EP0414301A1 - Procédé d'obtention de revêtement de phosphate sur des surfaces métalliques - Google Patents
Procédé d'obtention de revêtement de phosphate sur des surfaces métalliques Download PDFInfo
- Publication number
- EP0414301A1 EP0414301A1 EP90202148A EP90202148A EP0414301A1 EP 0414301 A1 EP0414301 A1 EP 0414301A1 EP 90202148 A EP90202148 A EP 90202148A EP 90202148 A EP90202148 A EP 90202148A EP 0414301 A1 EP0414301 A1 EP 0414301A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- phosphating
- water
- rinsing
- free
- 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
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 31
- 239000010452 phosphate Substances 0.000 title claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 title claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 26
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 22
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008237 rinsing water Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 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 claims abstract description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 nitrate ions Chemical class 0.000 claims abstract description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000010802 sludge Substances 0.000 claims description 7
- 239000013505 freshwater Substances 0.000 claims description 5
- 238000000909 electrodialysis Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 229910004074 SiF6 Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910002547 FeII Inorganic materials 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 3
- 235000021317 phosphate Nutrition 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000013589 supplement Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000680 Aluminized steel Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 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 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004062 sedimentation 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
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- HHIMNFJHTNVXBJ-UHFFFAOYSA-L zinc;dinitrite Chemical compound [Zn+2].[O-]N=O.[O-]N=O HHIMNFJHTNVXBJ-UHFFFAOYSA-L 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
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/22—Orthophosphates containing alkaline earth metal 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
- C23C22/362—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 zinc 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
- C23C22/73—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 characterised by the process
Definitions
- the invention relates to a wastewater-free process for producing phosphate coatings on metal surfaces by means of aqueous zinc phosphate solutions containing iron (II) and nitrate ions.
- the process of producing phosphate coatings by means of aqueous zinc phosphate solutions is widely used in the metalworking industry.
- the phosphate layers produced on the treated metal surfaces with this process are used in particular to facilitate sliding and non-cutting cold forming, as well as for corrosion protection and as a paint primer.
- Such phosphating baths usually have a pH between about 1.8 and 3.8 and contain zinc and phosphate ions as process-determining components.
- other cations e.g. Ammonium, calcium, cobalt, iron, potassium, copper, sodium, magnesium, manganese, may be present.
- the phosphating baths are generally oxidizing agents, e.g. Bromate, chlorate, nitrate, nitrite, organic nitro compounds, perborate, persulfate, hydrogen peroxide, added. Oxygen-containing gas can also be used for the oxidation of iron (II) to iron (III).
- 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 large number of different phosphating bath compositions.
- the phosphating baths are usually brought into contact with the workpiece surfaces to be treated in immersion, flooding or spraying. During the contact period between a few seconds up to half an hour and more, crystalline phosphate layers are firmly integrated by chemical reaction with the metal. Since residues of the phosphating solution remaining on the surface usually interfere with further processing, the water is thoroughly rinsed after the phosphating. In order to avoid harmful accumulation of the ingredients of the phosphating bath in the rinsing baths, these are operated with an inflow of fresh water and an overflow of contaminated rinsing water. The contaminated rinsing water contains environmentally hazardous substances and therefore requires special treatment before it can be discharged into the sewage system or a drain.
- the object of the invention is to provide a process for producing phosphate coatings on metals, in particular steel, galvanized steel, alloy-galvanized steel, aluminized steel and aluminum, with the aid of zinc phosphate solutions containing iron (II) and nitrate ions, which works free of waste water and the known ones , especially the aforementioned, does not have disadvantages.
- wastewater-free in the sense of the invention means that no water from the rinsing baths enters the sewage system or the receiving water with the intended effect of counteracting an accumulation of undesirable chemicals in the phosphating bath.
- the method according to the invention is particularly suitable for the surface treatment of iron and steel, low-alloy steel, galvanized steel, alloy-galvanized, i.e. e.g. steel coated with ZnAl, ZnFe and ZnNi, aluminized steel, aluminum and its alloys.
- the phosphating solutions contain Zn, P2O5 and NO3 as basic components. Other cations and / or anions can also be present. Phosphating solutions in which certain concentrations of bromate, chlorate, organic nitro compounds, perborate and / or persulfate have to be maintained during the work by supplementing them are not suitable for the wastewater-free procedure according to the invention. Likewise unsuitable are those to which alkali nitrite must be added as an accelerator from time to time or continuously.
- the metal surfaces are brought into contact with a phosphating solution which additionally up to 10 g / l Mg up to 20 g / l approx up to 20 g / l Mn up to 20 g / l Ni up to 10 g / l Co up to 0.02 g / l Cu up to 20 g / l Na and / or K and / or NH4 up to 8 g / l SiF6 up to 8 g / l BF4 up to 5 g / 1 F up to 10 g / l Cl contains.
- a phosphating solution which additionally up to 10 g / l Mg up to 20 g / l approx up to 20 g / l Mn up to 20 g / l Ni up to 10 g / l Co up to 0.02 g / l Cu up to 20 g / l Na and / or K and / or NH4 up to 8 g / l SiF
- the metal surfaces should be brought into contact with a phosphating solution in which the weight ratio (Mg + Ca + Mn + Ni + Co): Zn equal / less than 4: 1 and that of the components Mg, Ca, Mn, Fe, Ni, Co and Cu according to the molar ratio (Mg + Ca + Mn + Fe + Ni + Co + Cu): Zn equal to / less than 2 is added.
- a phosphating solution in which the weight ratio (Mg + Ca + Mn + Ni + Co): Zn equal / less than 4: 1 and that of the components Mg, Ca, Mn, Fe, Ni, Co and Cu according to the molar ratio (Mg + Ca + Mn + Fe + Ni + Co + Cu): Zn equal to / less than 2 is added.
- Fe (II) is usually not added as a chemical, but it accumulates during the throughput of iron and steel as a result of the pickling attack, provided that it has not been converted into the trivalent form by oxidizing agents and as iron ( III) -phosphate is precipitated.
- Fe (III) in the baths serves, among other things, to stabilize the phosphating balance.
- Mg and / or Ca and / or Mn phosphate coatings are obtained which, in addition to Zn and optionally Fe (II), also contain these cations.
- Mixed phosphates of this type are notable for increased alkali resistance and are therefore particularly suitable as a primer for paints. But they have also proven themselves as a lubricant carrier in non-cutting cold forming.
- Ni and / or Co are preferably used to reduce the aggressiveness of the baths Increase steel and improve the phosphating of zinc surfaces. Small amounts of copper have an accelerating effect.
- Alkaline cations and / or ammonium serve primarily to set the desired acid ratio.
- the anions F, BF4 and SiF6 generally increase the rate of phosphating and are advantageous for the treatment of aluminum-containing zinc surfaces.
- the presence of free fluoride (F ⁇ ) is essential for the crystalline phosphating of aluminum and its alloys.
- Cl can be used to adjust the electronic neutrality of the baths and in special cases also to increase their aggressiveness.
- the thickness or weight per unit area of the phosphate layers produced can be influenced by adding, for example, polyhydroxyarboxylic acid, such as tartaric acid and / or citric acid.
- the coordination of the type and amount of anions and cations in the phosphating solutions used to carry out the process according to the invention is carried out in such a way that the ratio of free P2O5 to total P2O5 (0.04 to 0.50): 1, with higher (lower ) Bath temperatures and / or concentrations in the phosphating solution each have to be chosen to be higher (lower) ratios.
- the concentration of Fe (II) should not exceed that of zinc, while the sum of the concentrations of Mg + Ca + Mn + Ni + Co should not exceed four times the zinc concentration.
- the molar ratio of (Mg + Ca + Mn + Fe + Ni + Co + Cu): Zn should be 2: 1.
- the supplement is particularly effective if, according to a further preferred embodiment of the invention, the metal surfaces are brought into contact with a phosphating solution, which by adding phosphate with a ratio of free P2O5 to total P2O5 when supplementing (- 0.4 to + 0.5): 1 is added.
- a phosphating solution which by adding phosphate with a ratio of free P2O5 to total P2O5 when supplementing (- 0.4 to + 0.5): 1 is added.
- the minus sign means that there is no free P2O5, but rather part of the phosphate is in the secondary phosphate stage.
- the value minus 0.19 means, for example, that 19% of the total P2O5 are present as secondary phosphate.
- the phosphate components in the supplement are in a range which is 40% secondary and 60% primary phosphate (calc. As P2O5 on the one hand and 50% primary phosphate and 50% free phosphoric acid (calc. As P2O5) on the other hand is limited.
- the supplementary components are usually added in the form of an acidic aqueous chemical concentrate. Since liquid supplement concentrates with a ratio of free P2O5 to total P2O5 less than 0.2: 1 are not stable, the supplement is then carried out with at least two separate concentrates.
- the rate of addition is expediently chosen such that the composition of the phosphating solution is at least largely constant even with fluctuating throughput, ie fluctuating consumption fades.
- Special portions of the necessary supplement can also be added to the bath separately from the actual supplement concentrate.
- An example is the addition of zinc oxide or zinc carbonate, which on the one hand increases the zinc concentration and on the other hand a correction of the ratio of free P2O5 to total P2O5 is possible.
- NO3 optionally together with oxygen-containing gas, H2O2 and / or nitrous gases are used as oxidation accelerators in the process according to the invention.
- a small amount of nitrite, about 0.05 to 0.15 g / l, for example as zinc nitrite or calcium nitrite is preferably added at the start of work.
- the nitrite generation from the nitrate can also be initiated by brief phosphating of zinc, zinc granules or zinc dust or by initially lower throughput density of steel.
- Alkali nitrite should only be used in exceptional cases when starting the bath, otherwise alkali will accumulate to a disruptive extent. Due to the absence of excess nitrite or H2O5 accumulates in the baths (Fe (II) when iron and steel are treated. Intensive contact of the solution with oxygen-containing gas, such as air, and / or H2O2 can enrich the iron via the Interference limit can be avoided.
- oxygen-containing gas such as air
- a phosphate cascade with at least two rinse baths follows the phosphating.
- the principle of the rinsing bath cascade is that fresh water is only supplied to the last rinsing bath and a corresponding overflow into the previous baths is triggered. In this way, a rinse water flow manufactured, which is opposite to the flow of the workpieces.
- At least as much low-salt or salt-free water is withdrawn from the phosphating bath by a suitable process that it can absorb the phosphate-rich overflow from the cascade.
- the characteristics of the cascade must be selected so that the degree of purity of the last rinsing bath is sufficient for the technical requirements of the further treatments.
- the effectiveness of a rinsing bath cascade can be increased even more by not overflowing directly from one bath into the previous one, but in such a way that the parts running out of the previous bath are sprayed off first and only then is it introduced into the rinsing bath itself.
- Further preferred embodiments of the method according to the invention consist in extracting the salt-free or low-salt water from the phosphating bath by means of single-stage or multi-stage evaporation, reverse osmosis or electrodialysis and returning it to the rinsing bath cascade as fresh water.
- a further preferred embodiment provides for the phosphate-containing rinsing water from the rinsing bath cascade to be concentrated, in particular by evaporation, electrodialysis or reverse osmosis, before they are introduced into the phosphating bath.
- a bath sludge is obtained, which is separated from the system continuously or from time to time, for example by sedimentation, filtration and the like. 50 to 90% of the phosphating solution adheres to this wet sludge.
- this phosphate sludge is washed with water after it has been separated off and introduced into the rinsing bath cascade or directly into the phosphating bath.
- the phosphate sludge can be washed in several stages, possibly in the manner of a cascade, with rinsing water from the individual rinsing baths.
- a 3-stage rinse bath cascade followed the phosphating. During the material throughput, 0.2 l / m2 of treated steel surface were evaporated from the phosphating bath. In the last rinsing bath of the cascade, 0.2 l of salt-free water per m2 of treated surface were added. The resulting overflow reached rinsing bath 2, rinsing bath 1 and finally the phosphating bath.
- the experiment shows that it is possible with the method according to the invention to produce flawless phosphate layers, - to keep the concentration of the phosphating solution stationary, - to work free of contaminated rinse water and - operate the last rinsing bath with a lower salt concentration (0.2 pt., corresponding to 0.23 g / l salt).
- Table 2 lists various phosphating bath compositions suitable for carrying out the process according to the invention and supplementary concentrates suitable therefor.
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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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT90202148T ATE85987T1 (de) | 1989-08-22 | 1990-08-07 | Verfahren zur erzeugung von phosphatueberzuegen auf metalloberflaechen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3927613 | 1989-08-22 | ||
| DE3927613A DE3927613A1 (de) | 1989-08-22 | 1989-08-22 | Verfahren zur erzeugung von phosphatueberzuegen auf metalloberflaechen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0414301A1 true EP0414301A1 (fr) | 1991-02-27 |
| EP0414301B1 EP0414301B1 (fr) | 1993-02-24 |
Family
ID=6387565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90202148A Expired - Lifetime EP0414301B1 (fr) | 1989-08-22 | 1990-08-07 | Procédé d'obtention de revêtement de phosphate sur des surfaces métalliques |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5203930A (fr) |
| EP (1) | EP0414301B1 (fr) |
| JP (1) | JP3000108B2 (fr) |
| AT (1) | ATE85987T1 (fr) |
| AU (1) | AU633611B2 (fr) |
| BR (1) | BR9004128A (fr) |
| CA (1) | CA2023663C (fr) |
| DD (1) | DD299661A5 (fr) |
| DE (2) | DE3927613A1 (fr) |
| ES (1) | ES2038483T3 (fr) |
| PL (1) | PL164655B1 (fr) |
| ZA (1) | ZA906672B (fr) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2056748A1 (es) * | 1992-09-17 | 1994-10-01 | Rieger Franz Metallveredelung | Baño para el tratamiento previo de metales ligeros, su procedimiento y objetos producidos por los mismos. |
| US5415701A (en) * | 1993-03-02 | 1995-05-16 | Metallgesellschaft Aktiengesellschaft | Process for facilitating cold-working operations |
| EP0751239A1 (fr) * | 1995-06-30 | 1997-01-02 | Metallgesellschaft Aktiengesellschaft | Procédé de remontage de solution de phosphatation |
| WO1999048819A1 (fr) * | 1998-03-25 | 1999-09-30 | Henkel Kommanditgesellschaft Auf Aktien | Traitement des eaux usees lors de la phosphatation |
| EP1156137A1 (fr) * | 2000-05-15 | 2001-11-21 | Nippon Paint Co., Ltd. | Procédé de traitement de surfaces métalliques |
| EP1225250A2 (fr) * | 2001-01-17 | 2002-07-24 | Nippon Paint Co., Ltd. | Procédé de traitement de surfaces métalliques |
| US6464879B1 (en) | 1997-12-05 | 2002-10-15 | Henkel Kommanditgesellschaft Auf Aktien | Treatment of phosphatizing waste water |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2654440B1 (fr) * | 1989-11-16 | 1993-07-30 | Produits Ind Cie Fse | Procede de conversion chimique de substrats metalliques, bain mis en óoeuvre dans ce procede et concentre pour la preparation du bain. |
| DE4307591A1 (de) * | 1992-06-22 | 1994-09-15 | Eisenmann Kg Maschbau | Verfahren zur Nitritkonzentrationssenkung in Phosphatbad-Anlagen |
| US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
| DE19743933B4 (de) * | 1997-10-04 | 2009-11-19 | Volkswagen Ag | Verfahren zur Oberflächenbehandlung fester Körper, insbesondere Kraftfahrzeug-Karosserien |
| JP3479609B2 (ja) | 1999-03-02 | 2003-12-15 | 日本パーカライジング株式会社 | スラッジ発生のないリン酸亜鉛処理液およびリン酸亜鉛処理方法 |
| JP4720830B2 (ja) * | 1999-07-08 | 2011-07-13 | Ｊｆｅスチール株式会社 | 耐穴あき性およびプレス加工性に優れた亜鉛めっき鋼板の製造方法 |
| BR0111737A (pt) * | 2000-06-16 | 2003-07-01 | Henkel Kgaa | Operação de fosfatação, e, composição |
| EP1327697A4 (fr) * | 2000-10-19 | 2009-11-11 | Jfe Steel Corp | Tole d'acier plaque de zinc et procede de preparation de cette tole, et procede de fabrication d'un article forme par usinage a la presse |
| US8062435B2 (en) * | 2001-06-18 | 2011-11-22 | Henkel Kommanditgesellschaft Auf Aktien | Phosphating operation |
| JP4544970B2 (ja) * | 2004-11-09 | 2010-09-15 | Ｊｆｅスチール株式会社 | 酸洗廃液の処理方法および酸洗廃液用処理装置 |
| JP2007190322A (ja) * | 2006-01-23 | 2007-08-02 | Aisin Seiki Co Ltd | ベッド装置 |
| KR102070497B1 (ko) * | 2018-02-01 | 2020-01-28 | 한양대학교 에리카산학협력단 | 나노 결정체를 포함하는 금속 구조물, 및 그 제조 방법 |
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|---|---|---|---|---|
| DE1031083B (de) * | 1952-11-12 | 1958-05-29 | Metallgesellschaft Ag | Verfahren zur Regenerierung von nitrit- und nitrathaltigen Zinkphosphatloesungen |
| US3533859A (en) * | 1966-06-18 | 1970-10-13 | Hooker Chemical Corp | Coating process for ferrous metal surfaces |
| DE2538347A1 (de) * | 1974-08-30 | 1976-03-11 | Nippon Paint Co Ltd | Zinkphosphatloesungen zur ausbildung von zinkphosphatschichten auf metallen |
| GB1460420A (en) * | 1974-11-21 | 1977-01-06 | Pyrene Chemical Services Ltd | Process for phosphating metal surfaces |
| FR2401236A1 (fr) * | 1977-08-25 | 1979-03-23 | Parker Ste Continentale | Procede de phosphatation au zinc avec preneutralisation |
| DE3345498A1 (de) * | 1983-12-16 | 1985-06-27 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur herstellung von phosphatueberzuegen |
| EP0175606A1 (fr) * | 1984-08-16 | 1986-03-26 | Compagnie Francaise De Produits Industriels | Procédé de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentré et bain utilisés pour la mise en oeuvre de ce procédé |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1361489A (en) * | 1971-05-12 | 1974-07-24 | Carrier Drysys Ltd | Removing sludge formed in solutions used in metal pre-treatment processes |
| DE3636390A1 (de) * | 1986-10-25 | 1988-04-28 | Metallgesellschaft Ag | Verfahren zur erzeugung von phosphatueberzuegen auf metallen |
| DE3840668A1 (de) * | 1988-12-02 | 1990-06-07 | Metallgesellschaft Ag | Verfahren beim phosphatieren von metalloberflaechen |
-
1989
- 1989-08-22 DE DE3927613A patent/DE3927613A1/de not_active Withdrawn
-
1990
- 1990-08-07 EP EP90202148A patent/EP0414301B1/fr not_active Expired - Lifetime
- 1990-08-07 ES ES199090202148T patent/ES2038483T3/es not_active Expired - Lifetime
- 1990-08-07 DE DE9090202148T patent/DE59000923D1/de not_active Expired - Fee Related
- 1990-08-07 AT AT90202148T patent/ATE85987T1/de not_active IP Right Cessation
- 1990-08-20 DD DD90343537A patent/DD299661A5/de not_active IP Right Cessation
- 1990-08-21 BR BR909004128A patent/BR9004128A/pt not_active Application Discontinuation
- 1990-08-21 CA CA002023663A patent/CA2023663C/fr not_active Expired - Fee Related
- 1990-08-21 AU AU61185/90A patent/AU633611B2/en not_active Ceased
- 1990-08-21 PL PL90286573A patent/PL164655B1/pl unknown
- 1990-08-21 US US07/570,350 patent/US5203930A/en not_active Expired - Lifetime
- 1990-08-22 ZA ZA906672A patent/ZA906672B/xx unknown
- 1990-08-22 JP JP2220941A patent/JP3000108B2/ja not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1031083B (de) * | 1952-11-12 | 1958-05-29 | Metallgesellschaft Ag | Verfahren zur Regenerierung von nitrit- und nitrathaltigen Zinkphosphatloesungen |
| US3533859A (en) * | 1966-06-18 | 1970-10-13 | Hooker Chemical Corp | Coating process for ferrous metal surfaces |
| DE2538347A1 (de) * | 1974-08-30 | 1976-03-11 | Nippon Paint Co Ltd | Zinkphosphatloesungen zur ausbildung von zinkphosphatschichten auf metallen |
| GB1460420A (en) * | 1974-11-21 | 1977-01-06 | Pyrene Chemical Services Ltd | Process for phosphating metal surfaces |
| FR2401236A1 (fr) * | 1977-08-25 | 1979-03-23 | Parker Ste Continentale | Procede de phosphatation au zinc avec preneutralisation |
| DE3345498A1 (de) * | 1983-12-16 | 1985-06-27 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur herstellung von phosphatueberzuegen |
| EP0175606A1 (fr) * | 1984-08-16 | 1986-03-26 | Compagnie Francaise De Produits Industriels | Procédé de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentré et bain utilisés pour la mise en oeuvre de ce procédé |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2056748A1 (es) * | 1992-09-17 | 1994-10-01 | Rieger Franz Metallveredelung | Baño para el tratamiento previo de metales ligeros, su procedimiento y objetos producidos por los mismos. |
| US5415701A (en) * | 1993-03-02 | 1995-05-16 | Metallgesellschaft Aktiengesellschaft | Process for facilitating cold-working operations |
| EP0751239A1 (fr) * | 1995-06-30 | 1997-01-02 | Metallgesellschaft Aktiengesellschaft | Procédé de remontage de solution de phosphatation |
| US6464879B1 (en) | 1997-12-05 | 2002-10-15 | Henkel Kommanditgesellschaft Auf Aktien | Treatment of phosphatizing waste water |
| WO1999048819A1 (fr) * | 1998-03-25 | 1999-09-30 | Henkel Kommanditgesellschaft Auf Aktien | Traitement des eaux usees lors de la phosphatation |
| EP1156137A1 (fr) * | 2000-05-15 | 2001-11-21 | Nippon Paint Co., Ltd. | Procédé de traitement de surfaces métalliques |
| US6458219B2 (en) | 2000-05-15 | 2002-10-01 | Nippon Paint Co., Ltd. | Metal surface-treating method |
| EP1225250A2 (fr) * | 2001-01-17 | 2002-07-24 | Nippon Paint Co., Ltd. | Procédé de traitement de surfaces métalliques |
| EP1225250A3 (fr) * | 2001-01-17 | 2003-07-16 | Nippon Paint Co., Ltd. | Procédé de traitement de surfaces métalliques |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0387375A (ja) | 1991-04-12 |
| BR9004128A (pt) | 1991-09-03 |
| AU6118590A (en) | 1991-02-28 |
| DE3927613A1 (de) | 1991-02-28 |
| US5203930A (en) | 1993-04-20 |
| DD299661A5 (de) | 1992-04-30 |
| ES2038483T3 (es) | 1993-07-16 |
| ZA906672B (en) | 1992-04-29 |
| ATE85987T1 (de) | 1993-03-15 |
| CA2023663C (fr) | 1998-11-03 |
| JP3000108B2 (ja) | 2000-01-17 |
| DE59000923D1 (de) | 1993-04-01 |
| PL164655B1 (pl) | 1994-08-31 |
| PL286573A1 (en) | 1991-07-15 |
| CA2023663A1 (fr) | 1991-02-23 |
| AU633611B2 (en) | 1993-02-04 |
| EP0414301B1 (fr) | 1993-02-24 |
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