在25±1℃。待150h后观察其膜层腐蚀形貌发现,实例1~5样品表面形貌由灰白色转变为黄棕色,整个样品表面弥散分布有5~8个左右尺寸较小的白色粒状产物,但并没有出现较为明显的腐蚀。其中,实施例1腐蚀形貌如图4所示。而对比例1在浸泡150h后其表面形貌同为黄棕色且存在少量尺寸较小的白色粒状产物,同时测试面的2个位置出现尺寸1~2mm大小的宏观点蚀(图3所示),耐蚀性能较实例1~5所制得的膜层更差,说明经过均匀化前处理工艺所制得的化学转化膜层耐蚀性能有明显提高。
Claims (8)
1.一种镁合金无铬转化膜均匀化的前处理方法,其特征在于,溶解镁合金表面存在的尺寸较大的第二相,获得化学成分和微观结构均匀的表面,有利于后续转化膜的均匀形核和生长,提高转化膜的耐蚀性,具体步骤如下:
(1)前置处理:将镁合金浸泡在碱性溶液中,控制其温度为30~90 ℃,浸泡时间为2~20 min,去除表面残留的油脂和污物,并在镁合金α基体相上形成一层薄的保护膜;
(2)均匀化处理:经前置处理后的镁合金浸泡在均匀化处理液中,常温操作,浸泡时间为30 s~5 min,溶解基体表面存在的尺寸较大的第二相;
均匀化处理液由20~120 g/l铵盐、2~30 g/l硅酸盐中的一种或其复配,并含有10~120 mg/l缓蚀剂,余量为水,pH值3~6;
(3)均匀化后处理:经均匀化处理后的镁合金浸泡在酸性溶液中,常温操作,处理时间为10 s~2 min,去除表面残留的盐类晶粒及较薄的氧化皮,并对样品表面起到活化作用;
(4)前处理后的镁合金放在无铬转化膜溶液中进行成膜处理。
2.按照权利要求1所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:前置处理溶液的成分包括30~120 g/l氢氧化物,10~50 g/l氟化物,2~30 g/l碳酸盐中的一种或两种以上复配的碱性水溶液,pH值11~14。
3.按照权利要求2所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:前置处理溶液中,氢氧化物选自氢氧化钠、氢氧化钾中的一种或其复配;氟化物选自氟化钾、氟化钠、氟化氢铵中的一种或其复配;碳酸盐选自碳酸钠、碳酸钾、碳酸氢钠中的一种或其复配。
4.按照权利要求1所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:均匀化处理液中,铵盐为磷酸铵、磷酸氢二铵、磷酸二氢铵中的一种或两种以上复配;硅酸盐为硅酸钠、硅酸钾中的一种或两者复配;缓蚀剂为硫酸羟胺、盐酸羟胺、偏钒酸铵、钒酸铵中的一种或两种以上复配。
5.按照权利要求1所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:均匀化后处理液由1~10 wt%的酸、50~300 mg/l的表面活性剂和余量的水组成,pH值1~4。
6.按照权利要求5所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:均匀化后处理液中,酸性溶液成分为磷酸、硝酸、柠檬酸、硫酸、盐酸中的一种或两种以上复配;表面活性剂为十二烷基磺酸钠、全氟辛基磺酸四乙胺、乙二胺四乙酸二钠中的一种或两种以上复配。
7.按照权利要求1所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:前置处理、均匀化处理、均匀化后处理每步操作之后,均需要进行水洗。
8.按照权利要求1所述的镁合金无铬转化膜均匀化的前处理方法,其特征在于:无铬转化膜溶液是工业应用的磷酸盐溶液,经过表面前处理后的样品进行磷酸盐转化膜的制备,形成磷酸盐转化膜,其厚度为3~8μm。
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