EP0817872A1 - Phosphating process with a metalliferous re-rinsing stage - Google Patents
Phosphating process with a metalliferous re-rinsing stageInfo
- Publication number
- EP0817872A1 EP0817872A1 EP96908083A EP96908083A EP0817872A1 EP 0817872 A1 EP0817872 A1 EP 0817872A1 EP 96908083 A EP96908083 A EP 96908083A EP 96908083 A EP96908083 A EP 96908083A EP 0817872 A1 EP0817872 A1 EP 0817872A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- sub
- solution
- ions
- range
- 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 56
- 230000008569 process Effects 0.000 title claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 27
- -1 m-nitrobenzenesulfonate ions Chemical class 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 239000008397 galvanized steel Substances 0.000 claims description 8
- 239000012487 rinsing solution Substances 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 235000021317 phosphate Nutrition 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 20
- 239000003973 paint Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 19
- 239000010452 phosphate Substances 0.000 description 19
- 239000010949 copper Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001844 chromium Chemical class 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
- 239000003086 colorant Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-M 2-nitrobenzoate Chemical compound [O-]C(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001499740 Plantago alpina Species 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RVGMCVRSUKTFHN-UHFFFAOYSA-G [F-].[Zr+4].[Al+3].[F-].[F-].[F-].[F-].[F-].[F-] Chemical class [F-].[Zr+4].[Al+3].[F-].[F-].[F-].[F-].[F-].[F-] RVGMCVRSUKTFHN-UHFFFAOYSA-G 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 230000002452 interceptive effect Effects 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
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 150000003754 zirconium Chemical class 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the invention relates to processes for phosphating metal surfaces with aqueous, acidic zinc-containing phosphating solutions.
- phosphating is followed by rinsing with a solution which contains lithium, copper and / or silver ions.
- the process is suitable as a pretreatment of the metal surfaces for a subsequent painting, in particular an electrocoating.
- the method is applicable for the treatment of surfaces made of steel, galvanized or galvanized alloy steel, aluminum, aluminized or alloy-aluminized steel.
- the phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers on the metal surface, which in themselves improve the corrosion resistance and, in conjunction with paints and other organic coatings, contribute to a substantial increase in paint adhesion and resistance to infiltration when exposed to corrosion.
- Such phosphating processes have long been known, and the low-zinc phosphating processes, in which the phosphating solutions have comparatively low zinc ion contents of, for example, 0.5 to 2 g / l, are particularly suitable for pretreatment prior to painting .
- An essential parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range> 8 and can assume values of up to 30.
- DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
- the phosphating baths described here contain, in addition to 0.2 to 10 g / 1 nitrate ions, further oxidizing agents which act as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.
- EP-A-60 716 discloses low-zinc phosphating baths which contain zinc and manganese as essential cations and which can contain nickel as an optional component.
- the necessary accelerator is preferably selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- EP-A-228 151 also describes phosphating baths which contain zinc and manganese as essential cations.
- the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, nitrobenzoate or p-nitrophenol.
- German patent application P 4341 041.3 describes a process for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc, manganese and phosphate ions and, as an accelerator, m-nitrobenzosulfonic acid or its water-soluble salts, the metal surfaces being contacted with a phosphating solution brings, which is free of nickel, cobalt, copper, nitrite and oxo anions of halogens and the
- the process of applying the phosphating solution to the metal surfaces and / or other process parameters the phosphate layer on the metal surfaces is not completely closed. Rather, there remain more or less large "pores", the area of which is in the order of 0.5 to 2% of the phosphated area and which must be closed in the course of a so-called "post-passivation” in order not to read any point of attack from corrosive influences on the metal surfaces ⁇ sen. Post-passivation further improves the adhesion of a subsequently applied lacquer.
- a major disadvantage of using solutions containing chromium salts is that such solutions are highly toxic.
- an undesired formation of bubbles is increasingly observed in the subsequent application of paints or other coating materials.
- a rinse solution which contains Al, Zr and fluoride ions, whereby the solution can be regarded as a mixture of complex fluorides or as a solution of aluminum hexafluorozirconate.
- the total amount of these 3 ions is in the range from 0.1 to 2.0 g / l.
- DE-A-21 00 497 relates to a process for the electrophoretic application of colors to iron-containing surfaces, the task being to apply white or other light colors to the iron-containing surfaces without discoloration.
- This object is achieved in that the surfaces, which may have been phosphated beforehand, are rinsed with copper-containing solutions. Copper concentrations between 0.1 and 10 g / l are proposed for this rinse solution.
- DE-A-34 00 339 also describes a copper-containing rinse solution for phosphated metal surfaces, with copper contents between 0.01 and 10 g / l being used. No attention was paid to the fact that these rinse solutions in connection with different phosphating processes lead to different results.
- Nickel-free phosphating processes in connection with a chrome-free rinsing currently do not yet reliably meet the requirements for paint adhesion and corrosion protection on all body materials used in the automotive industry. There is therefore still a need for rinse solutions which, in conjunction with a nickel- and nitrite-free phosphating and a subsequent cathodic electrocoating, reliably meet the requirements for corrosion protection and paint adhesion for different substrate materials.
- the object of the invention is to provide such a method combination of a phosphating process which is optimized with regard to environmental protection and occupational safety and a chromium-free rinse which is particularly suitable for this purpose prior to a cathodic electrocoating.
- This object is achieved by a process for the phosphating of surfaces made of steel, galvanized steel and / or aluminum and / or of alloys which consist of at least 50% by weight of iron, zinc or aluminum, phosphating with a zinc-containing acid phosphating solution and then rinsed with a rinse solution, characterized in that
- phosphate ions containing 5 to 40 g / 1 phosphate ions and at least one of the following accelerators: 0.2 to 2 g / 1 m-nitrobenzenesulfonate ions, 0.1 to 10 g / 1 hydroxylamine in free or bound
- aqueous solution with a pH in the range from 3 to 7, which contains 0.001 to 10 g / 1 of one or more of the following cations: lithium ions, copper ions and / or silver ions.
- the phosphating solution used in sub-step a) of the process sequence according to the invention preferably contains one or more further metal ions, the positive effect of which on the corrosion protection of zinc phosphate layers is known in the prior art.
- the phosphating solution can contain one or more of the following cations:
- the presence of manganese and / or lithium is particularly preferred.
- the possibility of the presence of divalent iron depends on the accelerator system described below.
- the presence of iron (II) in the concentration range mentioned requires an accelerator which does not have an oxidizing effect on these ions.
- hydroxylamine should be mentioned as an example.
- the phosphating baths are free from nickel and preferably also from cobalt. This means that these elements or ions are not deliberately added to the phosphating baths. In practice, however, it cannot be ruled out that such constituents may be traced into the phosphating baths via the material to be treated. In particular, it cannot be ruled out that when phosphating steel coated with zinc-nickel alloys, nickel ions are introduced into the phosphating solution. However, the expectation is placed on the phosphating baths that under technical conditions the nickel concentration in the baths is below 0.01 g / 1, in particular below 0.0001 g / 1.
- the phosphating baths preferably also contain no oxo anions from halogens.
- phosphating baths which are said to be suitable for different substrates, it has become common to use free and / or complex-bound fluoride in amounts of up to 2.5 g / 1 total fluoride, of which up to 800 mg / 1 free fluoride.
- the presence of such fluoride is also advantageous for the phosphating baths in the context of the invention.
- the aluminum content of the bath should not exceed 3 mg / 1.
- higher Al contents are tolerated as a result of the complex formation, provided the concentration of the non-complexed AI does not exceed 3 mg / 1.
- the use of fluoride-containing baths is therefore advantageous if the surfaces to be phosphated are at least partially made of aluminum or contain aluminum. In these cases it is favorable not to use fluoride bound to the complex, but only free fluoride, preferably in concentrations in the range from 0.5 to 1.0 g / l.
- the phosphating baths For the phosphating of zinc surfaces, it is not absolutely necessary that the phosphating baths contain so-called accelerators.
- the phosphating solution contain one or more accelerators.
- accelerators are known in the prior art as components of zinc phosphating baths. This is understood to mean substances which chemically bind the hydrogen produced by the acid attack on the metal surface by reducing them themselves. Oxidizing wir ⁇ kende accelerators also have the effect by the released iron Beizan ⁇ handle on steel surfaces (II) ions to trihydric stage to oxidize n 'so that it can turn (III) phosphate as iron.
- the accelerators which can be used in the phosphating bath of the process sequence according to the invention were listed further above.
- nitrate ions in amounts of up to 10 g / l can be present as co-accelerators, which is particularly the case with phosphating of steel surfaces can have a favorable effect.
- the phosphate solution contains as little nitrate as possible.
- Nitrate concentrations of 0.5 g / 1 should preferably not be exceeded, since there is a risk of so-called "speck formation" at higher nitrate concentrations. This means white, crater-like defects in the phosphate layer.
- Hydrogen peroxide is preferred for reasons of environmental friendliness, and hydroxylamine is particularly preferred as an accelerator for technical reasons because of the simplified formulation options for replenishing solutions. However, it is not advisable to use these two accelerators together, since hydroxylamine is decomposed by hydrogen peroxide. If hydrogen peroxide in free or bound form is used as an accelerator, concentrations of 0.005 to 0.02 g / l of hydrogen peroxide are particularly preferred.
- the hydrogen peroxide can be added as such to the phosphating solution. However, it is also possible to use hydrogen peroxide in bound form in the form of compounds which give hydrogen peroxide in the phosphating bath by hydrolysis reactions.
- Examples of such compounds are persalts, such as perborates, percarbonates, peroxosulfates or peroxodisulfates.
- Ionic peroxides such as, for example, alkali metal peroxides, are suitable as further sources of hydrogen peroxide.
- Hydroxylamine can be used as a free base, as a hydroxyl complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely be present as a hydroxylammonium cation due to the acidic nature of these solutions.
- the sulfates and the phosphates are particularly suitable. In the case of the phosphates are due to the preferred solubility preferred the acid salts.
- Hydroxylamine or its compounds are added to the phosphating bath in amounts such that the calculated concentration of the free hydroxylamine is between 0.1 and 10 g / 1, preferably between 0.2 and 6 g / 1 and in particular between 0.3 and 2 g / 1.
- the use of hydroxylamine as an accelerator on iron surfaces leads to particularly favorable spherical and / or columnar phosphate crystals.
- the post-rinsing to be carried out in sub-step b) is particularly suitable as post-passivation of such phosphate layers.
- the preferred concentrations of lithium ions are in the range from 0.4 to 1 g / l.
- Phosphating baths containing lithium as the only monovalent cation are particularly preferred.
- ammonia is preferably used, so that the lithium-containing phosphating baths can additionally contain ammonium ions in the range from about 0.5 to about 2 g / l.
- the use of basic sodium compounds such as sodium hydroxide solution is less preferred in this case, since the presence of sodium ions in the lithium-containing phosphating baths deteriorates the anti-corrosion properties of the layers obtained.
- the free acid is preferably adjusted by adding basic sodium compounds such as sodium carbonate or sodium hydroxide.
- phosphating baths which, apart from zinc and possibly lithium, contain manganese (II).
- the manganese content of the phosphating bath should are between 0.2 and 4 g / 1, since the lower influence of the manganese content no longer has a positive influence on the corrosion behavior of the phosphate layers, and no further positive effect occurs at higher manganese contents. Contents between 0.3 and 2 g / 1 and in particular between 0.5 and 1.5 g / 1 are preferred.
- the zinc content of the phosphating bath is preferably set to values between 0.45 and 2 g / l.
- the current zinc content of the working bath rises to up to 3 g / 1.
- the form in which the zinc and manganese ions are introduced into the phosphating baths is in principle irrelevant. It is particularly advisable to use the oxides and / or the carbonates as the zinc and / or manganese source.
- iron (II) ions When the phosphating process is used on steel surfaces, iron dissolves in the form of iron (II) ions. If the phosphating baths do not contain any substances which have a strongly oxidizing effect on iron (II), the divalent iron changes to the trivalent state primarily as a result of air oxidation, so that it can precipitate out as iron (III) phosphate. For this reason, iron (II) levels can be built up in the phosphating baths, which are significantly higher than the levels that contain baths containing oxidizing agents. This is the case, for example, in the phosphating baths containing hydroxylamine.
- iron (II) concentrations of up to 50 ppm are normal, wherein values even up to 500 ppm may occur in the short term in the production process'. Such iron (II) concentrations are not detrimental to the phosphating process according to the invention.
- the weight ratio of phosphate ions to zinc ions in the phosphate baths can vary within wide limits, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
- Phosphating can be carried out by spraying, dipping or spray-dipping.
- the exposure times are in the usual range between about 1 and about 4 minutes.
- the temperature of the phosphating solution is in the range between approximately 40 and approximately 60 ° C.
- An intermediate rinsing with water can take place between the phosphating according to sub-step a) and the final rinsing according to sub-step b). However, this is not necessary and it can even be advantageous to dispense with this intermediate rinsing, since then one Reaction of the rinse solution with the phosphating solution still adhering to the phosphated surface can take place, which has a favorable effect on the corrosion protection.
- the rinse solution used in sub-step b) preferably has a pH in the range from 3.4 to 6 and a temperature in the range from 20 to 50 ° C.
- the concentrations of the cations in the aqueous solution used in sub-step b) are preferably in the following ranges: lithium (I) 0.02 to 2, in particular 0.2 to 1.5 g / 1, copper (II) 0.002 to 1 g / 1, in particular 0.01 to 0.1 g / 1 and silver (I) 0.002 to 1 g / 1, in particular 0.01 to 0.1 g / 1.
- the metal ions mentioned can be present individually or in a mixture with one another. Post-rinse solutions which contain copper (II) are particularly preferred.
- metal ions mentioned are introduced into the rinse solution is in principle irrelevant, as long as it is ensured that the metal compounds are soluble in the concentration ranges of the metal ions mentioned.
- metal compounds with anions which are known to promote the tendency to corrode, such as chloride should be avoided. It is particularly preferred to use the metal ions as nitrates or as carboxylates, in particular as acetates. Phosphates are also suitable, provided they are soluble under the chosen concentration and pH conditions. The same applies to sulfates.
- the metal ions of lithium, copper and / or silver are used in the rinsing solutions together with hexafluorotitanate and / or, particularly preferably, hexafluorozirconate ions. It is preferred that the concentrations of the anions mentioned are in the range from 100 to 500 ppm.
- the sources of the hexafluoro anions mentioned come from them Acids or their salts which are water-soluble under the concentration and pH conditions mentioned, in particular their alkali metal and / or ammonium salts. It is particularly favorable to use the hexafluoro anions at least partially in the form of their acids and to dissolve basic compounds of lithium, copper and / or silver in the acidic solutions. For this purpose, for example, the hydroxides, oxides or carbonates of the metals mentioned come into consideration. This procedure avoids using the metals together with any interfering anions. If necessary, the pH can be adjusted with ammonia.
- the rinsing solutions can furthermore contain the ions of lithium, copper and / or silver together with ions of cerium (III) and / or cerium (IV), the total concentration of the cerium ions being in the range from 0.01 to 1 g / l.
- the rinse solution can also contain aluminum (III) compounds, the concentration of aluminum being in the range from 0.01 to 1 g / l.
- Suitable aluminum compounds are, in particular, polyaluminium compounds such as, for example, polymeric aluminum hydroxychloride or polymeric aluminum hydroxysulfate (WO 92/15724), or else complex aluminum-zirconium fluorides, as are known, for example, from EP-B-410497.
- the metal surfaces phosphated in sub-step a) can be brought into contact with the rinse solution by spraying, dipping or spray-dipping in sub-step b), the exposure time being in the range from 0.5 to 10 minutes and preferably being about 40 to about 120 seconds. Because of the simpler system technology, it is preferable to use the rinse solution in the partial step b) sprayed onto the metal surface phosphated in sub-step a).
- the metal surfaces phosphated in sub-step a) and rinsed in sub-step b) can be dried and coated without further rinsing, for example with a powder coating.
- the process is designed in particular as a pretreatment prior to cathodic electrocoating.
- the metal surfaces pretreated according to the invention can be dried before being introduced into the electrocoat. In the interest of a faster production cycle, however, such drying is preferably avoided.
- the free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Analogously, the total acid number indicates the consumption in ml up to a pH of 8.5.
- test sheets made of steel (St 1405) and electrolytically galvanized steel were phosphated in the general process described above with a phosphating solution with the following bath parameters using the immersion method:
- sample sheets were immersed for one minute at a temperature of 40 ° C. in the following rinsing solutions in deionized water (Table 4). The sheets were then rinsed with deionized water, dried and painted.
- the cathodic electrodeposition paint FT 85-7042 gray from BASF was used for painting.
- the corrosion protection test was carried out according to the VDA alternating climate test 621-415. As a result. Table 5 shows the paint infiltration at the Ritz.
- a paint adhesion test was carried out according to the VW stone impact test, which was assessed according to the K value. Higher K values mean poorer, lower K values better paint adhesion. The results are also shown in Table 5.
- Example 1.1 6 An outdoor weathering test according to VDE 621-414 was also carried out. For this purpose, a complete paint structure (VW white) was applied to the KTL-coated test panels. After 6 months of exposure, the following paint infiltration (half the scratch width) was found (Table 6):
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- Chemical Treatment Of Metals (AREA)
- Chemically Coating (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19511573A DE19511573A1 (en) | 1995-03-29 | 1995-03-29 | Process for phosphating with metal-containing rinsing |
DE19511573 | 1995-03-29 | ||
PCT/EP1996/001196 WO1996030559A1 (en) | 1995-03-29 | 1996-03-20 | Phosphating process with a metalliferous re-rinsing stage |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0817872A1 true EP0817872A1 (en) | 1998-01-14 |
EP0817872B1 EP0817872B1 (en) | 2000-01-19 |
Family
ID=7758087
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96908083A Expired - Lifetime EP0817872B1 (en) | 1995-03-29 | 1996-03-20 | Phosphating process with a metalliferous re-rinsing stage |
Country Status (19)
Country | Link |
---|---|
US (2) | US6090224A (en) |
EP (1) | EP0817872B1 (en) |
JP (1) | JP3883571B2 (en) |
KR (1) | KR100362549B1 (en) |
CN (1) | CN1079845C (en) |
AT (1) | ATE189010T1 (en) |
AU (1) | AU697424B2 (en) |
BR (1) | BR9607767A (en) |
CA (1) | CA2216925A1 (en) |
CZ (1) | CZ287867B6 (en) |
DE (2) | DE19511573A1 (en) |
ES (1) | ES2143186T3 (en) |
HU (1) | HUP9802380A3 (en) |
PL (1) | PL179316B1 (en) |
PT (1) | PT817872E (en) |
SK (1) | SK128997A3 (en) |
TR (1) | TR199701061T1 (en) |
WO (1) | WO1996030559A1 (en) |
ZA (1) | ZA962504B (en) |
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US8673091B2 (en) | 2007-08-03 | 2014-03-18 | Ppg Industries Ohio, Inc | Pretreatment compositions and methods for coating a metal substrate |
US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
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DE19933189A1 (en) * | 1999-07-15 | 2001-01-18 | Henkel Kgaa | Process for the protection against corrosion or aftertreatment of metal surfaces |
DE10056628B4 (en) * | 2000-11-15 | 2004-07-22 | Henkel Kgaa | Fractional regeneration of a weakly acidic ion exchanger loaded with nickel ions |
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-
1995
- 1995-03-29 DE DE19511573A patent/DE19511573A1/en not_active Withdrawn
-
1996
- 1996-03-20 AT AT96908083T patent/ATE189010T1/en not_active IP Right Cessation
- 1996-03-20 PT PT96908083T patent/PT817872E/en unknown
- 1996-03-20 CN CN96192795A patent/CN1079845C/en not_active Expired - Fee Related
- 1996-03-20 AU AU51464/96A patent/AU697424B2/en not_active Ceased
- 1996-03-20 US US08/930,565 patent/US6090224A/en not_active Expired - Fee Related
- 1996-03-20 KR KR1019970706149A patent/KR100362549B1/en not_active IP Right Cessation
- 1996-03-20 BR BR9607767A patent/BR9607767A/en not_active Application Discontinuation
- 1996-03-20 CA CA002216925A patent/CA2216925A1/en not_active Abandoned
- 1996-03-20 CZ CZ19973061A patent/CZ287867B6/en not_active IP Right Cessation
- 1996-03-20 HU HU9802380A patent/HUP9802380A3/en unknown
- 1996-03-20 EP EP96908083A patent/EP0817872B1/en not_active Expired - Lifetime
- 1996-03-20 TR TR97/01061T patent/TR199701061T1/en unknown
- 1996-03-20 PL PL96321960A patent/PL179316B1/en not_active IP Right Cessation
- 1996-03-20 JP JP52888296A patent/JP3883571B2/en not_active Expired - Fee Related
- 1996-03-20 ES ES96908083T patent/ES2143186T3/en not_active Expired - Lifetime
- 1996-03-20 WO PCT/EP1996/001196 patent/WO1996030559A1/en active IP Right Grant
- 1996-03-20 DE DE59604232T patent/DE59604232D1/en not_active Expired - Fee Related
- 1996-03-20 SK SK1289-97A patent/SK128997A3/en unknown
- 1996-03-28 ZA ZA962504A patent/ZA962504B/en unknown
-
2000
- 2000-07-17 US US09/617,886 patent/US6395105B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO9630559A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8673091B2 (en) | 2007-08-03 | 2014-03-18 | Ppg Industries Ohio, Inc | Pretreatment compositions and methods for coating a metal substrate |
US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
Also Published As
Publication number | Publication date |
---|---|
CA2216925A1 (en) | 1996-10-03 |
ES2143186T3 (en) | 2000-05-01 |
CN1079845C (en) | 2002-02-27 |
SK128997A3 (en) | 1998-12-02 |
PL321960A1 (en) | 1998-01-05 |
CN1179183A (en) | 1998-04-15 |
WO1996030559A1 (en) | 1996-10-03 |
ZA962504B (en) | 1996-09-30 |
DE19511573A1 (en) | 1996-10-02 |
CZ306197A3 (en) | 1998-03-18 |
AU697424B2 (en) | 1998-10-08 |
PT817872E (en) | 2000-07-31 |
DE59604232D1 (en) | 2000-02-24 |
MX9707328A (en) | 1998-07-31 |
KR100362549B1 (en) | 2003-02-11 |
BR9607767A (en) | 1999-01-19 |
ATE189010T1 (en) | 2000-02-15 |
JP3883571B2 (en) | 2007-02-21 |
PL179316B1 (en) | 2000-08-31 |
US6090224A (en) | 2000-07-18 |
US6395105B1 (en) | 2002-05-28 |
HUP9802380A2 (en) | 1999-02-01 |
CZ287867B6 (en) | 2001-02-14 |
KR19980702742A (en) | 1998-08-05 |
EP0817872B1 (en) | 2000-01-19 |
TR199701061T1 (en) | 1998-01-21 |
JPH11502569A (en) | 1999-03-02 |
AU5146496A (en) | 1996-10-16 |
HUP9802380A3 (en) | 1999-03-29 |
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