EP0796356A1 - Procede d'application de revetements de phosphate sur des surfaces metalliques - Google Patents
Procede d'application de revetements de phosphate sur des surfaces metalliquesInfo
- Publication number
- EP0796356A1 EP0796356A1 EP95941068A EP95941068A EP0796356A1 EP 0796356 A1 EP0796356 A1 EP 0796356A1 EP 95941068 A EP95941068 A EP 95941068A EP 95941068 A EP95941068 A EP 95941068A EP 0796356 A1 EP0796356 A1 EP 0796356A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- phosphate
- phosphating
- solution
- alloys
- 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.)
- Granted
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 61
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 60
- 239000010452 phosphate Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title abstract description 17
- 239000002184 metal Substances 0.000 title abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 48
- 239000011701 zinc Substances 0.000 claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 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
- 238000009736 wetting Methods 0.000 claims abstract description 10
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 4
- 239000008397 galvanized steel Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 15
- 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 abstract description 5
- 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 3
- 239000004411 aluminium Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 46
- 239000011248 coating agent Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000203 mixture Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000003973 paint Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000008237 rinsing water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium 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
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005246 galvanizing Methods 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
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium 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
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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 compound 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent 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
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 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
- 239000007800 oxidant agent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 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
- 238000004448 titration Methods 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
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
-
- 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
- C23C22/34—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
Definitions
- the invention relates to a method for applying phosphate coatings on surfaces of zinc, iron, aluminum or their alloys by wetting them with a phosphate solution containing divalent cations and phosphate and then drying the liquid film.
- the process of producing phosphate coatings using aqueous zinc phosphate solutions is widely used in the metalworking industry.
- the phosphate layers created with this process on the treated metal surfaces are used in particular to facilitate sliding, to prepare for non-cutting cold forming, as well as to protect against corrosion and as a paint primer.
- Such phosphating solutions usually have a pH between about 1.8 and 3.8 and contain zinc and phosphate ions as process-determining components.
- zinc in addition to the cation zinc, other cations, for example ammonium, calcium, cobalt, iron, potassium, copper, sodium, magnesium, manganese, may also be present.
- oxidizing agents such as bromate, chlorate, nitrate, nitrite, organic nitro compounds, perborate, persulfate or hydrogen peroxide are generally added to the phosphating solutions.
- additives such as Fluoride, silicon fluoride, boron fluoride, citrate and tartrate. Due to the large number of individual components and their possible combinations, there are a multitude of different compositions of the phosphating solutions.
- the so-called low-zinc processes represent a special embodiment of the phosphating processes.
- the phosphating solutions used here contain zinc in concentrations of only about 0.4 to 1.7 g / l and, particularly on steel, produce phosphate layers with a high proportion of phosphophyllite, which is better Provides paint adhesion and a higher resistance to paint infiltration when exposed to corrosion than is customary in the production of phosphate layers based on Hopeit from phosphating solutions with a higher zinc content.
- phosphating processes which experts call the trication process.
- These are low-zinc phosphating processes, in which the use of nickel in e.g. Quantities of 0.3 - 2.0 g / 1 and manganese in quantities of e.g. 0.5 - 1.5 g / 1 phosphate coatings are obtained, which are characterized by an increased alkali resistance and are therefore of importance for cathodic electrocoating, in particular for car bodies.
- a common feature of the aforementioned phosphating processes is that the phosphating solution is brought into contact with the workpiece surfaces to be treated in immersion, flooding or spraying. After the chemical reaction has taken place and the solid, Critalline phosphate layer requires a rinsing treatment to remove any phosphating chemicals remaining on the surface, which is usually carried out in several stages. This results in rinsing solutions that cannot be disposed of in this form, but must be sent to a wastewater treatment plant.
- One such method which is intended for preparing metal surfaces for subsequent coating with organic coatings, is to wet the metal surface with a phosphating liquid which has a pH of 1.5 to 3, is chromium-free and contains, in addition to metal phosphate, soluble molybdate, tungstate, vanadate, niobate and / or tantalate ions (EP-B-15 020).
- the cationic component of the metal phosphate in the solution can be formed by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese.
- a disadvantage of the last-mentioned process is that due to the necessary additions of molydate, tungstate, vanadate, niobate and tantalate ions, the process is more cost-intensive than the conventional phosphating processes, another that the phosphate coatings obtained do not meet all requirements today e.g. B. with regard to alkali resistance and thus resistance in a subsequent cathodic electrocoating and the desired corrosion resistance, in particular in connection with a subsequent painting, are sufficient.
- the object of the invention is to provide a method for applying phosphate coatings on surfaces of zinc, iron, aluminum or their alloys, which does not have the known, in particular the aforementioned disadvantages, is nevertheless inexpensive and simple to carry out and leads to high-quality phosphate coatings.
- the object is achieved by the method of the type mentioned according to the invention is designed such that the
- Alloys necessarily contain 0.5 to 5 g / 1 zinc and in the case the phosphating of surfaces made of zinc or zinc alloys can contain zinc ions.
- the aforementioned formulation with regard to the zinc content is intended to express that in the case of the treatment of surfaces made of iron, aluminum or their alloys, a zinc content in the concentrations mentioned is essential.
- the phosphating solution can also contain zinc, but a zinc content is not required.
- Elements of the 5th and 6th subgroup of the Periodic Table of the Elements are vanadium, niobium, tantalum, chromium, molybdenum and tungsten.
- the S value is expediently set with nickel oxide, manganese oxide or possibly zinc oxide or with ammonia solution.
- An expedient embodiment of the invention provides that, in the case of the treatment of zinc or zinc alloys, the surfaces are wetted with a phosphating solution which is zinc-free. In this particular case, the amount of zinc required to form the coating comes from the surface of the treated material.
- the wetting of the respective metal surfaces can e.g. by immersion and subsequent draining, by pouring over and spinning off, by brushing, by spraying with compressed air, air-les and electrostatically.
- a particularly elegant method of applying the phosphating solution is carried out by rolling with structured or smooth rollers in the same direction or in the opposite direction.
- the drying following the wetting of the metal surface can in principle already take place at room temperature. However, it is advantageous to work at higher temperatures because this considerably reduces the time for the formation of the phosphate layer. Drying is preferably carried out at temperatures between 50 and 200'C, but an object temperature of 90 "C should not be exceeded.
- a preferred development of the invention is that
- Aluminum or its alloys contains 0.8 to 4 g / 1 zinc.
- the aforementioned embodiment of the invention leads to particularly high quality phosphate coatings.
- Hydrogen fluoride or their aqueous solution introduced. These additives in particular bring about the formation of a uniform and closed coating which practically does not tend to stick.
- Further advantageous embodiments of the invention consist of wetting the surfaces with a phosphating solution which has an S value of 0.5 to 0.7 or wetting the surfaces with the phosphating solution in such a way that after drying a phosphate layer weight of 0, 5 to 2 g / m : results.
- the setting of the preferred S value of 0.5 to 0.7 is particularly important in the treatment of zinc surfaces with zinc-free phosphating solutions, since the pickling attack of the phosphating solution on the zinc surface responsible for the zinc content of the phosphate coating is particularly optimal runs.
- the embodiment of the invention with a phosphate coating weight of 0.5 to 2 g / m * enables the phosphate coating to be formed in a particularly short time and, moreover, of particularly high quality.
- Phosphate layers produced that 0.5 to 3 wt .-% nickel
- the metal surfaces must be sufficiently clean to ensure proper wetting with the phosphating solution. This is generally the case when e.g. B. strip material is treated immediately after the galvanizing by the method according to the invention. However, if the metal surface is oiled or dirty, degreasing or cleaning must be carried out using methods known per se and then rinsed.
- Phosphating solution is expediently used at a temperature in the range from 20 to 80 ° C.
- the amount of the solution is usually between 2 and 10 ml per m 2 of metal surface Surface, ie after an exposure time of about 0.5 to 5 see.
- the present invention provides a method capable of producing phosphate coatings in a matter of seconds. Another advantage over known processes is that an activating pretreatment before phosphating can be omitted.
- the phosphate coatings produced are particularly of high quality with regard to the adhesion imparting of subsequently applied paints, plastics or adhesives. Their quality is similar to that of the phosphate layers produced using the so-called trication process. This is surprising insofar as the phosphate coatings obtained by the process according to the invention are generally are amorphous, whereas the layers formed by the trication method are always crystalline.
- Another important advantage of the invention is that phosphate layers are produced which significantly improve the forming behavior of the metals treated in this way, without the weldability being significantly impaired thereby.
- phosphate coatings produced using the method according to the invention can be used well in all fields in which phosphate coatings are used.
- a particularly advantageous application is the preparation of the metal surfaces for the subsequent painting, in particular the electrocoating.
- the method according to the invention is of particularly outstanding importance for its application to the phosphating of galvanized or alloy-galvanized steel strips.
- galvanized or alloy-galvanized steel strip is understood to mean strips which are a coating of Elektroytzmk (ZE), hot-dip zinc (Z), alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / aluminum (ZA or AZ) ) exhibit. To the latter, alloys with z. B. 55 wt .-% Al and 45 wt .-% Zn counted.
- the total number of points is determined by titrating 1 ml of the phosphating solution after dilution with water to about 50 ml using phenolphthalein as an indicator until the color changes from colorless to red.
- the number of ml n / 10 sodium hydroxide used for this gives the total number of points.
- the so-called S value is obtained by dividing the free acid by the total P, 0 5 .
- the total P 2 0 5 is determined by, following the determination of the free acid, the titration solution after adding 20 ml of 30% strength neutral potassium oxalate solution against phenolphthalein as an indicator until the color changes to red with n / 10 NaOH is titrated.
- the consumption of ml n / 10 NaOH between the envelope with dimethyl yellow and the envelope with phenolphthalein gives the total P, 0 5 .
- Phosphating solution applied which contained the following components - dissolved in deionized water.
- the phosphating solution had a temperature of 25 * C, a pH value of 1.7 and an S value of 0.6.
- the content was
- the application of the phosphating solution was carried out with the help of a roll coating machine (roll coater), as it is also used for coil coating.
- the applied wet film of 5 ml phosphating solution per m 2 of metal surface was dried after an exposure time of 2 seconds in a continuous furnace at 200 "C. When leaving the furnace, the strip had an object temperature of 60 * C.
- the phosphate coating applied was uniform, closed and had a dry layer weight of
- the tape provided with a phosphate coating by the process according to the invention showed excellent behavior during deformation, both in the lacquered and in the unpainted state.
- the adhesion and corrosion protection values of subsequently applied organic coatings also met today's requirements.
- the strip phosphated by the process according to the invention can also pass through the process usual in the automotive plant. This means that the individual body parts can first be shaped in a customary manner and assembled by welding to form the body and then the treatment system cleaning-rinsing-activating-
- Phosphating solution is:
- the free acid content was 1.5 and the total acid content 27.8
- the phosphate coating produced in this way has a weight per unit area of 2.56 g / m 2 and contained 31% by weight of P 2 O 5 , 35% by weight of zinc, 6.4% by weight of manganese 1.7% by weight. % Nickel.
- the bodies are first provided with a cathodic electrodeposition paint and then with the customary automotive paint structure.
- Test sheets with which the aforementioned process was simulated were subjected to the following tests:
- the solution had an S value of 0.62, a free acid content of 10.3 and a total acid content of 29.7 (based on a
- the solution had an S value of 0.56, a free acid content of 9.4 and a total acid content of 29.2 (based on 1 ml
- the dry phosphate layer had a basis weight of 1.95 g / ⁇ r and a composition of 37% by weight p, 0 3 3.9% by weight manganese, 1.5% by weight nickel and 1.9% by weight zinc here were the properties of the phosphate layer in terms of adhesion and Corrosion protection in connection with a subsequently applied coating as expected.
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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)
- Materials For Medical Uses (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4443882 | 1994-12-09 | ||
DE4443882A DE4443882A1 (de) | 1994-12-09 | 1994-12-09 | Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen |
PCT/EP1995/004774 WO1996017977A1 (fr) | 1994-12-09 | 1995-12-05 | Procede d'application de revetements de phosphate sur des surfaces metalliques |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0796356A1 true EP0796356A1 (fr) | 1997-09-24 |
EP0796356B1 EP0796356B1 (fr) | 1998-11-04 |
Family
ID=6535385
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95941068A Expired - Lifetime EP0796356B1 (fr) | 1994-12-09 | 1995-12-05 | Procede d'application de revetements de phosphate sur des surfaces metalliques |
Country Status (13)
Country | Link |
---|---|
US (1) | US5904786A (fr) |
EP (1) | EP0796356B1 (fr) |
JP (1) | JPH10510322A (fr) |
KR (1) | KR970707322A (fr) |
CN (1) | CN1066207C (fr) |
AT (1) | ATE173034T1 (fr) |
AU (1) | AU700492B2 (fr) |
CA (1) | CA2207932C (fr) |
DE (2) | DE4443882A1 (fr) |
ES (1) | ES2124032T3 (fr) |
MX (1) | MX9704126A (fr) |
WO (1) | WO1996017977A1 (fr) |
ZA (1) | ZA9510440B (fr) |
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WO2001066826A1 (fr) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Procede de phosphatation utilisation des pieces en metal ainsi phosphatees |
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DE19749508A1 (de) | 1997-11-08 | 1999-05-12 | Henkel Kgaa | Korrosionsschutz von verzinkten und legierungsverzinkten Stahlbändern |
CN1111569C (zh) * | 1998-04-13 | 2003-06-18 | 赵全玺 | 无机磷酸盐涂料 |
US6235111B1 (en) * | 1998-11-25 | 2001-05-22 | Ez Environmental Solutions, Corporation | Closed-loop phosphatizing system and method |
CA2358625A1 (fr) | 2000-10-10 | 2002-04-10 | Henkel Corporation | Revetement de conversion au phosphate |
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 |
WO2011052269A1 (fr) * | 2009-10-26 | 2011-05-05 | 新日本製鐵株式会社 | Tôle d'acier allié, galvanisé par immersion à chaud, et procédé de fabrication associé |
JP5168417B2 (ja) * | 2009-10-26 | 2013-03-21 | 新日鐵住金株式会社 | 成形性及び接着後の耐剥離性に優れた合金化溶融亜鉛めっき鋼板とその製造方法 |
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 |
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 |
CN112410768B (zh) * | 2020-10-30 | 2023-06-23 | 马鞍山钢铁股份有限公司 | 一种镀锌钢板表面处理剂、表面处理剂的制备方法及自润滑镀锌钢板、钢板的制备方法 |
CN115838925A (zh) * | 2021-07-13 | 2023-03-24 | 山东大学 | 一种表面包覆磷酸锌膜层的改性锌合金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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- 1994-12-09 DE DE4443882A patent/DE4443882A1/de not_active Withdrawn
-
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- 1995-12-05 KR KR1019970702491A patent/KR970707322A/ko not_active Application Discontinuation
- 1995-12-05 DE DE59504172T patent/DE59504172D1/de not_active Expired - Lifetime
- 1995-12-05 JP JP8517316A patent/JPH10510322A/ja active Pending
- 1995-12-05 MX MX9704126A patent/MX9704126A/es unknown
- 1995-12-05 US US08/860,350 patent/US5904786A/en not_active Expired - Lifetime
- 1995-12-05 CN CN95196688A patent/CN1066207C/zh not_active Expired - Lifetime
- 1995-12-05 WO PCT/EP1995/004774 patent/WO1996017977A1/fr not_active Application Discontinuation
- 1995-12-05 CA CA002207932A patent/CA2207932C/fr not_active Expired - Fee Related
- 1995-12-05 AU AU42599/96A patent/AU700492B2/en not_active Ceased
- 1995-12-05 EP EP95941068A patent/EP0796356B1/fr not_active Expired - Lifetime
- 1995-12-05 AT AT95941068T patent/ATE173034T1/de active
- 1995-12-05 ES ES95941068T patent/ES2124032T3/es not_active Expired - Lifetime
- 1995-12-08 ZA ZA9510440A patent/ZA9510440B/xx unknown
Non-Patent Citations (1)
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001066826A1 (fr) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Procede de phosphatation utilisation des pieces en metal ainsi phosphatees |
US7208053B2 (en) | 2000-03-07 | 2007-04-24 | Chemetall Gmbh | Method for applying a phosphate covering and use of metal parts thus phospated |
Also Published As
Publication number | Publication date |
---|---|
ZA9510440B (en) | 1997-06-09 |
AU700492B2 (en) | 1999-01-07 |
ES2124032T3 (es) | 1999-01-16 |
WO1996017977A1 (fr) | 1996-06-13 |
CA2207932A1 (fr) | 1996-06-13 |
AU4259996A (en) | 1996-06-26 |
KR970707322A (ko) | 1997-12-01 |
DE4443882A1 (de) | 1996-06-13 |
ATE173034T1 (de) | 1998-11-15 |
DE59504172D1 (de) | 1998-12-10 |
US5904786A (en) | 1999-05-18 |
CN1169165A (zh) | 1997-12-31 |
JPH10510322A (ja) | 1998-10-06 |
CN1066207C (zh) | 2001-05-23 |
EP0796356B1 (fr) | 1998-11-04 |
CA2207932C (fr) | 2007-05-08 |
MX9704126A (es) | 1998-02-28 |
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