EP0817872B1 - Phosphating process with a metalliferous re-rinsing stage - Google Patents
Phosphating process with a metalliferous re-rinsing stage Download PDFInfo
- Publication number
- EP0817872B1 EP0817872B1 EP96908083A EP96908083A EP0817872B1 EP 0817872 B1 EP0817872 B1 EP 0817872B1 EP 96908083 A EP96908083 A EP 96908083A EP 96908083 A EP96908083 A EP 96908083A EP 0817872 B1 EP0817872 B1 EP 0817872B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- ions
- solution used
- rinse solution
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 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 21
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- -1 m-nitrobenzene sulfonate ions Chemical class 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 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
- 239000004411 aluminium Substances 0.000 claims 2
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000003973 paint Substances 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 20
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 235000021317 phosphate Nutrition 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 239000010452 phosphate Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 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
- 229910052748 manganese Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000010422 painting Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 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
- 230000009189 diving Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000002349 favourable effect Effects 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
- 238000004519 manufacturing process Methods 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
- 238000005554 pickling Methods 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten 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
- 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
- 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
- 230000015572 biosynthetic process 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
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000007921 spray Substances 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
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229910004844 Na2B4O7.10H2O Inorganic materials 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
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-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
- 230000003213 activating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 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
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 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
- 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
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 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
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000011010 flushing procedure 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
- 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
- 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
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DYLSCLYVTVPEFF-UHFFFAOYSA-N lithium manganese(2+) Chemical compound [Li+].[Mn+2] DYLSCLYVTVPEFF-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer 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
- 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 230000035882 stress Effects 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
- 238000005303 weighing Methods 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
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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 methods for phosphating metal surfaces with aqueous, acidic zinc-containing phosphating solutions.
- a rinse with a solution containing lithium, Contains copper and / or silver ions is suitable as a pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting.
- the procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized steel, aluminum, aluminized or alloy aluminized Steel.
- the phosphating of metals pursues the goal on the metal surface to produce firmly adherent metal phosphate layers already improve the corrosion resistance and in Connection with paints and other organic coatings too a significant increase in paint adhesion and resistance to Infiltration under corrosion stress contribute.
- Such phosphating processes have been known for a long time.
- the low-zinc phosphating processes are particularly suitable, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l.
- the weight ratio of phosphate ions to zinc ions which is usually is in the range> 8 and can take values up to 30.
- phosphate layers have disadvantages in that Nickel and nickel compounds from the point of view of environmental protection and occupational hygiene can be classified as critical.
- Low zinc phosphating processes are increasingly being described the too qualitative without using nickel similar high-quality phosphate layers as the nickel-containing processes to lead.
- nitrite and nitrate Concerns have been raised about possible formation of nitrous gases.
- the phosphating of galvanized steel with nickel-free phosphating baths Corrosion protection and insufficient paint adhesion results if the phosphating baths contain larger quantities (> 0.5 g / l) nitrate.
- DE-A-39 20 296 describes a phosphating process that dispenses with nickel and besides zinc and manganese ions Magnesium ions used.
- the phosphating baths described here contain, in addition to 0.2 to 10 g / l nitrate ions, other accelerators acting oxidizing agents selected from nitrite, chlorate or an organic oxidizing agent.
- EP-A-60 716 discloses low-zinc phosphating baths, which are essential cations zinc and Contain manganese and which contain nickel as an optional component can.
- the necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- Phosphating baths are also described in EP-A-228 151, which contain zinc and manganese as essential cations.
- the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzoate or p-nitrophenol.
- the process of applying the phosphating solution on the metal surfaces and / or other process parameters the phosphate layer on the metal surfaces is not complete closed. Rather, there are more or less large ones "Pores” whose area is on the order of 0.5 to 2% of phosphated surface is located in the course of a so-called "Post-passivation” must be closed to be corrosive To leave influences on the metal surfaces no point of attack. Post-passivation further improves the liability of one then applied paint.
- a rinse solution is known from EP-B-410 497 which contains Al, Zr and contains fluoride ions, the solution being a complex mixture Fluoride or as a solution of aluminum hexafluorozirconate can be understood.
- 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 method for electrophoretic Applying paints to ferrous surfaces, doing the job should be solved, white on the ferrous surfaces or apply other bright colors without discoloration.
- This The object is achieved in that the surfaces that have previously been phosphated can be rinsed with copper-containing solutions. Copper concentrations are between for this rinse solution 0.1 and 10 g / l suggested.
- DE-A-34 00 339 describes also a copper-containing rinse solution for phosphated metal surfaces, with copper contents between 0.01 and 10 g / l is worked. It was not observed that this Rinse solutions in connection with different phosphating processes lead to different results.
- Nickel-free phosphating process in connection with a Chrome-free rinsing currently does not reach all body materials used reliably in the automotive industry the requirements for paint adhesion and corrosion protection. Therefore there is still a need for rinse aid solutions that are related with a nickel- and nitrite-free phosphating and one subsequent cathodic electrocoating the requirements corrosion protection and paint adhesion for different substrate materials reliably meet.
- the invention turns the Task, such a combination of methods from a Environmental and occupational safety optimized phosphating processes and a particularly suitable chrome-free rinse before to provide cathodic electrocoating.
- iron (II) in the concentration range mentioned requires an accelerator that does not react to these ions has an oxidizing effect. Hydroxylamine in particular is an example of this to call.
- the phosphating baths are free of nickel and preferably also of Cobalt. This means that these elements or ions the phosphating baths not be added deliberately. However, it is in the Practice does not rule out that such constituents go beyond that Treating material entered in traces in the phosphating baths become. In particular, it cannot be ruled out that at Phosphating of steel coated with zinc-nickel alloys Nickel ions are introduced into the phosphating solution. However is the expectation of the phosphating baths that under technical conditions under the nickel concentration in the baths 0.01 g / l, in particular below 0.0001 g / l. Preferably included the phosphating baths also do not contain oxo anions from halogens.
- accelerators are in the state of the art Technology known as components of zinc phosphating baths. Below are understood substances that are caused by the pickling attack the hydrogen on the metal surface bind chemically so that they themselves are reduced. Oxidizing Accelerators continue to have the effect of pickling Iron (II) ions released on steel surfaces become trivalent Oxidize stage, so that it as iron (III) phosphate can fail.
- the process sequence according to the invention in the phosphating bath usable accelerators were listed above.
- nitrate ions can be used as co-accelerators in quantities of up to 10 g / l be present, which is particularly the case with phosphating of steel surfaces can have a favorable effect.
- the phosphating solution contains as little nitrate as possible.
- Nitrate concentrations of 0.5 g / l should preferably not be exceeded, since at higher nitrate concentrations the risk of a so-called "Speck formation" exists. These are white, crater-like defects in the phosphate layer meant.
- hydroxylamine is an accelerator particularly preferred. Sharing these two accelerators however, is not advisable since hydroxylamine is made of hydrogen peroxide is decomposed. If you put hydrogen peroxide in free or bound form as an accelerator, so are concentrations from 0.005 to 0.02 g / l of hydrogen peroxide are particularly preferred. Here the hydrogen peroxide of the phosphating solution as such be added. However, it is also possible to add hydrogen peroxide use bound form in the form of compounds in the phosphating bath deliver hydrogen peroxide by hydrolysis reactions.
- persalts such as perborates, Percarbonates, peroxosulfates or peroxodisulfates.
- persalts such as perborates, Percarbonates, peroxosulfates or peroxodisulfates.
- ionic peroxides such as Alkali metal peroxides into consideration.
- Hydroxylamine can be used as a free base, as a hydroxylamine complex or in Form of hydroxylammonium salts can be used.
- the hydroxylammonium salt are the sulfates and the phosphates 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 such quantities that the calculated concentration of free hydroxylamine between 0.1 and 10 g / l, preferably between 0.2 and 6 g / l and in particular is between 0.3 and 2 g / l.
- hydroxylamine as an accelerator on iron surfaces to particularly favorable spherical and / or leads to columnar phosphate crystals.
- the one to be carried out in sub-step b) Rinsing is a post-passivation of such phosphate layers particularly suitable.
- lithium-containing phosphating baths the preferred ones Concentrations of lithium ions in the range from 0.4 to 1 g / l. Phosphating baths, lithium, are particularly preferred as the only monovalent cation. Depending on what you want Ratio of phosphate ions to divalent cations and However, lithium ions may be required to adjust the desired free acid the phosphating baths further basic Add substances. In this case, ammonia is preferably used a, so that the lithium-containing phosphating baths in addition Contain ammonium ions in the range from about 0.5 to about 2 g / l can.
- the use of basic sodium compounds such as in this case sodium hydroxide solution is less preferred because the presence of sodium ions in the lithium-containing phosphating baths the corrosion protection properties of the layers obtained worsened.
- the free acid preferably by adding basic sodium compounds such as sodium carbonate or sodium hydroxide.
- phosphating baths obtained which, in addition to zinc and possibly lithium manganese (II) contain The manganese content of the phosphating bath should are between 0.2 and 4 g / l, since the lower the manganese content positive influence on the corrosion behavior of the phosphate layers is no longer available and with higher manganese contents no more positive effect occurs. Contents between 0.3 and 2 g / l and especially between 0.5 and 1.5 g / l are preferred.
- the zinc content of the phosphating bath is preferably set to values between 0.45 and 2 g / l.
- the current The zinc content of the working bath increases up to 3 g / l.
- the zinc and manganese ions in the phosphating baths is basically irrelevant. It offers itself in particular, as the zinc and / or manganese source, the oxides and / or to use the carbonates.
- iron (II) ions When using the phosphating process on steel surfaces iron dissolves in the form of iron (II) ions. If the phosphating baths do not contain any substances that are have a strong oxidizing effect, the divalent iron mainly goes into Consequence of air oxidation into the trivalent state so that it can precipitate as iron (III) phosphate. Therefore, in the Phosphate baths build up iron (II) contents that are significantly higher than the Laid down containing baths containing oxidizing agents. This is, for example, in the hydroxylamine-containing phosphating baths the case. In this sense, iron (II) concentrations are up to 50 ppm normal, with values up to in the short term in the production process 500 ppm can occur. For the phosphating process according to the invention such iron (II) concentrations are not harmful.
- the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided that it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
- the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3- . Accordingly, the known fact that the pH values of the phosphating baths, which are usually in the range from about 3 to about 3.4, is only neglected in the form of the triple negative at the pH values of the phosphating baths charged anions. At these pH values, it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogenphosphate anion, together with smaller amounts of non-associated phosphoric acid and double negatively charged hydrogenphosphate anions.
- the phosphating can be done in spraying, diving or spray diving respectively.
- 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 about 40 and about 60 ° C.
- front phosphating are the usual steps in the prior art cleaning and activation, preferably with activation baths containing titanium phosphate.
- the rinse solution used in sub-step b) preferably has a pH in the range of 3.4 to 6 and a temperature in the range from 20 to 50 ° C.
- the concentrations of the cations in the The aqueous solution used in sub-step b) is preferably in the following areas: lithium (I) 0.02 to 2, in particular 0.2 to 1.5 g / l, copper (II) 0.002 to 1 g / l, in particular 0.01 to 0.1 g / l and silver (I) 0.002 to 1 g / l, in particular 0.01 to 0.1 g / l.
- the metal ions mentioned can be used individually or as a mixture with one another available.
- Rinse solutions containing copper (II) are particularly preferred. contain.
- metal ions mentioned in the rinse solution are introduced is irrelevant in principle, as long as guaranteed is that the metal compounds in the concentration ranges mentioned the metal ions are soluble.
- metal connections should with anions that prevent the tendency to corrode known to promote, such as chloride.
- the metal ions are nitrates or as Carboxylates, especially as acetates.
- phosphates also suitable, provided that they are below the selected concentration and pH conditions are soluble. The same applies to sulfates.
- the metal ions of Lithium, copper and / or silver together in the rinse solutions with hexafluorotitanate and / or, particularly preferably, Hexafluoro zirconia It is preferred that the concentrations of the anions mentioned in the range from 100 to 500 ppm lie.
- the sources of the hexafluoro anions mentioned come from them Acids or their acids under the concentration and pH conditions mentioned water-soluble salts, especially their alkali metal and / or ammonium salts. It is particularly cheap Use hexafluoro anions at least partially in the form of their acids and in the acidic solutions basic compounds of lithium, Dissolve copper and / or silver. For example, come here the hydroxides, oxides or carbonates of the metals mentioned in Consideration. By doing this, you avoid the metals together with any interfering anions.
- the pH can if necessary, adjust with ammonia.
- the rinse solutions can also contain the ions of lithium and copper and / or silver together with ions of cerium (III) and / or cerium (IV) included, with the total concentration of cerium ions in the range from 0.01 to 1 g / l.
- the rinse solution can Copper and / or silver also contain aluminum (III) compounds, the concentration of aluminum in the range of 0.01 to 1 g / l lies.
- the aluminum compounds in particular come on the one hand Polyaluminium compounds such as polymer Aluminum hydroxychloride or polymeric aluminum hydroxysulfate in Consideration (WO 92/15724), or else complex aluminum-zirconium fluorides, as they are known for example from EP-B-410 497.
- the metal surfaces phosphated in sub-step a) can Sub-step b) with the rinse solution by spraying, dipping or Spray diving can be brought into contact with the exposure time should be in the range of 0.5 to 10 minutes and preferably about Is 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 phosphated metal surface in sub-step a).
- Rinsing off the treatment solution after the end of the exposure period and before the subsequent painting is basically not required.
- phosphated metal surfaces rinsed in sub-step b) can be dried and varnished without further rinsing, for example with a powder coating.
- the procedure is however, especially as a pretreatment before a cathodic one Electro dip coating designed.
- the rinse solution from the metal surfaces rinse off preferably with low salt or desalinated Water.
- the metal surfaces pretreated according to the invention are dried. In the interest of a faster production cycle, however, is omitted preferably such drying.
- 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.
- the paint infiltration at the Ritz is entered in Table 5.
- 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.
- Corrosion protection values and paint adhesion parameters Rinse solution Paint infiltration (mm) K value steel galvanized steel steel galvanized steel completely desalinated water 1.8 4 - 5 7-8 9 Compare 4 1.3 3-4 6 8th Ex. P 1.2 6 Ex. Q 1.0 2.5 - 3.5 6 8th Ex. R 1.2 2.1 - 3 6 8th Ex 1.1 6
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Abstract
Description
Die Erfindung betrifft Verfahren zur Phosphatierung von Metalloberflächen mit wäßrigen, sauren zinkhaltigen Phosphatierlösungen. Zur Verbesserung des Korrosionsschutzes und der Lackhaftung folgt auf die Phosphatierung eine Nachspülung mit einer Lösung, die Lithium-, Kupfer- und/oder Silberionen enthält. Das Verfahren eignet sich als Vorbehandlung der Metalloberflächen für eine anschließende Lackierung, insbesondere eine Elektrotauchlackierung. Das Verfahren ist anwendbar zur Behandlung von Oberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium, aluminiertem oder legierungsaluminiertem Stahl.The invention relates to methods for phosphating metal surfaces with aqueous, acidic zinc-containing phosphating solutions. To improve corrosion protection and paint adhesion follows on the phosphating, a rinse with a solution containing lithium, Contains copper and / or silver ions. The procedure is suitable as a pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting. The procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized steel, aluminum, aluminized or alloy aluminized Steel.
Die Phosphatierung von Metallen verfolgt das Ziel, auf der Metalloberfläche festverwachsene Metallphosphatschichten zu erzeugen, die für sich bereits die Korrosionsbeständigkeit verbessern und in Verbindung mit Lacken und anderen organischen Beschichtungen zu einer wesentlichen Erhöhung der Lackhaftung und der Resistenz gegen Unterwanderung bei Korrosionsbeanspruchung beitragen. Solche Phosphatierverfahren sind seit langem bekannt. Für die Vorbehandlung vor der Lackierung eignen sich insbesondere die Niedrig-Zink-Phosphatierverfahren, bei denen die Phosphatierlösungen vergleichsweise geringe Gehalte an Zinkionen von z. B. 0,5 bis 2 g/l aufweisen. Ein wesentlicher Parameter in diesen Niedrig-Zink-Phosphatierbädern ist das Gewichtsverhältnis Phosphationen zu Zinkionen, das üblicherweise im Bereich > 8 liegt und Werte bis zu 30 annehmen kann.The phosphating of metals pursues the goal on the metal surface to produce firmly adherent metal phosphate layers already improve the corrosion resistance and in Connection with paints and other organic coatings too a significant increase in paint adhesion and resistance to Infiltration under corrosion stress contribute. Such phosphating processes have been known for a long time. For pretreatment Before painting, the low-zinc phosphating processes are particularly suitable, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l. On is an essential parameter in these low-zinc phosphating baths the weight ratio of phosphate ions to zinc ions, which is usually is in the range> 8 and can take values up to 30.
Es hat sich gezeigt, daß durch die Mitverwendung anderer mehrwertiger Kationen in den Zink-Phosphatierbädern Phosphatschichten mit deutlich verbesserten Korrosionsschutz- und Lackhaftungseigenschaften ausgebildet werden können. Beispielsweise finden Niedrig-Zink-Verfahren mit Zusatz von z. B. 0,5 bis 1,5 g/l Manganionen und z. B. 0,3 bis 2,0 g/l Nickelionen als sogenannte Trikation-Verfahren zur Vorbereitung von Metalloberflächen für die Lackierung, beispielsweise für die kathodische Elektrotauchlackierung von Autokarosserien, weite Anwendung.It has been shown that by using others more valuable Cations in the zinc phosphating baths with phosphate layers significantly improved corrosion protection and paint adhesion properties can be trained. For example, find low zinc processes with the addition of z. B. 0.5 to 1.5 g / l of manganese ions and Z. B. 0.3 to 2.0 g / l of nickel ions as a so-called trication method to prepare metal surfaces for the Painting, for example for the cathodic Electrocoating of car bodies, wide application.
Der hohe Gehalt an Nickelionen in den Phosphatierlösungen der Trikation-Verfahren und von Nickel und Nickelverbindungen in den gebildeten Phosphatschichten bringt jedoch insofern Nachteile, als Nickel und Nickelverbindungen aus der Sicht des Umweltschutzes und der Arbeitsplatzhygiene als kritisch eingestuft werden. In letzter Zeit werden daher zunehmend Niedrig-Zink-Phosphatierverfahren beschrieben, die ohne eine Mitverwendung von Nickel zu qualitativ ähnlich hochwertigen Phosphatschichten wie die nickelhaltigen Verfahren führen. Auch gegen die Beschleuniger Nitrit und Nitrat werden wegen möglicher Bildung Nitroser Gase zunehmend Bedenken geäußert. Darüber hinaus hat sich gezeigt, daß die Phosphatierung von verzinktem Stahl mit nickelfreien Phosphatierbädern zu unzureichendem Korrosionsschutz und unzureichender Lackhaftung führt, wenn die Phosphatierbäder größere Mengen (> 0,5 g/l) Nitrat enthalten.The high content of nickel ions in the phosphating solutions of the trication processes and of nickel and nickel compounds in the formed However, phosphate layers have disadvantages in that Nickel and nickel compounds from the point of view of environmental protection and occupational hygiene can be classified as critical. In the last Low zinc phosphating processes are increasingly being described the too qualitative without using nickel similar high-quality phosphate layers as the nickel-containing processes to lead. Also against the accelerators nitrite and nitrate Concerns have been raised about possible formation of nitrous gases. In addition, it has been shown that the phosphating of galvanized steel with nickel-free phosphating baths Corrosion protection and insufficient paint adhesion results if the phosphating baths contain larger quantities (> 0.5 g / l) nitrate.
Beispielsweise beschreibt die DE-A-39 20 296 ein Phosphatierverfahren, das auf Nickel verzichtet und neben Zink und Manganionen Magnesiumionen verwendet. Die hier beschriebenen Phosphatierbäder enthalten außer 0,2 bis 10 g/l Nitrationen weitere als Beschleuniger wirkende Oxidationsmittel, ausgewählt aus Nitrit, Chlorat oder einem organischen Oxidationsmittel. EP-A-60 716 offenbart Niedrig-Zink-Phosphatierbäder, die als essentielle Kationen Zink und Mangan enthalten und die als fakultativen Bestandteil Nickel beinhalten können. Der notwendige Beschleuniger wird vorzugsweise ausgewählt aus Nitrit, m-Nitrobenzolsulfonat oder Wasserstoffperoxid. Auch in der EP-A-228 151 werden Phosphatierbäder beschrieben, die als essentielle Kationen Zink und Mangan enthalten. Der Phosphatierbeschleuniger wird ausgewählt aus Nitrit, Nitrat, Wasserstoffperoxid, m-Nitrobenzoat oder p-Nitrophenol.For example, DE-A-39 20 296 describes a phosphating process that dispenses with nickel and besides zinc and manganese ions Magnesium ions used. The phosphating baths described here contain, in addition to 0.2 to 10 g / l nitrate ions, other accelerators acting oxidizing agents selected from nitrite, chlorate or an organic oxidizing agent. EP-A-60 716 discloses low-zinc phosphating baths, which are essential cations zinc and Contain manganese and which contain nickel as an optional component can. The necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide. Phosphating baths are also described in EP-A-228 151, which contain zinc and manganese as essential cations. The phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzoate or p-nitrophenol.
Die deutsche Patentanmeldung P 43 41 041.3 beschreibt ein Verfahren
zur Phosphatierung von Metalloberflächen mit wäßrigen, sauren
Phosphatierlösungen, die Zink-, Mangan- und Phosphationen und als
Beschleuniger m-Nitrobenzosulfonsäure oder deren wasserlösliche
Salze enthalten, wobei man die Metalloberflächen mit einer Phosphatierlösung
in Berührung bringt, die frei von Nickel, Kobalt,
Kupfer, Nitrit und Oxo-Anionen von Halogenen ist und die
Ein ähnliches Verfahren wird in der DE-A-43 30 104 beschrieben, wobei als Beschleuniger anstelle des Nitrobenzolsulfonats 0,1 bis 5 g Hydroxylamin eingesetzt werden.A similar process is described in DE-A-43 30 104, being 0.1 to 5 as the accelerator instead of the nitrobenzenesulfonate g of hydroxylamine can be used.
In Abhängigkeit von der Zusammensetzung der für die Phosphatierung verwendeten Lösung, dem für das Phosphatierverfahren verwendeten Beschleuniger, dem Verfahren der Aufbringung der Phosphatierlösung auf die Metalloberflächen und/oder auch weiteren Verfahrensparametern ist die Phosphatschicht auf den Metalloberflächen nicht vollständig geschlossen. Es verbleiben vielmehr mehr oder weniger große "Poren", deren Fläche in der Größenordnung von 0,5 bis 2 % der phosphatierten Fläche liegt und die im Zuge einer sogenannten "Nachpassivierung" geschlossen werden müssen, um korrodierenden Einflüssen auf die Metalloberflächen keinen Angriffspunkt zu lassen. Weiterhin verbessert eine Nachpassivierung die Haftung eines anschließend aufgebrachten Lackes.Depending on the composition of the phosphating used solution, that used for the phosphating process Accelerator, the process of applying the phosphating solution on the metal surfaces and / or other process parameters the phosphate layer on the metal surfaces is not complete closed. Rather, there are more or less large ones "Pores" whose area is on the order of 0.5 to 2% of phosphated surface is located in the course of a so-called "Post-passivation" must be closed to be corrosive To leave influences on the metal surfaces no point of attack. Post-passivation further improves the liability of one then applied paint.
Es ist seit langer Zeit bekannt, für diese Zwecke Chromsalze enthaltende Lösungen zu verwenden. Insbesondere wird die Korrosionsbeständigkeit der durch Phosphatierung erzeugten Überzüge durch eine Nachbehandlung der Oberflächen mit Lösungen, die Chrom(VI) enthalten, erheblich verbessert. Die Verbesserung des Korrosionsschutzes resultiert in erster Linie daraus, daß ein Teil des auf der Metalloberfläche abgeschiedenen Phosphats in einen Metall(II)-Chrom-Spinell umgewandelt wird.It has long been known to contain chromium salts for these purposes To use solutions. In particular, the corrosion resistance of the coatings produced by phosphating post-treatment of the surfaces with solutions containing chromium (VI) included, significantly improved. Improving corrosion protection results primarily from the fact that part of the of the metal surface deposited phosphate in a metal (II) chromium spinel is converted.
Ein wesentlicher Nachteil der Verwendung von Chromsalze enthaltenden Lösungen besteht darin, daß derartige Lösungen hochtoxisch sind. Außerdem wird verstärkt eine unerwünschte Blasenbildung bei der nachfolgenden Applikation von Lacken oder anderen Überzugsmaterialien beobachtet.A major disadvantage of using chromium salts containing Solutions is that such solutions are highly toxic are. In addition, unwanted blistering is increased the subsequent application of paints or other coating materials observed.
Deswegen wurden zahlreiche weitere Möglichkeiten zur Nachpassivierung phosphatierter Metalloberflächen vorgeschlagen, wie z. B. die Verwendung von Zirkoniumsalzen (NL-PS 71 16 498), Cersalzen (EP-A-492 713), polymeren Aluminiumsalzen (WO 92/15724), Oligo- oder Polyphosphorsäureestern des Inosits in Verbindung mit einem wasserlöslichen Alkali- oder Erdalkalimetallsalz dieser Ester (DE-A-24 03 022) oder auch Fluoriden verschiedener Metalle (DE-A-24 28 065).That is why there were numerous other options for re-passivation phosphated metal surfaces proposed such. B. the Use of zirconium salts (NL-PS 71 16 498), cerium salts (EP-A-492 713), polymeric aluminum salts (WO 92/15724), oligo- or Polyphosphoric esters of inosite in combination with a water soluble alkali or alkaline earth metal salt of these esters (DE-A-24 03 022) or fluorides of various metals (DE-A-24 28,065).
Aus der EP-B-410 497 ist eine Nachspüllösung bekannt, die Al-, Zr- und Fluoridionen enthält, wobei die Lösung als Gemisch komplexer Fluoride oder auch als eine Lösung von Aluminium-hexafluorozirkonat aufgefaßt werden kann. Die Gesamtmenge dieser 3 Ionen liegt im Bereich von 0,1 bis 2,0 g/l.A rinse solution is known from EP-B-410 497 which contains Al, Zr and contains fluoride ions, the solution being a complex mixture Fluoride or as a solution of aluminum hexafluorozirconate can be understood. The total amount of these 3 ions is in the range from 0.1 to 2.0 g / l.
Die DE-A-21 00 497 betrifft ein Verfahren zum elektrophoretischen Aufbringen von Farben auf eisenhaltige Oberflächen, wobei die Aufgabe gelöst werden soll, auf den eisenhaltigen Oberflächen weiße oder sonstige helle Farben ohne Verfärbung aufzubringen. Diese Aufgabe wird dadurch gelöst, daß die Oberflächen, die zuvor phosphatiert sein können, mit kupferhaltigen Lösungen gespült werden. Dabei werden für diese Nachspüllösung Kupferkonzentrationen zwischen 0,1 und 10 g/l vorgeschlagen. Die DE-A-34 00 339 beschreibt ebenfalls eine kupferhaltige Nachspüllösung für phosphatierte Metalloberflächen, wobei mit Kupfergehalten zwischen 0,01 und 10 g/l gearbeitet wird. Dabei wurde jeweils nicht beachtet, daß diese Nachspüllösungen in Verbindung mit unterschiedlichen Phosphatierverfahren zu unterschiedlichen Ergebnissen führen.DE-A-21 00 497 relates to a method for electrophoretic Applying paints to ferrous surfaces, doing the job should be solved, white on the ferrous surfaces or apply other bright colors without discoloration. This The object is achieved in that the surfaces that have previously been phosphated can be rinsed with copper-containing solutions. Copper concentrations are between for this rinse solution 0.1 and 10 g / l suggested. DE-A-34 00 339 describes also a copper-containing rinse solution for phosphated metal surfaces, with copper contents between 0.01 and 10 g / l is worked. It was not observed that this Rinse solutions in connection with different phosphating processes lead to different results.
Von den vorstehend zitierten Verfahren zur Nachspülung von Phosphatschichten haben sich - außer chromhaltigen Nachspüllösungen - nur solche Verfahren durchgesetzt, bei denen mit Lösungen komplexer Fluoride von Titan und/oder Zirkon gearbeitet wird. Daneben werden organisch-reaktive Nachspüllösungen auf der Basis von aminsubstituierten Polyvinylphenolen eingesetzt. In Verbindung mit einem nickelhaltigen Phosphatierverfahren erfüllen diese chromfreien Nachspüllösungen die hohen Anforderungen, die beispielsweise in der Automobilindustrie an Lackhaftung und Korrosionsschutz gestellt werden. Aus Umwelt- und Arbeitsschutzgründen ist man jedoch bestrebt, Phosphatierprozesse einzuführen, bei denen in allen Behandlungsstufen sowohl auf den Einsatz von Nickel- als auch von Chromverbindungen verzichtet werden kann. Nickelfreie Phosphatierverfahren in Verbindung mit einer chromfreien Nachspülung erreichen derzeit noch nicht auf allen in der Automobilindustrie verwendeten Karosseriematerialien zuverlässig die Anforderungen an Lackhaftung und Korrosionsschutz. Daher besteht immer noch ein Bedarf an Nachspüllösungen, die in Verbindung mit einer nickel- und nitritfreien Phosphatierung und einer nachfolgenden kathodischen Elektrotauchlackierung die Anforderungen an Korrosionsschutz und Lackhaftung für unterschiedliche Substratmaterialien zuverlässig erfüllen. Die Erfindung stellt sich die Aufgabe, eine derartige Verfahrenskombination aus einem hinsichtlich Umwelt- und Arbeitsschutz optimierten Phosphatierverfahren und einer hierfür besonders geeigneten chromfreien Nachspülung vor einer kathodischen Elektrotauchlackierung zur Verfügung zu stellen.Of the methods cited above for rinsing phosphate layers have - apart from chrome-containing rinse solutions - enforced only those procedures where solutions are more complex Fluoride of titanium and / or zircon is worked. Besides become organic reactive rinse solutions based on amine-substituted polyvinylphenols used. Combined with a nickel-containing phosphating process meet these Chrome-free rinse solutions meet the high requirements, for example in the automotive industry on paint adhesion and Corrosion protection can be provided. For environmental and occupational safety reasons however, efforts are being made to introduce phosphating processes, in which both the use of Nickel and chrome compounds can be dispensed with. Nickel-free phosphating process in connection with a Chrome-free rinsing currently does not reach all body materials used reliably in the automotive industry the requirements for paint adhesion and corrosion protection. Therefore there is still a need for rinse aid solutions that are related with a nickel- and nitrite-free phosphating and one subsequent cathodic electrocoating the requirements corrosion protection and paint adhesion for different substrate materials reliably meet. The invention turns the Task, such a combination of methods from a Environmental and occupational safety optimized phosphating processes and a particularly suitable chrome-free rinse before to provide cathodic electrocoating.
Diese Aufgabe wird gelöst durch ein Verfahren zur Phosphatierung
von Oberflächen aus Stahl, verzinktem Stahl und/oder Aluminium
und/oder aus Legierungen, die zu mindestens 50 Gew.-% aus Eisen,
Zink oder Aluminium bestehen, wobei man mit einer zinkhaltigen
sauren Phosphatierlösung phosphatiert und anschließend mit einer
Nachspüllösung nachspült, dadurch gekennzeichnet, daß man
Die im Teilschritt a) der erfindungsgemäßen Verfahrensabfolge eingesetzte
Phosphatierlösung enthält vorzugsweise eines oder mehrere
weitere Metallionen, deren positive Wirkung auf den Korrosionsschutz
von Zinkphosphatschichten im Stand der Technik bekannt ist.
Hierbei kann die Phosphatierlösung eines oder mehrere der folgenden
Kationen enthalten:
Dabei ist die Anwesenheit von Mangan und/oder Lithium besonders bevorzugt. Die Möglichkeit der Anwesenheit von zweiwertigem Eisen hängt von dem weiter unten beschriebenen Beschleunigersystem ab. The presence of manganese and / or lithium is special prefers. The possibility of the presence of divalent iron depends on the accelerator system described below.
Die Gegenwart von Eisen(II) im genannten Konzentrationsbereich setzt einen Beschleuniger voraus, der gegenüber diesen Ionen nicht oxidierend wirkt. Hierfür ist insbesondere Hydroxylamin als Beispiel zu nennen.The presence of iron (II) in the concentration range mentioned requires an accelerator that does not react to these ions has an oxidizing effect. Hydroxylamine in particular is an example of this to call.
Die Phosphatierbäder sind frei von Nickel und vorzugsweise auch von Kobalt. Dies bedeutet, daß diese Elemente bzw. Ionen den Phosphatierbädern nicht bewußt zugesetzt werden. Es ist jedoch in der Praxis nicht auszuschließen, daß solche Bestandteile über das zu behandelnde Material in Spuren in die Phosphatierbäder eingetragen werden. Insbesondere ist es nicht auszuschließen, daß bei der Phosphatierung von mit Zink-Nickel-Legierungen beschichtetem Stahl Nickelionen in die Phosphatierlösung eingetragen werden. Jedoch wird an die Phosphatierbäder die Erwartung gestellt, daß unter technischen Bedingungen die Nickelkonzentration in den Bädern unter 0,01 g/l, insbesondere unter 0,0001 g/l liegt. Vorzugsweise enthalten die Phosphatierbäder auch keine Oxoanionen von Halogenen.The phosphating baths are free of nickel and preferably also of Cobalt. This means that these elements or ions the phosphating baths not be added deliberately. However, it is in the Practice does not rule out that such constituents go beyond that Treating material entered in traces in the phosphating baths become. In particular, it cannot be ruled out that at Phosphating of steel coated with zinc-nickel alloys Nickel ions are introduced into the phosphating solution. However is the expectation of the phosphating baths that under technical conditions under the nickel concentration in the baths 0.01 g / l, in particular below 0.0001 g / l. Preferably included the phosphating baths also do not contain oxo anions from halogens.
Ähnlich wie in der EP-A-321 059 beschrieben, bringt auch in der erfindungsgemäßen Verfahrensfolge die Gegenwart löslicher Verbindungen des sechswertigen Wolframs im Phosphatierbad Vorteile hinsichtlich Korrosionswiderstand und Lackhaftung. In den erfindungsgemäßen Phosphatierverfahren können Phosphatierlösungen Verwendung finden, die 20 bis 800 mg/l, vorzugsweise 50 bis 600 mg/l, Wolfram in Form wasserlöslicher Wolframate, Silicowolframate und/oder Borowolframate enthalten. Dabei können die genannten Anionen in Form ihrer Säuren und/oder ihrer wasserlöslichen Salze, vorzugsweise Ammoniumsalze, eingesetzt werden. Die Verwendung von Cu(II) ist aus der EP-A-459 541 bekannt.Similar to that described in EP-A-321 059, also brings in the sequence of processes according to the invention the presence of soluble compounds advantages of the hexavalent tungsten in the phosphating bath Corrosion resistance and paint adhesion. In the Phosphating processes according to the invention can use phosphating solutions Find the use of 20 to 800 mg / l, preferably 50 to 600 mg / l, tungsten in the form of water-soluble tungstates, silicotungstates and / or contain borotungstates. The anions mentioned can in the form of their acids and / or their water-soluble salts, preferably ammonium salts can be used. The use of Cu (II) is known from EP-A-459 541.
Bei Phosphatierbädern, die für unterschiedliche Substrate geeignet sein sollen, ist es üblich geworden, freies und/oder komplexgebundenes Fluorid in Mengen bis zu 2,5 g/l Gesamtfluorid, davon bis zu 800 mg/l freies Fluorid zuzusetzen. Die Anwesenheit solcher Fluoridmengen ist auch für die Phosphatierbäder im Rahmen der Erfindung von Vorteil. Bei Abwesenheit von Fluorid soll der Aluminiumgehalt des Bades 3 mg/l nicht überschreiten. Bei Gegenwart von Fluorid werden infolge der Komplexbildung höhere Al-Gehalte toleriert, sofern die Konzentration des nicht komplexierten Al 3 mg/l nicht übersteigt. Die Verwendung fluoridhaltiger Bäder ist daher vorteilhaft, wenn die zu phosphatierenden Oberflächen zumindest teilweise aus Aluminium bestehen oder Aluminium enthalten. In diesen Fällen ist es günstig, kein komplexgebundenes, sondern nur freies Fluorid, vorzugsweise in Konzentrationen im Bereich 0,5 bis 1,0 g/l, einzusetzen.For phosphating baths that are suitable for different substrates , it has become common, free and / or complex-bound fluoride in amounts up to 2.5 g / l total fluoride, Add up to 800 mg / l of free fluoride. The presence such amounts of fluoride is also within the scope of the phosphating baths the invention of advantage. In the absence of fluoride, the The aluminum content of the bath should not exceed 3 mg / l. In the present Due to the complex formation of fluoride, higher Al contents tolerated, provided the concentration of the non-complexed Al 3 mg / l does not exceed. The use of fluoride baths is therefore advantageous if the surfaces to be phosphated at least partly consist of aluminum or contain aluminum. In In these cases it is favorable, not complex, but only free fluoride, preferably in concentrations in the range 0.5 to 1.0 g / l.
Für die Phosphatierung von Zinkoberflächen ist es nicht zwingend erforderlich, daß die Phosphatierbäder sogenannte Beschleuniger enthalten. Für die Phosphatierung von Stahloberflächen ist es jedoch erforderlich, daß die Phosphatierlösung einen oder mehrere Beschleuniger enthält. Solche Beschleuniger sind im Stand der Technik als Komponenten von Zinkphosphatierbädern geläufig. Hierunter werden Substanzen verstanden, die den durch den Beizangriff der Säure an der Metalloberfläche entstehenden Wasserstoff dadurch chemisch binden, daß sie selbst reduziert werden. Oxidierend wirkende Beschleuniger haben weiterhin den Effekt, durch den Beizangriff auf Stahloberflächen freigesetzte Eisen(II)-Ionen zur dreiwertigen Stufe zu oxidieren, so daß sie als Eisen(III)-Phosphat ausfallen können. Die im Phosphatierbad der erfindungsgemäßen Verfahrensfolge einsetzbaren Beschleuniger wurden weiter oben aufgeführt.It is not mandatory for the phosphating of zinc surfaces required that the phosphating baths so-called accelerators contain. However, it is for the phosphating of steel surfaces required that the phosphating solution one or more Contains accelerator. Such accelerators are in the state of the art Technology known as components of zinc phosphating baths. Below are understood substances that are caused by the pickling attack the hydrogen on the metal surface bind chemically so that they themselves are reduced. Oxidizing Accelerators continue to have the effect of pickling Iron (II) ions released on steel surfaces become trivalent Oxidize stage, so that it as iron (III) phosphate can fail. The process sequence according to the invention in the phosphating bath usable accelerators were listed above.
Als Cobeschleuniger können zusätzlich Nitrationen in Mengen bis zu 10 g/l zugegen sein, was sich insbesondere bei der Phosphatierung von Stahloberflächen günstig auswirken kann. Bei der Phosphatierung von verzinktem Stahl ist es jedoch vorzuziehen, daß die Phosphatierlösung möglichst wenig Nitrat enthält. Nitratkonzentrationen von 0,5 g/l sollten vorzugsweise nicht überschritten werden, da bei höheren Nitratkonzentrationen die Gefahr einer sogenannten "Stippenbildung" besteht. Hiermit sind weiße, kraterartige Fehlstellen in der Phosphatschicht gemeint.Additional nitrate ions can be used as co-accelerators in quantities of up to 10 g / l be present, which is particularly the case with phosphating of steel surfaces can have a favorable effect. When phosphating of galvanized steel, however, it is preferable that the phosphating solution contains as little nitrate as possible. Nitrate concentrations of 0.5 g / l should preferably not be exceeded, since at higher nitrate concentrations the risk of a so-called "Speck formation" exists. These are white, crater-like defects in the phosphate layer meant.
Aus Gründen der Umweltfreundlichkeit ist Wasserstoffperoxid, aus den technischen Gründen der vereinfachten Formulierungsmöglichkeiten für Nachdosierlösungen ist Hydroxylamin als Beschleuniger besonders bevorzugt. Die gemeinsame Verwendung dieser beiden Beschleuniger ist jedoch nicht ratsam, da Hydroxylamin von Wasserstoffperoxid zersetzt wird. Setzt man Wasserstoffperoxid in freier oder gebundener Form als Beschleuniger ein, so sind Konzentrationen von 0,005 bis 0,02 g/l Wasserstoffperoxid besonders bevorzugt. Dabei kann das Wasserstoffperoxid der Phosphatierlösung als solches zugegeben werden. Es ist jedoch auch möglich, Wasserstoffperoxid in gebundener Form in Form von Verbindungen einzusetzen, die im Phosphatierbad durch Hydrolysereaktionen Wasserstoffperoxid liefern. Beispiele solcher Verbindungen sind Persalze, wie Perborate, Percarbonate, Peroxosulfate oder Peroxodisulfate. Als weitere Quellen für Wasserstoffperoxid kommen ionische Peroxide wie beispielsweise Alkalimetallperoxide in Betracht.For environmental reasons, hydrogen peroxide is off the technical reasons for the simplified formulation options for replenishing solutions, hydroxylamine is an accelerator particularly preferred. Sharing these two accelerators however, is not advisable since hydroxylamine is made of hydrogen peroxide is decomposed. If you put hydrogen peroxide in free or bound form as an accelerator, so are concentrations from 0.005 to 0.02 g / l of hydrogen peroxide are particularly preferred. Here the hydrogen peroxide of the phosphating solution as such be added. However, it is also possible to add hydrogen peroxide use bound form in the form of compounds in the phosphating bath deliver hydrogen peroxide by hydrolysis reactions. Examples of such compounds are persalts, such as perborates, Percarbonates, peroxosulfates or peroxodisulfates. As another Sources of hydrogen peroxide come from ionic peroxides such as Alkali metal peroxides into consideration.
Hydroxylamin kann als freie Base, als Hydroxylaminkomplex oder in Form von Hydroxylammoniumsalzen eingesetzt werden. Fügt man freies Hydroxylamin dem Phosphatierbad oder einem Phosphatierbad-Konzentrat zu, wird es aufgrund des sauren Charakters dieser Lösungen weitgehend als Hydroxylammonium-Kation vorliegen. Bei einer Verwendung als Hydroxylammonium-Salz sind die Sulfate sowie die Phosphate besonders geeignet. Im Falle der Phosphate sind aufgrund der besseren Löslichkeit die sauren Salze bevorzugt. Hydroxylamin oder seine Verbindungen werden dem Phosphatierbad in solchen Mengen zugesetzt, daß die rechnerische Konzentration des freien Hydroxylamins zwischen 0,1 und 10 g/l, vorzugsweise zwischen 0,2 und 6 g/l und insbesondere zwischen 0,3 und 2 g/l liegt. Aus der EP-B-315 059 ist bekannt, daß die Verwendung von Hydroxylamin als Beschleuniger auf Eisenoberflächen zu besonders günstigen kugelartigen und/oder säulenartigen Phosphatkristallen führt. Die im Teilschritt b) auszuführende Nachspülung ist als Nachpassivierung solcher Phosphatschichten besonders geeignet.Hydroxylamine can be used as a free base, as a hydroxylamine complex or in Form of hydroxylammonium salts can be used. One adds free Hydroxylamine the phosphating bath or a phosphating bath concentrate too, it becomes due to the acidic nature of these solutions largely present as a hydroxylammonium cation. When using the hydroxylammonium salt are the sulfates and the phosphates 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 such quantities that the calculated concentration of free hydroxylamine between 0.1 and 10 g / l, preferably between 0.2 and 6 g / l and in particular is between 0.3 and 2 g / l. From EP-B-315 059 is known to use hydroxylamine as an accelerator on iron surfaces to particularly favorable spherical and / or leads to columnar phosphate crystals. The one to be carried out in sub-step b) Rinsing is a post-passivation of such phosphate layers particularly suitable.
Wählt man lithiumhaltige Phosphatierbäder, so liegen die bevorzugten Konzentrationen an Lithiumionen im Bereich von 0,4 bis 1 g/l. Dabei sind Phosphatierbäder besonders vorzuziehen, die Lithium als einziges einwertiges Kation enthalten. Je nach gewünschtem Verhältnis von Phosphationen zu den zweiwertigen Kationen und den Lithiumionen kann es jedoch erforderlich sein, zum Einstellen der erwünschten freien Säure den Phosphatierbädern weitere basische Substanzen zuzugeben. In diesem Falle setzt man vorzugsweise Ammoniak ein, so daß die lithiumhaltigen Phosphatierbäder zusätzlich Ammoniumionen im Bereich von etwa 0,5 bis etwa 2 g/l enthalten können. Die Verwendung basischer Natriumverbindungen wie beispielsweise Natronlauge ist in diesem Fall weniger bevorzugt, da die Gegenwart von Natriumionen in den lithiumhaltigen Phosphatierbädern die Korrosionsschutzeigenschaften der erhaltenen Schichten verschlechtert. Bei lithiumfreien Phosphatierbädern stellt man die freie Säure vorzugsweise durch Zugabe basischer Natriumverbindungen wie Natriumcarbonat oder Natriumhydroxid ein.If one chooses lithium-containing phosphating baths, the preferred ones Concentrations of lithium ions in the range from 0.4 to 1 g / l. Phosphating baths, lithium, are particularly preferred as the only monovalent cation. Depending on what you want Ratio of phosphate ions to divalent cations and However, lithium ions may be required to adjust the desired free acid the phosphating baths further basic Add substances. In this case, ammonia is preferably used a, so that the lithium-containing phosphating baths in addition Contain ammonium ions in the range from about 0.5 to about 2 g / l can. The use of basic sodium compounds such as In this case, sodium hydroxide solution is less preferred because the presence of sodium ions in the lithium-containing phosphating baths the corrosion protection properties of the layers obtained worsened. In the case of lithium-free phosphating baths, the free acid preferably by adding basic sodium compounds such as sodium carbonate or sodium hydroxide.
Besonders gute Korrosionsschutzergebnisse werden mit Phosphatierbädern erhalten, die außer Zink und gegebenenfalls Lithium Mangan(II) enthalten. Der Mangangehalt des Phosphatierbades soll zwischen 0,2 und 4 g/l liegen, da bei geringeren Mangangehalten der positive Einfluß auf das Korrosionsverhalten der Phosphatschichten nicht mehr gegeben ist und bei höheren Mangangehalten kein weiterer positiver Effekt eintritt. Gehalte zwischen 0,3 und 2 g/l und insbesondere zwischen 0,5 und 1,5 g/l sind bevorzugt. Den Zinkgehalt des Phosphatierbades stellt man vorzugsweise auf Werte zwischen 0,45 und 2 g/l ein. Infolge des Beizabtrages bei der Phosphatierung zinkhaltiger Oberflächen ist es jedoch möglich, daß der aktuelle Zinkgehalt des arbeitenden Bades auf bis zu 3 g/l ansteigt. In welcher Form die Zink- und Manganionen in die Phosphatierbäder eingebracht werden, ist prinzipiell ohne Belang. Es bietet sich insbesondere an, als Zink- und/oder Manganquelle die Oxide und/oder die Carbonate zu verwenden.Particularly good corrosion protection results are achieved with phosphating baths obtained which, in addition to zinc and possibly lithium manganese (II) contain. The manganese content of the phosphating bath should are between 0.2 and 4 g / l, since the lower the manganese content positive influence on the corrosion behavior of the phosphate layers is no longer available and with higher manganese contents no more positive effect occurs. Contents between 0.3 and 2 g / l and especially between 0.5 and 1.5 g / l are preferred. The zinc content of the phosphating bath is preferably set to values between 0.45 and 2 g / l. As a result of the pickling removal during phosphating zinc-containing surfaces, however, it is possible that the current The zinc content of the working bath increases up to 3 g / l. In what form the zinc and manganese ions in the phosphating baths is basically irrelevant. It offers itself in particular, as the zinc and / or manganese source, the oxides and / or to use the carbonates.
Bei der Anwendung des Phosphatierverfahrens auf Stahloberflächen geht Eisen in Form von Eisen(II)-Ionen in Lösung. Falls die Phosphatierbäder keine Substanzen enthalten, die gegenüber Eisen(II) stark oxidierend wirken, geht das zweiwertige Eisen vornehmlich in Folge von Luftoxidation in den dreiwertigen Zustand über, so daß es als Eisen(III)-Phosphat ausfallen kann. Daher können sich in den Phosphatierbädern Eisen(II)-Gehalte aufbauen, die deutlich über den Gehalten liegen, die Oxidationsmittel-haltige Bäder enthalten. Dies ist beispielsweise in den Hydroxylamin-haltigen Phosphatierbädern der Fall. In diesem Sinne sind Eisen(II)-Konzentrationen bis zu 50 ppm normal, wobei kurzfristig im Produktionsablauf auch Werte bis zu 500 ppm auftreten können. Für das erfindungsgemäße Phosphatierverfahren sind solche Eisen(II)-Konzentrationen nicht schädlich.When using the phosphating process on steel surfaces iron dissolves in the form of iron (II) ions. If the phosphating baths do not contain any substances that are have a strong oxidizing effect, the divalent iron mainly goes into Consequence of air oxidation into the trivalent state so that it can precipitate as iron (III) phosphate. Therefore, in the Phosphate baths build up iron (II) contents that are significantly higher than the Laid down containing baths containing oxidizing agents. This is, for example, in the hydroxylamine-containing phosphating baths the case. In this sense, iron (II) concentrations are up to 50 ppm normal, with values up to in the short term in the production process 500 ppm can occur. For the phosphating process according to the invention such iron (II) concentrations are not harmful.
Das Gewichtsverhältnis Phosphationen zu Zinkionen in den Phosphatierbädern kann in weiten Grenzen schwanken, sofern es im Bereich zwischen 3,7 und 30 liegt. Ein Gewichtsverhältnis zwischen 10 und 20 ist besonders bevorzugt. Für diese Berechnung wird der gesamte Phosphorgehalt des Phosphatierbades als in Form von Phosphationen PO4 3- vorliegend angesehen. Demnach wird bei der Berechnung des Mengenverhältnisses die bekannte Tatsache außer acht gelassen, daß bei den pH-Werten der Phosphatierbäder, die üblicherweise im Bereich von etwa 3 bis etwa 3,4 liegen, nur ein sehr geringer Teil des Phosphats tatsächlich in Form der dreifach negativ geladenen Anionen vorliegt. Bei diesen pH-Werten ist vielmehr zu erwarten, daß das Phosphat vornehmlich als einfach negativ geladenes Dihydrogenphosphat-Anion vorliegt, zusammen mit geringeren Mengen an undisoziierter Phosphorsäure und an zweifach negativ geladenen Hydrogenphosphat-Anionen.The weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided that it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred. For this calculation, the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3- . Accordingly, the known fact that the pH values of the phosphating baths, which are usually in the range from about 3 to about 3.4, is only neglected in the form of the triple negative at the pH values of the phosphating baths charged anions. At these pH values, it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogenphosphate anion, together with smaller amounts of non-associated phosphoric acid and double negatively charged hydrogenphosphate anions.
Als weitere Parameter zur Steuerung von Phosphatierbädern sind dem Fachmann die Gehalte an freier Säure und an Gesamtsäure bekannt. Die in dieser Schrift verwendete Bestimmungsmethode dieser Parameter ist im Beispielteil angegeben. Werte der freien Säure zwischen 0 und 1,5 Punkten und der Gesamtsäure zwischen etwa 15 und etwa 30 Punkten liegen im technisch üblichen Bereich und sind im Rahmen dieser Erfindung geeignet.This is another parameter for controlling phosphating baths Those skilled in the art know the free acid and total acid contents. The method of determining these parameters used in this document is given in the example section. Free acid values between 0 and 1.5 points and the total acidity between about 15 and about 30 Points are in the technically usual range and are in the frame this invention.
Die Phosphatierung kann im Spritzen, im Tauchen oder im Spritztauchen erfolgen. Die Einwirkungszeiten liegen dabei im üblichen Bereich zwischen etwa 1 und etwa 4 Minuten. Die Temperatur der Phosphatierlösung liegt im Bereich zwischen etwa 40 und etwa 60 °C. Vor der Phosphatierung sind die im Stand der Technik üblichen Schritte der Reinigung und der Aktivierung, vorzugsweise mit titanphosphathaltigen Aktivierbädern, vorzunehmen.The phosphating can be done in spraying, diving or spray diving respectively. 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 about 40 and about 60 ° C. In front phosphating are the usual steps in the prior art cleaning and activation, preferably with activation baths containing titanium phosphate.
Zwischen der Phosphatierung gemäß Teilschritt a) und der Nachspülung gemäß Teilschritt b) kann eine Zwischenspülung mit Wasser erfolgen. Diese ist jedoch nicht erforderlich und es kann sogar Vorteile bieten, auf diese Zwischenspülung zu verzichten, da dann eine Reaktion der Nachspüllösung mit der an der phosphatierten Oberfläche noch anhaftenden Phosphatierlösung erfolgen kann, die sich günstig auf den Korrosionsschutz auswirkt.Between the phosphating according to sub-step a) and the rinsing According to sub-step b), an intermediate rinse with water can take place. However, this is not necessary and it can even have advantages offer to do without this intermediate rinse, because then a Reaction of the rinse solution with that on the phosphated surface still adhering phosphating solution can take place has a positive effect on corrosion protection.
Vorzugsweise weist die im Teilschritt b) verwendete Nachspüllösung einen pH-Wert im Bereich von 3,4 bis 6 und eine Temperatur im Bereich von 20 bis 50 °C auf. Die Konzentrationen der Kationen in der im Teilschritt b) eingesetzten wäßrigen Lösung liegen vorzugsweise in folgenden Bereichen: Lithium(I) 0,02 bis 2, insbesondere 0,2 bis 1,5 g/l, Kupfer(II) 0,002 bis 1 g/l, insbesondere 0,01 bis 0,1 g/l und Silber(I) 0,002 bis 1 g/l, insbesondere 0,01 bis 0,1 g/l. Dabei können die genannten Metallionen einzeln oder im Gemisch miteinander vorliegen. Besonders bevorzugt sind Nachspüllösungen, die Kupfer(II) enthalten.The rinse solution used in sub-step b) preferably has a pH in the range of 3.4 to 6 and a temperature in the range from 20 to 50 ° C. The concentrations of the cations in the The aqueous solution used in sub-step b) is preferably in the following areas: lithium (I) 0.02 to 2, in particular 0.2 to 1.5 g / l, copper (II) 0.002 to 1 g / l, in particular 0.01 to 0.1 g / l and silver (I) 0.002 to 1 g / l, in particular 0.01 to 0.1 g / l. Here the metal ions mentioned can be used individually or as a mixture with one another available. Rinse solutions containing copper (II) are particularly preferred. contain.
In welcher Form die genannten Metallionen in die Nachspüllösung eingebracht werden, ist prinzipiell unerheblich, so lange gewährleistet ist, daß die Metallverbindungen in den genannten Konzentrationsbereichen der Metallionen löslich sind. Jedoch sollten Metallverbindungen mit Anionen vermieden werden, die die Korrosionsneigung bekanntermaßen fördern, wie beispielsweise Chlorid. Besonders bevorzugt ist es, die Metallionen als Nitrate oder als Carboxylate, insbesondere als Acetate einzusetzen. Phosphate sind ebenfalls geeignet, sofern sie unter den gewählten Konzentrations- und pH-Bedingungen löslich sind. Gleiches gilt für Sulfate.In what form the metal ions mentioned in the rinse solution are introduced is irrelevant in principle, as long as guaranteed is that the metal compounds in the concentration ranges mentioned the metal ions are soluble. However, metal connections should with anions that prevent the tendency to corrode known to promote, such as chloride. Especially it is preferred to use the metal ions as nitrates or as Carboxylates, especially as acetates. Are phosphates also suitable, provided that they are below the selected concentration and pH conditions are soluble. The same applies to sulfates.
In einer besonderen Ausführungsform setzt man die Metallionen von Lithium, Kupfer und/oder Silber in den Nachspüllösungen zusammen mit Hexafluorotitanat- und/oder, besonders bevorzugt, Hexafluorozirkonationen ein. Dabei ist es bevorzugt, daß die Konzentrationen der genannten Anionen im Bereich von 100 bis 500 ppm liegen. Als Quelle der genannten Hexafluoro-Anionen kommen deren Säuren oder deren unter den genannten Konzentrations- und pH-Bedingungen wasserlösliche Salze, insbesondere deren Alkalimetall- und/oder Ammoniumsalze in Betracht. Besonders günstig ist es, die Hexafluoro-Anionen zumindest teilweise in Form ihrer Säuren einzusetzen und in den sauren Lösungen basische Verbindungen von Lithium, Kupfer und/oder Silber aufzulösen. Hierfür kommen beispielsweise die Hydroxide, Oxide oder Carbonate der genannten Metalle in Betracht. Durch dieses Vorgehen vermeidet man, die Metalle zusammen mit gegebenenfalls störenden Anionen einzusetzen. Der pH-Wert kann, falls erforderlich, mit Ammoniak eingestellt werden.In a special embodiment, the metal ions of Lithium, copper and / or silver together in the rinse solutions with hexafluorotitanate and / or, particularly preferably, Hexafluoro zirconia. It is preferred that the concentrations of the anions mentioned in the range from 100 to 500 ppm lie. The sources of the hexafluoro anions mentioned come from them Acids or their acids under the concentration and pH conditions mentioned water-soluble salts, especially their alkali metal and / or ammonium salts. It is particularly cheap Use hexafluoro anions at least partially in the form of their acids and in the acidic solutions basic compounds of lithium, Dissolve copper and / or silver. For example, come here the hydroxides, oxides or carbonates of the metals mentioned in Consideration. By doing this, you avoid the metals together with any interfering anions. The pH can if necessary, adjust with ammonia.
Weiterhin können die Nachspüllösungen die Ionen von Lithium, Kupfer und/oder Silber zusammen mit Ionen von Cer(III) und/oder Cer(IV) enthalten, wobei die Gesamtkonzentration der Cerionen im Bereich von 0,01 bis 1 g/l liegt.The rinse solutions can also contain the ions of lithium and copper and / or silver together with ions of cerium (III) and / or cerium (IV) included, with the total concentration of cerium ions in the range from 0.01 to 1 g / l.
Weiterhin kann die Nachspüllösung außer den Ionen von Lithium, Kupfer und/oder Silber auch Aluminium(III)-Verbindungen enthalten, wobei die Konzentration an Aluminium im Bereich von 0,01 bis 1 g/l liegt. Als Aluminiumverbindungen kommen dabei insbesondere einerseits Polyaluminiumverbindungen wie beispielsweise polymeres Aluminiumhydroxychlorid oder polymeres Aluminiumhydroxysulfat in Betracht (WO 92/15724), oder aber komplexe Aluminium-Zirkon-Fluoride, wie sie beispielsweise aus der EP-B-410 497 bekannt sind.In addition to the ions of lithium, the rinse solution can Copper and / or silver also contain aluminum (III) compounds, the concentration of aluminum in the range of 0.01 to 1 g / l lies. The aluminum compounds in particular come on the one hand Polyaluminium compounds such as polymer Aluminum hydroxychloride or polymeric aluminum hydroxysulfate in Consideration (WO 92/15724), or else complex aluminum-zirconium fluorides, as they are known for example from EP-B-410 497.
Die im Teilschritt a) phosphatierten Metalloberflächen können im Teilschritt b) mit der Nachspüllösung durch Spritzen, Tauchen oder Spritztauchen in Kontakt gebracht werden, wobei die Einwirkungszeit im Bereich von 0,5 bis 10 Minuten liegen soll und vorzugsweise etwa 40 bis etwa 120 Sekunden beträgt. Aufgrund der einfacheren Anlagentechnik ist es vorzuziehen, die Nachspüllösung im Teilschritt b) auf die im Teilschritt a) phosphatierte Metalloberfläche aufzuspritzen.The metal surfaces phosphated in sub-step a) can Sub-step b) with the rinse solution by spraying, dipping or Spray diving can be brought into contact with the exposure time should be in the range of 0.5 to 10 minutes and preferably about Is 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 phosphated metal surface in sub-step a).
Ein Abspülen der Behandlungslösung nach dem Ende der Einwirkungsdauer und vor der nachfolgenden Lackierung ist prinzipiell nicht erforderlich. Beispielsweise können die erfindungsgemäß im Teilschritt a) phosphatierten und im Teilschritt b) nachgespülten Metalloberflächen ohne weitere Spülung getrocknet und lackiert werden, beispielsweise mit einer Pulverbeschichtung. Das Verfahren ist jedoch insbesondere als Vorbehandlung vor einer kathodischen Elektrotauchlackierung konzipiert. Um eine Verunreinigung des Lackbades zu vermeiden, ist es hierbei vorzuziehen, nach der Nachspülung gemäß Teilschritt b) die Nachspüllösung von den Metalloberflächen abzuspülen, vorzugsweise mit salzarmem oder entsalztem Wasser. Vor dem Einbringen in das Elektrotauchlackbecken können die erfindungsgemäß vorbehandelten Metalloberflächen getrocknet werden. Im Interesse eines rascheren Produktionszyklus unterbleibt jedoch vorzugsweise eine derartige Trocknung.Rinsing off the treatment solution after the end of the exposure period and before the subsequent painting is basically not required. For example, according to the invention in the substep a) phosphated metal surfaces rinsed in sub-step b) can be dried and varnished without further rinsing, for example with a powder coating. The procedure is however, especially as a pretreatment before a cathodic one Electro dip coating designed. To avoid contamination of the To avoid lacquer bath, it is preferable to do this after rinsing according to sub-step b) the rinse solution from the metal surfaces rinse off, preferably with low salt or desalinated Water. Before they are placed in the electrocoat, the metal surfaces pretreated according to the invention are dried. In the interest of a faster production cycle, however, is omitted preferably such drying.
Die erfindungsgemäße Verfahrensfolge wurde an Stahlblechen, wie sie
im Automobilbau Verwendung finden, überprüft. Dabei wurde folgender
in der Karosseriefertigung gebräuchlicher Verfahrensgang im Tauchverfahren
ausgeführt:
Als Kurztest für die Korrosionsschutzwirkung der Schichten wurden Stromdichte-/Potentialmessungen durchgeführt. Dieses Verfahren ist beispielsweise beschrieben in A.Losch, J.W.Schultze, D.Speckmann: "A New Electrochemical Method for the Determination of the Free Surface of Phosphate Layers", Appl. Surf. Sci. 52, 29-38 (1991). Hierzu wurden die phosphatierten Probebleche unlackiert in einen Probenhalter aus Polyamid eingeklemmt, der eine zu untersuchende Oberfläche von 43 cm2 frei ließ. Die Messungen erfolgten unter sauerstofffreien Bedingungen (Spülung mit Stickstoff) in einem Elektrolyten mit pH = 7,1, der 0,32 M H3BO3, 0,026 M Na2B4O7·10H2O und 0,5 M NaNO3 enthielt. Als Referenzelektrode wurde eine Standard-Quecksilber-Elektrode mit einem Normalpotential E0 = 0,68 Volt verwendet. Die Proben wurden zunächst ohne Anlegen eines äußeren Potentials für 5 Minuten in die Elektrolytlösung getaucht. Danach wurden cyclische Voltamogramme zwischen -0,7 und 1,3 Volt gegenüber der Standard-Quecksilber-Elektrode mit einer Potentialänderung von 20 mV/s aufgenommen. Zur Auswertung wurde die Stromdichte bei einem Potential von -0,3 Volt, bezogen auf die Standard-Quecksilber-Elektrode, abgelesen. Negative Stromdichten bei einem Potential von -0,3 Volt zeigen eine Reduktion von Schichtbestandteilen an. Hohe Stromdichten zeigen eine schlechte Barrierewirkung, geringe Stromdichten eine gute Barrierwirkung der Phosphatschichten gegenüber korrosiven Strömen an.Current density / potential measurements were carried out as a short test for the corrosion protection effect of the layers. This method is described, for example, in A.Losch, JW Schulze, D. Speckmann: "A New Electrochemical Method for the Determination of the Free Surface of Phosphate Layers", Appl. Surf. Sci. 52: 29-38 (1991). For this purpose, the phosphated sample sheets were clamped unpainted in a sample holder made of polyamide, which left a surface of 43 cm 2 to be examined free. The measurements were carried out under oxygen-free conditions (flushing with nitrogen) in an electrolyte with pH = 7.1, which contained 0.32 MH 3 BO 3 , 0.026 M Na 2 B 4 O 7 .10H 2 O and 0.5 M NaNO 3 . A standard mercury electrode with a normal potential E 0 = 0.68 volts was used as the reference electrode. The samples were first immersed in the electrolyte solution for 5 minutes without applying an external potential. Then cyclic voltamograms between -0.7 and 1.3 volts compared to the standard mercury electrode with a potential change of 20 mV / s were recorded. For the evaluation, the current density was read at a potential of -0.3 volts, based on the standard mercury electrode. Negative current densities at a potential of -0.3 volts indicate a reduction in layer components. High current densities indicate a poor barrier effect, low current densities indicate a good barrier effect of the phosphate layers against corrosive currents.
Schichtgewichte wurden durch Wiegen der phosphatierten Bleche, Ablösen der Phosphatschicht in 0,5 Gew.-%iger Chromsäurelösung und erneutes Wiegen bestimmt.Layer weights were obtained by weighing the phosphated sheets, peeling them off the phosphate layer in 0.5 wt .-% chromic acid solution and determined again.
Bei den Nachspüllösungen gemäß Tabelle 2 wurden Li als Carbonat, Cu als Acetat und Ag als Sulfat eingesetzt, TiF6 2- und ZrF6 2- als freie Säuren. Ce(III) wurde als Nitrat, Ce(IV) als Sulfat und Al(III) als Polyaluminiumhydroxychlorid der ungefähren Zusammensetzung Al(OH)2,5Cl eingesetzt. pH-Werte wurden nach unten mit Phosphorsäure, nach oben mit Ammoniaklösung korrigiert. In the rinse solutions according to Table 2, Li was used as carbonate, Cu as acetate and Ag as sulfate, TiF 6 2- and ZrF 6 2- as free acids. Ce (III) was used as nitrate, Ce (IV) as sulfate and Al (III) as polyaluminium hydroxychloride with the approximate composition Al (OH) 2.5 Cl. pH values were corrected downwards with phosphoric acid and upwards with ammonia solution.
Für Korrosionsschutzprüfungen wurden Probebleche aus Stahl (St
1405) und elektrolytisch verzinktem Stahl im vorstehend beschriebenen
allgemeinen Verfahrensgang mit einer Phosphatierlösung mit
folgenden Badparametern im Tauchverfahren phosphatiert:
Die Probebleche wurden nach Zwischenspülung mit Stadtwasser für
eine Minute bei einer Temperatur von 40 °C in folgende Nachspüllösungen
in vollentsalztem Wasser (Tabelle 4) eingetaucht. Danach
wurden die Bleche mit vollentsalztem Wasser gespült, getrocknet und
lackiert.
Zur Lackierung wurde der kathodische Elektrotauchlack FT 85-7042
grau der Firma BASF verwendet. Die Korrosionsschutzprüfung erfolgte
nach dem VDA-Wechselklimatest 621-415. Als Ergebnis ist in Tabelle
5 die Lackunterwanderung am Ritz eingetragen. Zusätzlich erfolgte
eine Lackhaftungsprüfung nach VW Steinschlagtest, die nach K-Wert
beurteilt wurde. Höhere K-Werte bedeuten schlechtere, niedrige K-Werte
bessere Lackhaftung. Die Ergebnisse sind ebenfalls in Tabelle
5 enthalten.
Weiterhin wurde ein Freibewitterungstest nach VDE 621-414 durchgeführt.
Hierzu wurde auf den KTL-beschichteten Probeblechen ein
Lack-Komplettaufbau (VW weiß) aufgebracht. Nach 6 Monaten Auslagerungszeit
wurden folgende Lackunterwanderungen (halbe Ritzbreite)
gefunden (Tabelle 6):
Claims (12)
- A process for phosphating surfaces of steel, galvanized steel and/or aluminium and/or of alloys of which at least 50% by weight consist of iron, zinc or aluminium, the surfaces in question being phosphated with a zinc-containing acidic phosphating solution and then rinsed with an after-rinse solution, characterized in thata) a nitrite- and nickel-free solution with a pH value of 2.7 to 3.6 which contains 0.3 to 3 g/l of Zn(II), 5 to 40 g/l of phosphate ions and at least one of the following accelerators: 0.2 to 2 g/l of m-nitrobenzene sulfonate ions, 0.1 to 10 g/l of hydroxylamine in free or bound form, 0.05 to 2 g/l of m-nitrobenzoate ions, 0.05 to 2 g/l of p-nitrophenol, 1 to 70 mg/l of hydrogen peroxide in free or bound form is used for phosphating
and, after phosphating with or without intermediate rinsing with water,b) the surface thus phosphated is rinsed with an aqueous solution with a pH value of 3 to 7 which contains 0.001 to 10 g/l of one or more of the following cations: lithium ions, copper ions and/or silver ions. - A process as claimed in claim 1, characterized in that the phosphating solution used in step a) additionally contains one or more of the following cations: 0.2 to 4 g/l of manganese(II), 0.2 to 2.5 g/l of magnesium(II), 0.2 to 2.5 g/l of calcium(II), 0.01 to 0.5 g/l of iron(11), 0.2 to 1.5 g/l of lithium(I), 0.02 to 0.8 g/l of tungsten(VI), 0.001 to 0.03 g/l of copper(II).
- A process as claimed in one or both of claims 1 and 2, characterized in that the phosphating solution used in step a) additionally contains up to 2.5 g/l of total fluoride, including up to 0.8 g/l of free fluoride.
- A process as claimed in one or more of claims 1 to 3, characterized in that the after-rinse solution used in step b) has a pH value of 3.4 to 6.
- A process as claimed in one or more of claims 1 to 4, characterized in that the after-rinse solution used in step b) has a temperature of 20 to 50°C.
- A process as claimed in one or more of claims 1 to 5, characterized in that the after-rinse solution used in step b) contains the metal ions in the following quantity ranges: lithium(I) 0.02 to 2 g/l and/or copper(II) 0.002 to 1 g/l and/or silver(I) 0.002 to 1 g/l.
- A process as claimed in one or more of claims 1 to 6, characterized in that the after-rinse solution used in step b) additionally contains 100 to 500 mg/l of hexafluorotitanate and/or hexafluorozirconate ions.
- A process as claimed in one or more of claims 1 to 6, characterized in that the after-rinse solution used in step b) additionally contains 0.01 to 1 g/l of cerium(III) and/or cerium(IV) ions.
- A process as claimed in one or more of claims 1 to 6, characterized in that the after-rinse solution used in step b) additionally contains aluminium(III) in a quantity of 0.01 to 1 g/l.
- A process as claimed in one or more of claims 1 to 9, characterized in that the after-rinse solution used in step b) is sprayed onto the metal surface phosphated in step a).
- A process as claimed in one or more of claims 1 to 10, characterized in that the after-rinse solution used in step b) is allowed to act on the phosphated metal surface for 0.5 to 10 minutes.
- A process as claimed in one or more of claims 1 to 11, characterized in that no intermediate rinsing is carried out between steps a) and b).
Applications Claiming Priority (3)
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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 |
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EP0817872A1 EP0817872A1 (en) | 1998-01-14 |
EP0817872B1 true EP0817872B1 (en) | 2000-01-19 |
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ID=7758087
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EP96908083A Expired - Lifetime EP0817872B1 (en) | 1995-03-29 | 1996-03-20 | Phosphating process with a metalliferous re-rinsing stage |
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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) |
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DE4013483A1 (en) * | 1990-04-27 | 1991-10-31 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METAL SURFACES |
US5209788A (en) * | 1990-11-21 | 1993-05-11 | Ppg Industries, Inc. | Non-chrome final rinse for phosphated metal |
DE4041091A1 (en) * | 1990-12-21 | 1992-06-25 | Metallgesellschaft Ag | METHOD FOR REFILLING CONVERSION LAYERS |
US5128211A (en) * | 1991-02-28 | 1992-07-07 | Diversey Corporation | Aluminum based phosphate final rinse |
CA2150545A1 (en) * | 1992-12-22 | 1994-07-07 | Robert W. Miller | Substantially nickel-free phosphate conversion coating composition and process |
ATE162233T1 (en) * | 1993-09-06 | 1998-01-15 | Henkel Kgaa | NICKEL-FREE PHOSPHATING PROCESS |
DE4341041A1 (en) * | 1993-12-02 | 1995-06-08 | Henkel Kgaa | Phosphating solns contg hydroxylamine and/or nitrobenzene sulphonate |
DE4330104A1 (en) * | 1993-09-06 | 1995-03-09 | Henkel Kgaa | Nickel- and copper-free phosphating process |
JPH07278891A (en) * | 1994-04-12 | 1995-10-24 | Nippon Parkerizing Co Ltd | Pretreatment for coating of metal material |
MX9605901A (en) * | 1994-05-27 | 1997-12-31 | Herberts & Co Gmbh | Process for coating phosphatized metal substrates. |
DE19511573A1 (en) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Process for phosphating with metal-containing rinsing |
-
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
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009020794A2 (en) * | 2007-08-03 | 2009-02-12 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a metal substrate |
WO2009020794A3 (en) * | 2007-08-03 | 2009-03-26 | Ppg Ind Ohio Inc | Pretreatment compositions and methods for coating a metal substrate |
RU2447193C2 (en) * | 2007-08-03 | 2012-04-10 | Ппг Индастриз Огайо, Инк. | Pretreatment composition and method of applying coat on metal substrate |
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 |
EP0817872A1 (en) | 1998-01-14 |
TR199701061T1 (en) | 1998-01-21 |
JPH11502569A (en) | 1999-03-02 |
AU5146496A (en) | 1996-10-16 |
HUP9802380A3 (en) | 1999-03-29 |
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