CN1066207C - 在金属表面涂覆磷酸盐涂层的方法 - Google Patents
在金属表面涂覆磷酸盐涂层的方法 Download PDFInfo
- Publication number
- CN1066207C CN1066207C CN95196688A CN95196688A CN1066207C CN 1066207 C CN1066207 C CN 1066207C CN 95196688 A CN95196688 A CN 95196688A CN 95196688 A CN95196688 A CN 95196688A CN 1066207 C CN1066207 C CN 1066207C
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- China
- Prior art keywords
- zinc
- solution
- phosphating solution
- contain
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 48
- 239000010452 phosphate Substances 0.000 title claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title abstract description 5
- 239000002184 metal Substances 0.000 title abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 45
- 239000011701 zinc Substances 0.000 claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 6
- 238000009736 wetting Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 53
- 150000003016 phosphoric acids Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 4
- 239000008397 galvanized steel Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 23
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 phosphate radical Chemical class 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000005837 radical ions Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- JCYPECIVGRXBMO-FOCLMDBBSA-N methyl yellow Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1 JCYPECIVGRXBMO-FOCLMDBBSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- ABEWDFYANWOMJE-UHFFFAOYSA-N oxalic acid;potassium Chemical compound [K].OC(=O)C(O)=O ABEWDFYANWOMJE-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- OXHXATNDTXVKAU-UHFFFAOYSA-N phosphoric acid zinc Chemical compound [Zn].OP(O)(O)=O OXHXATNDTXVKAU-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- SPDJAIKMJHJYAV-UHFFFAOYSA-H trizinc;diphosphate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SPDJAIKMJHJYAV-UHFFFAOYSA-H 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C23C22/07—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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- 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)
- Materials For Medical Uses (AREA)
Abstract
兹提出一种用磷酸盐涂层涂覆锌、铁、铝或它们的合金表面的方法，其表面用一种不含元素周期表中第Ⅴ和第Ⅵ副族元素，而含有0.5-8g/l镍，2-20g/l锰，18-170g/l磷酸盐(按P2O5计算)并具有0.4-0.8的S值的磷酸盐化溶液以如下方式浸润，即在接下来的直接干燥之后其磷酸盐涂层重量达到0.3-3.0g/m2。在对铁、铝或其合金表面作磷化处理时，磷酸盐化溶液必需含有0.5-5g/l锌。而对锌及其锌合金表面作磷化处理时不必需含锌，最好不含锌。本发明的方法用于对镀锌或合金镀锌的钢带作磷化处理时尤其具有优点。
Description
本发明涉及一种在锌、铁、铝或其合金的表面通过用一种含有二价阳离子和磷酸根的磷酸盐化溶液浸润并接着对液体薄膜干燥而涂覆磷酸盐涂层的方法。
在金属加工工业中，借助磷酸锌水溶液制备磷酸盐涂层的方法被广泛采用。用这种方法在处理的金属表面获得的磷酸盐涂层尤其用于增加滑移、为无切屑冷变形做准备及防腐和作为漆底。
这种形式的磷酸盐化溶液，其通常pH值为1.8至3.8，并含有锌离子和磷酸根离子作为确定工艺的组份。除阳离子锌外，还可以有其它阳离子，如铵，钙，钴，铁，钾，铜，钠，镁，锰。为加速磷酸盐涂层的形成，通常向磷酸盐化溶液中加入氧化剂，如溴酸盐，氯酸盐，硝酸盐，亚硝酸盐，有机硝基化合物，过硼酸盐，过硫酸盐或过氧化氢。为优化在某些材料上的涂层结构，采用添加物，如氟化物，氟硅酸盐，氟硼酸盐、柠檬酸盐和酒石酸盐。由于大量的单一组份和它们的组合可能性，磷酸盐化溶液有许多不同的组成。
作为磷化法的一种特殊实施形式是所谓低锌法。在此所用的磷酸盐化溶液含锌的浓度仅约为0.4-1.7g/l，并尤其在钢上所获得的磷酸盐涂层具有高含量的磷酸千枚岩，它比通常用高锌含量的磷酸盐化溶液制得的磷锌矿基的磷酸盐涂层在腐蚀负荷条件下具有更好的漆粘附性和更高的耐漆渗透性。(DE-A-22 32 067，EP-A-15021，EP-A-39 093，EP-A-56 881，EP-A-64 790，K.Wittel：“现代磷酸锌处理法-低锌技术”，工业-喷漆操作，5/83，169页和6/83，210页)。
较新进展的磷化处理方法是在学术界被称之为的三阳离子法。这里，它也是一种低锌磷化处理法，其中，通过同时采用例如0.3-2.0g/l的镍和0.5-1.5g/l的锰，使所获得的磷酸盐涂层呈现较高的耐碱性并因此对于尤其是车身的阴极电浸渍上漆具有意义。
已研制出专门用于对电解镀锌或熔体浸渍镀锌的钢带作磷化处理的方法，与三阳离子法相当，它使磷酸盐涂层在3-8秒的接触时间内形成(EP-A-111246)。
上述磷化处理方法的共同点是，以浸渍，流涂或喷射方式使磷酸盐化溶液与待处理的工件表面接触。在有效的化学反应和致密结合的晶体磷酸盐涂层形成之后，为去除表面残留的磷化化合物需进行冲洗处理，冲洗通常分数阶段进行。由此同时产生冲洗溶液，这种形式的冲洗液不能排掉，而必须送去进行污水处理。
尽管已给出各种减少或完全排除冲洗用水量的建议，例如在所谓冲洗槽内冲洗就与大量减少附带产生的冲洗水有关。不过，少量产生的冲洗水的处理还是不可避免的。为避免冲洗水，建议采用锌磷化法，其磷酸盐化溶液以下面方式组成，即实际上所有组份都用氢氧化钾使其沉淀。以这种方式，冲洗水的处理被大大减少，同时该方法具有如下优点，即能回收对于该过程而言质量足够好的水(DE-C-2327304)。不过，上述方法的缺点是，由于所提出的磷酸盐化溶液组份的可沉淀性要求，使得磷酸盐化溶液的组成适应实际需要的自由度大大受到限制。最后公开了制备一种转换涂层的方法，在该方法中，在可能需要的清洗和水冲刷之后，涂层溶液被涂覆并接着被干燥。在此，处理溶液的使用可通过浸渍或喷涂接着挤压出多余的溶液，或通过辊压涂覆来实现，在辊压涂覆时，仅仅所需的液体量被涂在金属表面。在处理液体涂覆后，紧接着的干燥原则上在室温就已能完成。但通常采用较高的温度，其中，最好在50-100℃之间。一种对用于随后涂覆有机涂层的金属表面预处理的方法在于，用一种磷酸盐化液体浸润金属表面，该液体具有1.5-3的pH值，不含铬，并且除金属磷酸盐外还含有可溶解的钼酸根离子、钨酸根离子、钒酸根离子、铌酸根离子和/或钽酸根离子(EP-B-15020)。其中，溶液中存在的金属磷酸盐的阳离子组份可由钾、镁、钡、铝、锌、镉、铁、镍、钴和/或锰组成。
最后所述方法的缺点在于，由于需要添加钼酸根、钨酸根、钡酸根、铌酸根和/或钽酸根离子，该方法成本上比通常的磷化处理法昂贵，另外，所获得的磷酸盐涂层不满足所有目前所提出的要求，如耐碱性和由此产生的在接下来的阴极电浸渍涂漆时的电阻及所希望的尤其在与随后的涂漆结合时的耐腐蚀性。
本发明的目的在于，提供一种在锌、铁、铝或它们的合金表面涂覆磷酸盐涂层的方法，它不具有已公开的，尤其是前面所述的那些缺点，此外成本适宜和易于实施，并能获得高质量的磷酸盐涂层。
上述目的这样来达到，即按照本发明这样来实施开头所述形式的方法，即用一种不含有元素周期表中第Ⅴ和第Ⅵ副族元素，而含有0.5-8g/l镍、2-20g/l锰，18-170g/l磷酸盐(按P2O5计算)，并且其S值为0.4-0.8的磷酸盐化溶液以下面方式浸润表面，即在干燥之后，磷酸盐涂层重量达到0.3-3.0g/m2，其中，磷酸盐化溶液在对铁，铝或它们的合金表面作磷化处理时必需含有0.5-5g/l的锌，而对锌或锌合金表面作磷化处理时可以含锌离子。
前面所述有关锌含量的配方应表示为，在处理铁、铝或它们的合金表面时，上述浓度的锌含量必不可少。在处理锌或锌合金表面时，磷酸盐化溶液同样可以含有锌，不过锌含量不是要求的。元素周期表中第Ⅴ和第Ⅵ副族元素是钒，铌，钽，铬，钼和钨。
为避免磷酸盐涂层在干燥后含有溶于水的化合物，S值的调准相应地用氧化镍、氧化锰、或任选的氧化锌或也可用氨液来完成。
本发明的相应实施形式提出，在处理锌或锌合金时，表面用一种不含锌的磷酸盐化溶液浸润。在这种特别场合下，涂层形成所需的锌量来自所处理材料的表面。
各金属表面的润温例如可通过浸渍和紧接着滴干，通过浇涂和离心，通过刷涂，通过用高压空气、真空及静电方法喷射完成。一种应用磷酸盐化溶液特别完美的方法是通过用起纹理的或平滑的辊顺向或逆向辊压来实现。
紧接在金属表面润湿之后的干燥原则上在室温下就可完成。不过，在较高温度下工作是具有优点的，因为磷酸盐涂层形成的时间被大大缩短。干燥最好在50-200℃之间的温度下进行，其中，物体温度不应超过90℃。
本发明的一种优选实施形式在于，表面用下面这样一种磷酸盐化溶液润湿，它含有0.8-6g/l镍，3-16g/l锰，30-140g/l磷酸盐(按P2O5计)，以及在对铁或铝或它们的合金的表面作磷化处理时还含有0.8-4gl锌。本发明的前述实施形式能获得特别高质量的磷酸盐涂层。
如果按照本发明的一种具有优点的实施形式，用一种此外还含有2-10g/l SiO2和0.05-0.5g/l氟化物(按F计算)的磷酸盐化溶液润湿其表面，则可进一步地改善磷酸盐涂层的质量。作为SiO2，由于其可分散性。尤其热解硅酸是适合的。它最好被分散在水中。按照目的，氟化物以氟化氢及其水溶液形式加入。这些添加物所起的作用特别是形成均匀且封闭的涂层，它们实际中不易粘附。
本发明的其它有利实施形式在于，用一种磷酸盐化溶液润湿表面，该溶液的S值为0.5-0.7，或用磷酸盐化溶液以如下方式润湿表面，即干燥后磷酸盐涂层重量达到0.5-2g/m2。
尤其用不含锌的磷酸盐化溶液处理锌表面时，将优选的S值调到0.5-0.-是重要的，因为，与磷酸盐涂层中锌含量有关的磷酸盐化溶液对锌表面的浸蚀反应进行得尤其适宜。
将磷酸盐涂层重量调准到0.5-2g/m2的本发明实施形式使得磷酸盐涂层在特别短的时间内形成并由此具有特别高的质量成为可能。
采用本发明方法获得的磷酸盐涂层含有0.5至3重量％的镍，1.5-8重量％镁，1.0-35重量％锌，25-40重量％磷酸盐(按P2O5计)。
为确保磷酸盐化溶液充分润温，金属表面必须足够清洁。通常是这种情况，如果带材在镀锌之后直接按本发明方法处理的话。如果金属表面被弄上油或弄脏，要采用已公开的方法脱脂或清洗并紧接着冲刷。
在本发明方法中所采用的磷酸盐化溶液相应地在20至80℃之间的温度下使用，溶液的量一般在每平方米金属表面2至10毫升之间。干燥，只要它在热作用下发生，实际上在表面润湿之后立刻，即作用时间约0.5至5秒之后完成。
按照本发明，提供了这样一种方法，即能在数秒钟内获得磷酸盐涂层。比已公开的方法所具有的其它优点在于，可取消磷化前的活化预处理。所获得的磷酸盐涂层尤其在与随后涂上的漆、合成物或粘合剂的附着方面具有更高的质量。它在质量上与借助所谓三阳离子法获得的磷酸盐涂层相同。令人惊奇的是，按照本发明方法所获得的磷酸盐涂层通常是非晶态的，而按照三阳离子法形成的涂层始终是晶态的。
本发明的另一重要优点在于，所获得的磷酸盐涂层明显改善了所处理金属的变形性能，而对其可焊接性没有大大损害。
采用本发明方法获得的磷酸盐涂层可很好地用于所有应用磷酸盐涂层的领域。一个尤其适宜的应用场合是，为随后要涂漆，尤其是电浸渍涂漆的金属表面作前处理。
本发明的方法用于对镀锌或合金镀锌的钢带作磷化处理具有尤其重要的意义。对于镀锌或合金镀锌钢带可理解为这样的带材，即它们具有电解镀锌(ZE)层、热镀锌(Z)层、锌/镍(ZNE)合金层、锌/铁(ZF)合金层或锌/铝(ZA或AZ)合金层。后者通常也包括含有例如55重量％Al和45重量％Zn的合金在内。
参照下面的实施例将对本发明进一步举例说明。
实施例中所指的游离酸和总酸的含量如下确定：
为确定游离酸含量，将1毫升电解液用蒸馏水稀释至50毫升，如果需要的话加入K3(Co(CN)6)或K4(Fe(CN)6)以去除干扰金属离子，在采用二甲基黄作为指示剂条件下用n/10 NaOH滴定至由粉红色变成黄色。由所用的n/10 NaOH可得出游离酸的量。1毫升n/10 NaOH溶液对应于7.098毫克游离P2O5。
总酸量这样确定，1毫升磷酸盐化溶液用水稀释到约50毫升之后，用酚酞作指示剂滴定至由无色转变成红色。由所用的n/10 NaOH溶液求出总酸量。
所谓的S值由游离酸除以总P2O5量而求得。其中，总P2O5量这样来确定，即在确定游离酸后，滴定溶液被加入20毫升30％的中性乙二酸钾溶液后，相对于酚酞指示剂用n/10 NaOH滴定至由无色变为红色。由用二甲基黄转换和用酚酞转变之间的n/10 NaOH耗用量给出总P2O5量。(参照W.Rausch“金属的磷化处理”“Eugen G.Leuze-出版社，1988年S.300ff”)
实施例1：
在钢带熔体浸渍镀锌之后，紧接着直接将磷酸盐化溶液涂在仍保持在35℃的带表面上，该磷酸盐化溶液含有如下溶于完全不含盐的水中的组份，磷酸盐 69g/l(按P2O5计)锰 7.5g/l镍 2.7g/l
磷酸盐化溶液的温度为25℃，其pH值为1.7，而S值为0.6。其游离酸含量为5.9ml，总酸含量为17.1ml。
磷酸盐化溶液的涂覆借助一个例如也可用于带材涂漆的辊涂层机来完成。所涂覆的每平方米金属面积含有5毫升磷酸盐化溶液的湿膜在一直通炉内在200℃下在2秒钟作用时间后被干燥。离开炉子时，该带的温度为60℃。
所涂覆的磷酸盐涂层为均匀的，封闭的，其干涂层重量为1.1g/m2。它含有30重量％P2O5，20重量％锌，3.5重量％锰和1.4重量％镍。
带有按本发明方法制备的磷酸盐涂层的带材无论在涂漆状态还是不涂漆状态下都显示出极好的变形性能。随后涂覆的有机涂层的粘附性和防腐性也满足今天通常的要求。
按照本发明方法所磷化处理的带材也能在汽车厂通常的工艺过程中见到。即先按通常的方法将其形成为单个的汽车车身部件并通过焊接组合成车身，然后，由处理设备进行清洁-冲刷-活化-磷化-冲刷-后冲刷。其中，磷化处理在3.5分钟的时间内和磷酸盐化溶液温度为52℃条件下完成。磷酸盐化溶液的组成为：
14g/l磷酸盐(按P2O5计)
1.4g/l锌
1.0g/l锰
1.0g/l镍
70mg/l亚硝酸钠
185mg/l游离氟化物
游离酸的含量为1.5点，而总酸的含量为27.8点，各用10ml电解液来测量。S值调整到0.08。
采用上述方式所获得的磷酸盐涂层其单位面积重量为2.56g/m2，并含有31重量％P2O5、35重量％锌，6.4重量％锰，1.7重量％镍。
汽车车身在磷化处理后，首先涂覆阴极电浸渍漆，然后涂通常的汽车漆。
对用上述工艺过程模拟的试片进行如下测试：
碎石试验+VDA-变换试验，露天风化试验，切格+240小时冷凝水-恒定气候试验。
试验表明，在各方面的结果都满足所提出的期望值。尤其表明，第一阶段的磷化处理就具有与按通常的三阳离子法进行的磷化处理一样好的结果。
实施例2：
借助辊涂层机将27℃的磷酸盐化溶液涂在电解镀锌的带材表面，该磷酸盐化溶液具有以下组成：
磷酸盐 134g/l(按P2O5计算)
锰 14.8g/l
镍 5.42g/l
该溶液的S值为0.62，游高酸含量为10.3，总酸含量为29.7(就1ml电解液而言)。带材表面上的溶液湿膜为3ml/m2。
温膜在200℃炉温下干燥后便获得均匀的、封闭的磷酸盐涂层，涂层重量为1.6g/m2。
对磷酸盐涂层在其组成，可变形性，可焊接性，随后涂覆的有机漆涂层的粘附性和防腐性方面的检测显示这样的结果，即采用通常的磷化处理方法所获得的结果可与三阳离子法的相当。
实施例3：
借助一辊式碾在室温下将5ml/m2的磷酸盐化溶液湿膜涂在被清洁和冲刷的钢带表面，该磷酸盐化溶液具有如下组成：
134g/l磷酸盐(按P2O5计算)
14.8g/l锰
5.42g/l镍
3.33g/l锌
该溶液的S值为0.56，游离酸含量为9.4，总酸含量为29.2(基于1ml电解液)。
温膜在150℃下干燥后获得一均匀的、封闭的磷酸盐涂层，其涂层重量为1.0g/m2。它具有以下组成：
37重量％P2O5，4.2重量％锰，1.6重量％镍，2.1重量％锌。
对磷酸盐涂层就其随后涂覆的有机漆涂层的粘附性和防腐方面的检测表明，可完全满足所提出的要求。
实施例4：
将实施例3中磷酸盐化溶液借助一压辊以6ml/m2在室温下涂覆在被清洗和冲刷的AlMgSi合金的铝板表面，其湿膜在一直通式炉内在150℃温度下在15秒钟内被干燥。干燥的磷酸盐涂层具有1.95g/m2的面积重量和37重量％P2O5、3.9重量％锰，1.5重量％镍，1.5重量％锌的组成。在此，磷酸盐涂层就其与后面涂层相关的粘附和防腐方面的性能也能满足期望值。
Claims (7)
1．一种在锌、铁、铝或它们的合金表面通过用一种含有二价阳离子和磷酸根的磷酸盐化溶液润湿并紧接着对液体膜干燥而涂覆磷酸盐涂层的方法，其特征是，用一种不含元素周期表中第Ⅴ和Ⅵ副族元素，而含有0.5-8g/l镍，2-20g/l锰，18-170g/l磷酸盐(按P2O5计算)，并具有0.4-0.8的S值的磷酸盐化溶液以如下方式浸润表面，即干燥之后磷酸盐涂层重量达到0.3-3.0g/m2，其中，在磷化处理铁、铝或其合金的表面时，磷酸盐化溶液必需含0.5-5g/l锌，而在磷化处理锌或锌合金的表面时可以含锌。
2．按照权利要求1所述的方法，其特征是，在磷化处理锌或锌合金的表面时，采用不含锌的磷酸盐化溶液。
3．按照权利要求1所述的方法，其特征是，用一种磷酸盐化溶液浸润表面，溶液含有0.8-6g/l镍、3-16g/l锰、30-140g/l磷酸盐(按P2O5计算)，以及在磷化处理铁、铝或其合金的表面时含有0.8-4g/l锌。
4．按照权利要求1、2或3所述的方法，其特征是，用一种磷酸盐化溶液浸润表面，溶液另外还含有2-10g/l SiO2和0.05-0.5g/l氟化物(按F计算)。
5．按照权利要求1至4之一项或多项所述的方法，其特征是，用一种磷酸盐化溶液浸润表面，溶液具有0.5至0.7的S值。
6．按照权利要求1至5一项或多项所述的方法，其特征是，用磷酸盐化溶液以如下方式浸润表面，即干燥之后磷酸盐涂层重量达到0.5-2g/m2。
7．按照权利要求1至6之一项或多项所述的方法用于磷化处理镀锌或合金镀锌的钢带。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4443882A DE4443882A1 (de) | 1994-12-09 | 1994-12-09 | Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen |
| DEP4443882.6 | 1994-12-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1169165A CN1169165A (zh) | 1997-12-31 |
| CN1066207C true CN1066207C (zh) | 2001-05-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95196688A Expired - Lifetime CN1066207C (zh) | 1994-12-09 | 1995-12-05 | 在金属表面涂覆磷酸盐涂层的方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5904786A (zh) |
| EP (1) | EP0796356B1 (zh) |
| JP (1) | JPH10510322A (zh) |
| KR (1) | KR970707322A (zh) |
| CN (1) | CN1066207C (zh) |
| AT (1) | ATE173034T1 (zh) |
| AU (1) | AU700492B2 (zh) |
| CA (1) | CA2207932C (zh) |
| DE (2) | DE4443882A1 (zh) |
| ES (1) | ES2124032T3 (zh) |
| MX (1) | MX9704126A (zh) |
| WO (1) | WO1996017977A1 (zh) |
| ZA (1) | ZA9510440B (zh) |
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| CN102666903A (zh) * | 2009-10-26 | 2012-09-12 | 新日本制铁株式会社 | 成形性及粘接后的耐剥离性优异的合金化熔融镀锌钢板及其制造方法 |
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| CN1111569C (zh) * | 1998-04-13 | 2003-06-18 | 赵全玺 | 无机磷酸盐涂料 |
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| DE10010355A1 (de) | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile |
| US6530999B2 (en) | 2000-10-10 | 2003-03-11 | Henkel Corporation | Phosphate conversion coating |
| US20040188323A1 (en) * | 2003-03-24 | 2004-09-30 | Tzatzov Konstantin K. | Active coating system for reducing or eliminating coke build-up during petrochemical processes |
| CN100338260C (zh) * | 2004-05-14 | 2007-09-19 | 深圳市成功科技有限公司 | 铝合金暖气片复合镀镍方法 |
| US20060002832A1 (en) * | 2004-05-19 | 2006-01-05 | Ez Environmental Solutions Corporation, A California Corporation | Selectable closed-loop phosphatizing wash & rinse system and method |
| US7514153B1 (en) | 2005-03-03 | 2009-04-07 | The United States Of America As Represented By The Secretary Of The Navy | Method for deposition of steel protective coating |
| CN100366796C (zh) * | 2005-04-22 | 2008-02-06 | 吉林大学 | 一种在水溶液中制备无机磷酸盐薄膜的方法 |
| US8137805B2 (en) * | 2007-06-21 | 2012-03-20 | Caterpillar Inc. | Manganese based coating for wear and corrosion resistance |
| US8137761B2 (en) * | 2008-06-13 | 2012-03-20 | Caterpillar Inc. | Method of coating and induction heating a component |
| CN101660164B (zh) * | 2008-08-26 | 2011-12-28 | 宝山钢铁股份有限公司 | 一种润滑性电镀锌钢板及其生产方法 |
| KR101405781B1 (ko) * | 2009-10-26 | 2014-06-10 | 신닛테츠스미킨 카부시키카이샤 | 합금화 용융 아연 도금 강판과 그 제조 방법 |
| JP5189691B1 (ja) * | 2011-06-17 | 2013-04-24 | 株式会社神戸製鋼所 | 圧粉磁心用鉄基軟磁性粉末およびその製造方法、ならびに圧粉磁心 |
| DE102017117080A1 (de) * | 2017-07-28 | 2019-01-31 | Thyssenkrupp Ag | Stahlblech mit einer Konversionsschicht, Verfahren zur Herstellung eines konversionsbeschichteten Stahlblechs und Behandlungsmittel zur Applizierung einer Konversionsschicht auf einem Stahlblech |
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| CN112522689B (zh) * | 2020-10-30 | 2023-06-23 | 马鞍山钢铁股份有限公司 | 一种合金化镀锌钢板表面处理剂、制备方法及合金化镀锌钢板、热成形零部件 |
| CN113529062A (zh) * | 2021-07-13 | 2021-10-22 | 山东大学 | 一种锌合金表面磷酸锌化学转化膜及其制备方法和应用 |
| CN115068699B (zh) * | 2022-06-30 | 2024-06-04 | 卓阮医疗科技（苏州）有限公司 | 一种可吸收固定钉、其制备方法及其在固定口腔引导骨再生屏障膜中的应用 |
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| CN102666903A (zh) * | 2009-10-26 | 2012-09-12 | 新日本制铁株式会社 | 成形性及粘接后的耐剥离性优异的合金化熔融镀锌钢板及其制造方法 |
| CN102666903B (zh) * | 2009-10-26 | 2015-04-15 | 新日铁住金株式会社 | 成形性及粘接后的耐剥离性优异的合金化熔融镀锌钢板及其制造方法 |
| US9040168B2 (en) | 2009-10-26 | 2015-05-26 | Nippon Steel & Sumitomo Metal Corporation | Galvannealed steel sheet having excellent formability and exfoliation resistance after adhesion and production method thereof |
| US9903022B2 (en) | 2009-10-26 | 2018-02-27 | Nippon Steel 7 Sumitomo Metal Corporation | Production method of galvannealed steel sheet having excellent formability and exfoliation resistance after adhesion |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE173034T1 (de) | 1998-11-15 |
| JPH10510322A (ja) | 1998-10-06 |
| ZA9510440B (en) | 1997-06-09 |
| EP0796356A1 (de) | 1997-09-24 |
| CN1169165A (zh) | 1997-12-31 |
| AU700492B2 (en) | 1999-01-07 |
| CA2207932C (en) | 2007-05-08 |
| EP0796356B1 (de) | 1998-11-04 |
| US5904786A (en) | 1999-05-18 |
| DE59504172D1 (de) | 1998-12-10 |
| MX9704126A (es) | 1998-02-28 |
| WO1996017977A1 (de) | 1996-06-13 |
| CA2207932A1 (en) | 1996-06-13 |
| AU4259996A (en) | 1996-06-26 |
| ES2124032T3 (es) | 1999-01-16 |
| KR970707322A (ko) | 1997-12-01 |
| DE4443882A1 (de) | 1996-06-13 |
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