WO1997016581A2 - Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate - Google Patents
Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate Download PDFInfo
- Publication number
- WO1997016581A2 WO1997016581A2 PCT/EP1996/004541 EP9604541W WO9716581A2 WO 1997016581 A2 WO1997016581 A2 WO 1997016581A2 EP 9604541 W EP9604541 W EP 9604541W WO 9716581 A2 WO9716581 A2 WO 9716581A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ions
- phosphating
- zinc
- free
- phosphating solution
- Prior art date
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910002651 NO3 Inorganic materials 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 58
- 230000008569 process Effects 0.000 claims abstract description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 10
- 239000010959 steel Substances 0.000 claims abstract description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 9
- 239000008397 galvanized steel Substances 0.000 claims abstract description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 22
- -1 chlorate ions Chemical class 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000010422 painting Methods 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001603 reducing effect Effects 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 17
- 235000021317 phosphate Nutrition 0.000 description 17
- 239000010452 phosphate Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000680 Aluminized steel Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 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 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- RBLWMQWAHONKNC-UHFFFAOYSA-N hydroxyazanium Chemical compound O[NH3+] RBLWMQWAHONKNC-UHFFFAOYSA-N 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000008163 sugars 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
- 231100000027 toxicology Toxicity 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
Definitions
- the invention relates to a process for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc and phosphate ions and accelerators in free or bound form, and to their use as pretreatment of the metal surfaces for subsequent painting, in particular electrocoating.
- the method can be used for the treatment of surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
- the phosphating of metals pursues the goal of producing firmly adhered metal phosphate layers on the metal surface, which in themselves improve corrosion resistance and, in conjunction with lacquers and other organic coatings, to a substantial increase in adhesion and resistance to migration under corrosion contribute.
- Such phosphating processes have long been known in the prior art.
- the low-zinc phosphating processes in which the phosphating solutions are comparatively low in zinc ion contents of z. B. 0.5 to Have 2 g / 1.
- An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range> 12 and can take values up to 30.
- phosphate layers with significantly improved corrosion protection and paint adhesion properties can be formed.
- z. B. 0.5 to 1.5 g / 1 manganese ions and z. B. 0.3 to 2.0 g / 1 of nickel ions as a so-called trication process for preparing metal surfaces for painting, for example for the cathodic electrocoating of car bodies, widely used.
- DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
- the phosphating baths described here contain, in addition to 0.2 to 10 g / 1 nitrate ions, further oxidizing agents which act as accelerators, selected from nitrite, chlorate or an organic oxidizing agent. Concerns about the accelerators nitrite and nitrate are being raised due to the possible formation of nitrous gases.
- the phosphating process disclosed in WO 86/04931 works without nitrates.
- the accelerator system is based on a combination of bromate and m-nitrobenzenesulfonate. Only zinc is given as the essential polyvalent cation, and nickel, manganese or cobalt is given as further optional cations.
- the phosphating solutions preferably contain at least 2 of these optional metals.
- DE-A-40 13 483 discloses phosphating processes with which good corrosion protection properties can be achieved as with the trication processes. These processes do without nickel and instead use copper in low concentrations, 0.001 to 0.03 g / 1.
- Oxygen and / or other oxidizing agents having the same effect are used to oxidize the divalent iron formed in the pickling reaction of steel surfaces to the trivalent stage.
- Nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds, such as nitrobenzenesulfonate, are specified as such.
- the German patent application DE 42 10513 modifies this process by adding hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / 1 hydroxylamine as a modifying agent for the morphology of the phosphate crystals formed.
- EP-A-315059 specifies as a special effect of the use of hydroxylamine in phosphating baths the fact that on steel the phosphate crystals are still formed in a desired columnar or knot-like form when the zinc concentration in the phosphating bath is the same for low-zinc Ver ⁇ driving exceeds the usual range. This makes it possible to operate the phosphating baths with zinc concentrations of up to 2 g / 1 and with weight ratios of phosphate to zinc down to 3.7. No further statements are made about advantageous cation combinations of these phosphating baths, but nickel is used in all patent examples.
- Nitrates and nitric acid are also used in the patent examples, even if the description of the presence of nitrate in large amounts is not advised in the description.
- the required hydroxylamine concentration is given as 0.5 to 50 g / 1, preferably 1 to 10 g / 1.
- the incorporation of nickel and manganese in the phosphate layers compensated for disadvantages with regard to paint adhesion and corrosion protection, which resulted from the fact that only hopeit crystals, but no phosphophyllite crystals, were formed on galvanized substrates.
- This object is achieved by a method for phosphating steel, galvanized or alloy-galvanized steel and / or aluminum or its alloys by treatment with a zinc phosphating solution in the immersion, spray or spray immersion process, characterized in that the zinc phosphating solution paints a maximum Has nitrate ion content of 0.5 g / 1 and is free of manganese, nickel and cobalt ions and that they
- the phosphating baths are free from manganese, nickel and cobalt ions means that these ions are not deliberately added to the phosphating baths.
- phosphating metal surfaces which contain these metals as alloy components, it cannot be ruled out that small amounts of the corresponding cations may get into the phosphating baths as a result of the pickling attack. This can be the case in particular when steel coated with a zinc-nickel alloy is phosphated. In practice, however, the expectation is placed on the phosphating baths that they contain less than 0.05 g / 1 of the cations mentioned.
- phosphating baths In addition to zinc ions, phosphating baths generally contain sodium, potassium and / or ammonium ions to adjust the free acid.
- the term free acid is familiar to those skilled in the phosphating field. The method of determining free acid and total acid selected in this document is given in the example section.
- the process according to the invention is preferably characterized in that the phosphating solution additionally contains one or more of the following cations:
- the weight ratio of phosphate ions to zinc ions in the phosphate baths can vary within wide limits, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
- the skilled worker is familiar with the free acid and total acid contents as further parameters for controlling phosphating baths. The method of determining these parameters used in this document is given in the example section. Values of the free acid between about 0.3 and about 1.5 points and the total acid between about 15 and about 35 points are in the technically customary range and are suitable for the purposes of this invention.
- nitrate content of the phosphating bath When phosphating surfaces containing zinc, it has proven to be advantageous to limit the nitrate content of the phosphating bath to a maximum of 0.5 g / l. This suppresses the problem of so-called speck formation and improves corrosion protection. Phosphating baths containing less than 0.05 g / l and in particular no nitrate are particularly preferred.
- phosphating baths which are said to be suitable for different substrates, it has become customary to add free and / or complex-bound fluoride in amounts of up to 2.5 g / 1 total fluoride, of which up to 800 mg / l free fluoride.
- the presence of such amounts of fluoride is also advantageous for the phosphating baths according to the invention.
- the aluminum content of the bath should not exceed 3 mg / l.
- the concentration of the non-complexed AI does not exceed 3 mg / l.
- Suitable accelerators are the substances listed above and known in the prior art. On the one hand, these accelerate the layer formation, since they have a “depolarizing” effect by oxidizing the elemental hydrogen which forms on the metal surface during the pickling attack to water. However, certain accelerators such as hydroxylamine can also influence the shape of the phosphate crystals that are formed. Oxidizing accelerators also lead to the fact that iron (II) ions formed on steel surfaces during the pickling reaction are oxidized to the trivalent stage, so that they precipitate out as iron (III) phosphate.
- nitrite could also be used within the scope of the invention. However, this is less preferred since the present invention is intended to provide a phosphating process which has particularly few toxicological and disposal problems. From the point of view of occupational safety, however, nitrite is to be assessed as particularly critical, since nitrous gases which are harmful to health can be generated when it is used. Furthermore, when nitrite is used, nitrate could be formed by its oxidation, so that the low nitrate contents according to the invention would be exceeded.
- the accelerators listed above can be used individually, but in chemical compatibility they can also be used in combination.
- a preferred embodiment of the invention is that a combination of chlorate ions and hydrogen peroxide is used in the phosphating in the immersion process.
- the hydrogen peroxide can 7/16581 PO7EP96 / 04541
- the concentration of chlorate can be, for example, in the range from 2 to 4 g / l, the concentration of hydrogen peroxide in the range from 10 to 50 ppm.
- reducing sugars as accelerators is known from US-A-5 378 292. In the context of the present invention, they can be used in amounts between about 0.01 and about 10 g / 1, preferably in amounts between about 0.5 and about 1.5 g / 1. Examples of such sugars are galactose, mannose and in particular glucose (dextrose).
- Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely be present as a hydroxylammonium cation due to the acidic nature of these solutions.
- the sulfates and the phosphates are particularly suitable. In the case of the phosphates, the acid salts are preferred because of their better solubility.
- Hydroxylamine or its compounds are added to the phosphating bath in amounts such that the calculated concentration of the free hydroxylamine is between 0.1 and 10 g / 1, preferably between 0.3 and 5 g / 1. It is preferred that the phosphating baths contain hydroxylamine as the sole accelerator, at most together with a maximum of 0.5 g / l of nitrate. Accordingly, in a preferred Embodiment phosphating baths are used which do not contain any of the other known accelerators such as nitrite, oxo anions of halogens, peroxides or nitrobenzenesulfonate.
- the accelerator hydroxylamine can be slowly inactivated even if no metal parts to be phosphated are introduced into the phosphating bath. It has surprisingly been found that the inactivation of the hydroxylamine can be significantly slowed down if one or more aliphatic hydroxycarboxylic acids having 3 to 6 carbon atoms in a total amount of 0.5 to 1.5 g / l are added to the phosphating bath .
- the hydroxycarboxylic acids are preferably selected from lactic acid, gluconic acid, tartronic acid, malic acid, tartaric acid and citric acid, citric acid being particularly preferred.
- the zinc content of the phosphating bath will be set according to EP-A-315059 to values between 0.45 and 1.1 g / 1.
- the current zinc content of the working bath is above a value of 1.1 g / l.
- Zinc levels up to 2 g / l are harmless in the context of the present invention.
- zinc contents of up to 2 g / l can also reduce the risk of rust formation during phosphating.
- the form in which the cations are introduced into the phosphating baths is in principle irrelevant. It is particularly useful to use oxides and / or carbonates as the cation source.
- iron (II) ions When the phosphating process is used on steel surfaces, iron dissolves in the form of iron (II) ions. Since the phosphating baths according to the invention preferably do not contain any substances contain that have an oxidizing effect on iron (II), the divalent iron only changes into the trivalent state as a result of air oxidation, so that it can precipitate out as iron (III) phosphate. Therefore, iron (II) contents can be built up in the phosphate baths according to the invention which are clearly above the contents which contain baths containing oxidizing agents. In this sense, iron (II) concentrations of up to 50 ppm are normal, although values of up to 500 ppm can also occur briefly in the production process.
- the phosphating baths can further contain the hardness-forming cations Mg (II) and Ca (II) in a total concentration of up to 7 mmol / l.
- Mg (II) or Ca (II) can also be added to the phosphate bath in amounts of up to 2.5 g / l.
- a phosphate solution is used which is the only one containing cations with an actual or potential oxidation state of> 1 zinc and copper ions.
- Zinc and copper ions will generally be present in oxidation level 2 in the phosphate solution.
- accelerators with a principally reducing action such as, for example, hydroxylamine, can at least partially reduce the copper ions to the monovalent stage.
- this preferred phosphating solution can also contain sodium, potassium and / or ammonium ions, which, as usual, can be used in the form of their basic compounds to adjust the free acidity of the phosphating solution.
- the phosphating solution contains 3 to 20 mg / l copper ions when used in the dipping process and 1 to 10 mg / l copper ions when used in the spraying process.
- the temperature of the phosphating solution is preferably in the range between about 40 and about 60 ° C. It has emerged as a positive side effect of the phosphating process according to the invention that hydroxylamine concentrations above approximately 1.5 g / l significantly reduce the risk of rust formation at insufficiently flooded areas of the components to be phosphated.
- the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
- the materials mentioned can also be present side by side, as is becoming increasingly common in automobile construction.
- Parts of the bodywork can also consist of material that has already been pretreated, such as is produced using the Bonazink R process.
- the base material is first chromated or phosphated and then coated with an organic resin.
- the phosphating process according to the invention then leads to phosphating on damaged areas of this pretreatment layer or on untreated rear sides.
- the method can be used in particular in automotive engineering, where treatment times between 1 and 8 minutes are common. It is intended in particular for the treatment of the metal surfaces mentioned before painting, in particular before cathodic electrocoating, as is customary in automobile construction.
- the phosphating process is to be seen as a sub-step of the technically usual pretreatment chain. In this chain, the steps of cleaning / degreasing, rinsing and activating are usually preceded by the phosphating, the activation usually being carried out using activating agents containing titanium phosphate.
- the phosphating according to the invention can be followed, if appropriate after an intermediate rinse, by a passivating aftertreatment. For such a passivating aftertreatment, treatment baths containing chromic acid are widespread.
- the phosphating processes according to the invention and comparative processes were checked on electrolytically galvanized steel sheets, as are used in automobile construction.
- the following process step, customary in body production, was carried out as an immersion process:
- the free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.5.
- the mass per unit area was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942.
- the phosphated test sheets were coated with a cathodic dip coating from BASF (FT 85-7042).
- the corrosion protection effect was tested in an alternating climate test according to VDA 621-415 over 10 rounds.
- Table 1 also contains the results of a stone chip test according to the VW standard as "K values”.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Coating With Molten Metal (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU72960/96A AU7296096A (en) | 1995-10-27 | 1996-10-18 | Low-nitrate, manganese-free zinc phosphatization |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1995140085 DE19540085A1 (de) | 1995-10-27 | 1995-10-27 | Nitratarme, manganfreie Zinkphosphatierung |
DE19540085.2 | 1995-10-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1997016581A2 true WO1997016581A2 (fr) | 1997-05-09 |
WO1997016581A3 WO1997016581A3 (fr) | 1997-06-19 |
Family
ID=7775975
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/004541 WO1997016581A2 (fr) | 1995-10-27 | 1996-10-18 | Phosphatation au zinc, a l'aide d'une solution sans manganese et a faible teneur en nitrate |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU7296096A (fr) |
DE (1) | DE19540085A1 (fr) |
WO (1) | WO1997016581A2 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH10204649A (ja) * | 1997-01-24 | 1998-08-04 | Nippon Parkerizing Co Ltd | 金属表面のりん酸塩処理水溶液及び処理方法 |
US6179934B1 (en) | 1997-01-24 | 2001-01-30 | Henkel Corporation | Aqueous phosphating composition and process for metal surfaces |
DE10006338C2 (de) * | 2000-02-12 | 2003-12-04 | Chemetall Gmbh | Verfahren zur Beschichtung von Metalloberflächen, wässeriges Konzentrat hierzu und Verwendung der beschichteten Metallteile |
DE102008017523A1 (de) | 2008-03-20 | 2009-09-24 | Henkel Ag & Co. Kgaa | Optimierte Elektrotauchlackierung von zusammengefügten und teilweise vorphosphatierten Bauteilen |
CN107937892A (zh) * | 2017-12-26 | 2018-04-20 | 廊坊京磁精密材料有限公司 | 高效环保钕铁硼磁体的磷化防锈方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU30515A1 (fr) * | ||||
DE860307C (de) * | 1942-10-17 | 1952-12-18 | Parker Rust Proof Company | Verfahren zur Vorbereitung von Eisenblechen zur Anfertigung von Behaeltern |
CH391420A (de) * | 1959-09-23 | 1965-04-30 | Metallgesellschaft Ag | Verfahren zur Aufbringung von Phosphatüberzügen mit chlorathaltigen Phosphatierungslösungen |
FR1312108A (fr) * | 1961-11-29 | 1962-12-14 | Parker Ste Continentale | Procédé de régénération de solutions de phosphate de zinc chloratées et bromatées pour la phosphatation du fer et de l'acier |
GB1272772A (en) * | 1968-08-16 | 1972-05-03 | Ici Ltd | Phosphating solutions |
JPS52119435A (en) * | 1976-04-01 | 1977-10-06 | Nippon Packaging Kk | Phosphating process |
JPS5811514B2 (ja) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
ES8606528A1 (es) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Procedimiento para el fosfatado de superficies metalicas, especialmente ferreas |
DE3630246A1 (de) * | 1986-09-05 | 1988-03-10 | Metallgesellschaft Ag | Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung |
US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
DE4210513A1 (de) * | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-freie Phosphatierverfahren |
DE4214992A1 (de) * | 1992-05-06 | 1993-11-11 | Henkel Kgaa | Kupfer enthaltendes, nickelfreies Phosphatierverfahren |
DE69326021T2 (de) * | 1992-12-22 | 1999-12-23 | Henkel Corp., Plymouth Meeting | Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren |
DE19500562A1 (de) * | 1995-01-11 | 1996-07-18 | Henkel Kgaa | Silberhaltige Zinkphosphatierlösung |
DE19500927A1 (de) * | 1995-01-16 | 1996-07-18 | Henkel Kgaa | Lithiumhaltige Zinkphosphatierlösung |
BR9607700A (pt) * | 1995-03-07 | 1998-07-07 | Henkel Corp | Composição líquido aquosa e processo para formar um revestimento de conversão de fosfato em uma superfície de metal |
-
1995
- 1995-10-27 DE DE1995140085 patent/DE19540085A1/de not_active Withdrawn
-
1996
- 1996-10-18 WO PCT/EP1996/004541 patent/WO1997016581A2/fr active Application Filing
- 1996-10-18 AU AU72960/96A patent/AU7296096A/en not_active Abandoned
Also Published As
Publication number | Publication date |
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DE19540085A1 (de) | 1997-04-30 |
WO1997016581A3 (fr) | 1997-06-19 |
AU7296096A (en) | 1997-05-22 |
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