EP2358922A1 - Conversion layers for surfaces containing zinc - Google Patents
Conversion layers for surfaces containing zincInfo
- Publication number
- EP2358922A1 EP2358922A1 EP09760833A EP09760833A EP2358922A1 EP 2358922 A1 EP2358922 A1 EP 2358922A1 EP 09760833 A EP09760833 A EP 09760833A EP 09760833 A EP09760833 A EP 09760833A EP 2358922 A1 EP2358922 A1 EP 2358922A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- treatment solution
- group
- solution according
- aqueous treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 title claims description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- -1 chromium (III) ions Chemical class 0.000 claims description 19
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 2
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 claims description 2
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 2
- PPDRLQLKHRZIJC-UHFFFAOYSA-N 5-nitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC=C1O PPDRLQLKHRZIJC-UHFFFAOYSA-N 0.000 claims description 2
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004761 hexafluorosilicates Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 229910052752 metalloid Inorganic materials 0.000 claims 1
- 150000002738 metalloids Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 29
- 239000007800 oxidant agent Substances 0.000 abstract description 15
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003929 acidic solution Substances 0.000 abstract description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001436 Cr3+ Inorganic materials 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 7
- 239000002609 medium Substances 0.000 description 6
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 6
- 238000002161 passivation Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001204 N-oxides Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000004532 chromating Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
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- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- GOLXRNDWAUTYKT-UHFFFAOYSA-N 3-(1H-indol-3-yl)propanoic acid Chemical compound C1=CC=C2C(CCC(=O)O)=CNC2=C1 GOLXRNDWAUTYKT-UHFFFAOYSA-N 0.000 description 2
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- 229960002885 histidine Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003290 indole 3-propionic acid Substances 0.000 description 1
- IENZCGNHSIMFJE-UHFFFAOYSA-N indole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2NC=CC2=C1 IENZCGNHSIMFJE-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- SRJOCJYGOFTFLH-UHFFFAOYSA-N isonipecotic acid Chemical compound OC(=O)C1CCNCC1 SRJOCJYGOFTFLH-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 1
- 229960004963 mesalazine Drugs 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- JPGZDTDZZDLVHW-UHFFFAOYSA-N quinoline-2,4-dicarboxylic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC(C(O)=O)=C21 JPGZDTDZZDLVHW-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- ONJSZLXSECQROL-UHFFFAOYSA-N salicyluric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1O ONJSZLXSECQROL-UHFFFAOYSA-N 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 1
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 1
- IFGCUJZIWBUILZ-UHFFFAOYSA-N sodium 2-[[2-[[hydroxy-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyphosphoryl]amino]-4-methylpentanoyl]amino]-3-(1H-indol-3-yl)propanoic acid Chemical compound [Na+].C=1NC2=CC=CC=C2C=1CC(C(O)=O)NC(=O)C(CC(C)C)NP(O)(=O)OC1OC(C)C(O)C(O)C1O IFGCUJZIWBUILZ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229960002898 threonine Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-HNQUOIGGSA-N trans-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C/C(O)=O GTZCVFVGUGFEME-HNQUOIGGSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- JACRWUWPXAESPB-UHFFFAOYSA-N tropic acid Chemical compound OCC(C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-UHFFFAOYSA-N 0.000 description 1
- 229960004441 tyrosine Drugs 0.000 description 1
- FBZONXHGGPHHIY-UHFFFAOYSA-N xanthurenic acid Chemical compound C1=CC=C(O)C2=NC(C(=O)O)=CC(O)=C21 FBZONXHGGPHHIY-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
- C23C22/05—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
- C23C22/07—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
- C23C22/10—Orthophosphates containing oxidants
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the invention relates to the corrosion protection of metallic materials, in particular of those which are provided with a conversion layer.
- the coating of the metallic workpiece to be protected with a coating of another metal is a widely used and established method in the art.
- the coating metal can behave in the corrosive medium either electrochemically nobler or less noble than the material base metal alone. If the coating metal behaves less noble, it acts as a sacrificial anode in the corrosive medium in the sense of cathodic protection against the base metal. Although this is associated with the formation of corrosion products of the coating metal protection function is indeed desirable, but the corrosion products of the coating often lead even to undesirable decorative and often to functional impairments of the workpiece.
- so-called conversion layers are often used especially on cathodically protective base coating metals such as zinc and its alloys. These are reaction products of the base metal which are insoluble in aqueous media over a wide pH range with the reaction solution.
- conversion layers are, for example, so-called phosphating and chromating.
- phosphating the layer to be protected is dipped in an acidic solution containing phosphate ions.
- the acidic medium leads to the partial dissolution of zinc from the coating.
- the liberated Zn 2+ cations form a sparingly soluble zinc phosphate layer on the surface with the phosphate ions of the reaction solution. Since zinc phosphate coatings themselves form only a comparatively bad corrosion protection, but an excellent primer for this On applied paints and paints, their main application is in the function of a primer for coatings and paints.
- the surface to be treated is dipped in an acidic solution containing chromium (VI) ions.
- chromium (VI) ions For example, if it is a zinc surface, some of the zinc will dissolve.
- chromium (VI) is reduced to chromium (III), which in the hydrogenation more alkaline surface film i.a. as chromium (III) - hydroxide or as sparingly soluble ⁇ -oxo or ⁇ -hydroxo-bridged chromium (III) - complex is deposited.
- sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well protects against corrosion attack by electrolytes conversion coating on the zinc surface.
- chromium (VI) compounds are distinguished by their high carcinogenic potential, so that it is necessary to replace the processes associated with these compounds.
- chromating processes with hexavalent chromium compounds a large number of processes have now been established which use different complexes of trivalent chromium compounds.
- a decisive step in the course of the deposition is a reaction by which the pH at the interface of the zinc surface or zinc-containing surface to the solution increases to such an extent that the deposition of the conversion layer takes place.
- Chromium (III) is not suitable in the sense described above as an oxidizing agent for zinc. Reduction to chromium (II) is possible due to redox potential, but does not increase the pH at the interface. It is therefore necessary, in order to build up a conversion layer from an aqueous acidic solution of chromium (III) ions, to additionally add a suitable oxidizing agent which increases the concentration of zinc ions as well as the pH at the zinc or zinc alloy interface in that the components of the conversion layer which are soluble in the inside of the solution in solution on the metal surface are converted into a sparingly soluble hydrolysis form.
- Nitrate is first reduced to nitrite under the usual reaction conditions of the treatment solutions.
- nitrite is in the acidic medium of the treatment solutions, the pH is usually between pH 1 and pH 3.5, not stable but tends to disproportionation in nitrate and nitrogen monoxide:
- Nitrogen oxides are toxic gases and must be extracted by suction above the surface of the solution.
- Patent EP 1 816 234 A1 describes an aqueous reaction solution and a process for the passivation of zinc and zinc alloys.
- the reaction solutions contain nicotinic acid, its salts or their derivatives. From such reaction solutions, colored passivation layers are produced on zinc and zinc alloys. Nicotinic acid is not suitable as an oxidizing agent in chromium (III) -containing treatment solutions for producing conversion coatings on zinc-containing surfaces.
- the patents EP 1 005 578 B1 and GB 715,607 describe processes for the production of phosphating layers.
- the accelerators used here are organic nitro compounds and organic N-oxides.
- the phosphating layers described here are porous and therefore offer no corrosion protection.
- organic oxidizing agents of the invention selected from aliphatic nitro compounds, aromatic nitro compounds, N-oxides and quinones. Substitution of nitrates by water-soluble, organic oxidants does not result in gaseous, toxic reaction products.
- nitrate ions can be present in the solution without the negative properties being problematic.
- the solution does not contain nitrate.
- an aqueous treatment solution for producing substantially chromium (VI) -free black conversion layers on zinc or zinc alloy layers which contains, inter alia, the following components:
- R 1 to R 5 are independent of one another
- Preferred organic compounds are selected from the group consisting of compounds according to formulas I, III, IV and V where R 1 to R 5 are independently of one another
- Particularly preferred organic compounds are selected from the group consisting of compounds of the formula I., wherein R 1 to R 5 independently
- Suitable classes of compounds are e.g. Nitrobenzoic acids, nitrosalicylic acids, nitrophenols, dinitrophenols, trinitrophenols, nitropropionic acid, pyridine-N-oxides, morpholine-N-oxides and benzoquinones.
- Suitable compounds in the meaning of the invention are therefore, e.g. m-nitrobenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3,5-dinitrosalicylic acid, 2,4-dinitrophenol, m-nitrobenzenesulfonic acid, N-methylmorpholine N-oxide, pyridine N-oxide and p-benzoquinone.
- Equation 1 Examples of reduction reactions of suitable organic oxidants in an acidic medium.
- Another advantage of the components of the invention is that they have no free nitrate and thus can be used in solutions for the production of conversion layers containing dyes with amino groups.
- the disadvantage of the use of nitrate ions known in the art for producing the conversion layer is that the nitrate is reduced to nitrite. This nitrite can undergo diazotization reactions in the strongly acidic solution to form the conversion layer with amino-containing dyes, which react to Undefined dye products, which no longer give the desired surface color of the conversion layer. Such reactions go organically bound NO groups according to the formulas I. - III. not a.
- Aqueous treatment solutions according to the invention contain between 0.2 g / l and 20 g / l chromium (III), preferably between 0.5 g / l and 15 g / l chromium (III) ions and more preferably between 1 g / l and 5 g / l chromium (III) ions.
- no Cr (VI) salts are added to the solution.
- Suitable anions are methanesulfonate, sulfate, hydrogensulfate, borates and the anions of acidic boric esters, phosphate, hydrogenphosphate, dihydrogenphosphate, nitrate, nitrite, chloride, iodide, fluoride, hexafluorosilicate, hexafluorotitanate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, phosphate, Hydrogen phosphate, dihydrogen phosphate or corresponding anions of esters of phosphoric acid.
- Chromium (III) may be added to the solutions either in the form of a chromium (III) salt such as basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chlorite, potassium chromium ( III) sulfate or chromium (III) salts of organic acids such as chromium (III) methanesulfonate, chromium (III) citrate.
- a chromium (III) salt such as basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chlorite, potassium chromium ( III) sulfate or chromium (III) salts of organic acids such as chromium (III) methanesulfonate, chromium (III) citrate.
- complexing agents can be used, such as, for example, polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids.
- carboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, tartaric acid, citric acid, malic acid, ascorbic acid, ethylenedinithlotetraacetic acid, tetrahydrofuran-2-carboxylic acid, maleic acid , Ethylenediaminetetraacetic acid, diethylenediaminopentaacetic acid, nithlotriacetic acid, lactic acid, adipic acid, 4-aminohippuric acid, 4-aminobenzoic acid, 5-aminoisophthalic acid, L-aspartic acid, L
- Dihydroxybenzoic acid 4- (dimethylamino) benzoic acid, glucuronic acid, citrazinic acid, indole-3-carboxylic acid, indole-5-carboxylic acid, butane-1, 2,3,4-tetracarboxylic acid, DL-leucine, 2,2-bis- (hydroxymethyl) propionic acid, quinoline-2,4-dicarboxylic acid, 2-aminopyridine-3-carboxylic acid, 5-amino-2-hydroxybenzoic acid, anthranilic acid, benzene-1, 2,4-tricarboxylic acid, 3,5-diaminobenzoic acid, 4,8-dihydroxyquinoline-2-carboxylic acid, 3,3-dimethylglutaric acid, trans, trans-2,4-haxadienoic acid, 3-hydroxybutyric acid, o-hydroxyhippuric acid, (4-hydroxyphenyl) -acetic acid, imidazole-4-acrylic acid, indole
- the concentration of complexing agents in The treatment solutions may be between 0.05 g / l and the solubility limit of the complexing agents.
- the treatment solutions may further comprise one or more surfactants such as e.g. Oxo alcohol ethoxylates (eg Lugalvan ON110, BASF), fatty alcohol ethoxylates (eg Ethylan CPG 660, Julius Hoesch GmbH), or surfactants with fluorinated radicals (eg Novec FC-4432, 3M) and between 0.01 g / l and 10 g / l another metal ion or metalloidion such as Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P.
- surfactants such as e.g. Oxo alcohol ethoxylates (eg Lugalvan ON110, BASF), fatty alcohol ethoxylates (eg Ethylan CPG 660, Julius Hoesch GmbH), or surfactants with fluorinated radicals (eg Novec FC-4432, 3M) and between 0.01 g / l and
- An aqueous treatment solution is prepared which contains 3.0 g / l Cr 3+ (from chromium (III) chloride hexahydrate), 2 g / l Co 2+ (from cobalt sulfate heptahydrate) and 8 g / l PO 4 3 " (from ortho Phosphoric acid) and 2.5 g / l Fe 2+ (from iron (III) sulfate heptahydrate) and a compound according to the invention or nitrate according to the comparative example according to Table 1.
- the treatment solution is adjusted to a pH of 1.6 with nitric acid / sodium hydroxide
- nitric acid / sodium hydroxide In an alkaline galvanizing process (Protolux 3000, Atotech Deutschland GmbH), a sheet of low-alloy steel is coated with 10 ⁇ m zinc
- the sheet is activated in 0.3% by weight nitric acid for 10 s, washed three times with demineralized water and left for 60 s immersed in the above-described treatment solution. the solution is stirred in this case. After removal of the plate, this is rinsed three times with demin. water at 80 0 C for 10 min in a circulating air oven.
- the black sheet is in the neutral salt spray according to DIN EN ISO 9227 after 6 h initial approaches to zinc corrosion.
- a analogously prepared sheet is treated with an organic-silicate sealant (eg Corrosil Plus 501, Atotech Germany GmbH) and dried in a circulating air oven at 80 0 C for 10 min.
- the sheet is tested in the neutral salt spray test according to DIN EN ISO 9227. The time in h, until the first signs of zinc corrosion are visible, is shown in Table 1.
- Table 1 Experiments with conversion coatings
Abstract
The invention relates to a method for producing a corrosion-protecting overcoat layer, wherein a surface to be treated is brought into contact with an aqueous treatment solution comprising at least one chromium (III) ion source and at least one organic compound which acts as an oxidizer relative to zinc in weakly acidic or acidic solutions. The decorative and functional properties of the surfaces are retained or improved in the process. Also, the known problems involved with using chromium (VI) compounds are avoided.
Description
Konversionsschichten für zinkhaltige Oberflächen Conversion layers for zinc-containing surfaces
Gebiet der ErfindungField of the invention
Die Erfindung betrifft den Korrosionsschutz von metallischen Werkstoffen, insbesondere von solchen, die mit einer Konversionsschicht versehen sind.The invention relates to the corrosion protection of metallic materials, in particular of those which are provided with a conversion layer.
Hintergrund der ErfindungBackground of the invention
Zum Schutz metallischer Werkstoffoberflächen vor korrosiven Umwelteinflüssen stehen im Stand der Technik unterschiedliche Methoden zur Verfügung. Die Beschich- tung des zu schützenden metallischen Werkstücks mit einem Überzug aus einem anderen Metall ist dabei eine in der Technik weit verbreitete und etablierte Methode. Das Beschichtungsmetall kann sich im korrodierenden Medium dabei entweder elektrochemisch edler oder unedler verhalten als das Werkstoffgrundmetall alleine. Verhält sich das Beschichtungsmetall unedeler, so fungiert es im korrodierenden Medium im Sinne eines kathodischen Korrosionsschutzes gegenüber dem Basismetall als Opferanode. Diese mit der Bildung von Korrosionsprodukten des Überzugmetalls verbundene Schutzfunktion ist damit zwar erwünscht, die Korrosionsprodukte des Überzugs führen aber oft selbst zu unerwünschten dekorativen und nicht selten auch zu funktionellen Beeinträchtigungen des Werkstücks. Um die Korrosion des Überzugmetalls zu reduzieren bzw. möglichst lange zu verhindern, werden speziell auf kathodisch schützenden unedlen Überzugsmetallen wie z.B. Zink sowie dessen Legierungen oft sogenannte Konversionsschichten eingesetzt. Hierbei handelt es sich um in wässri- gen Medien in einem weiten pH-Bereich unlösliche Reaktionsprodukte des unedlen Beschichtungsmetalls mit der Reaktionslösung. Beispiele für diese sogenannten Konversionsschichten sind z.B. sogenannte Phosphatierungen und Chromatierungen. Im Falle von Phosphatierungen wird die zu schützende Schicht in eine Phosphationen enthaltende saure Lösung getaucht. Das saure Medium führt zur partiellen Auflösung von Zink aus der Beschichtung. Prinzipiell bilden die freigesetzten Zn2+-Kationen mit den Phosphationen der Reaktionslösung eine schwerlösliche Zinkphosphatschicht auf der Oberfläche aus. Da Zinkphosphatschichten selbst nur einen vergleichsweise schlechten Korrosionsschutz ausbilden, aber ein ausgezeichneter Haftgrund für hier-
auf aufgebrachte Lacke und Farben sind, liegt ihr Anwendungsschwerpunkt in der Funktion als Grundierung für Lackierungen und Anstriche.To protect metallic material surfaces from corrosive environmental influences, different methods are available in the prior art. The coating of the metallic workpiece to be protected with a coating of another metal is a widely used and established method in the art. The coating metal can behave in the corrosive medium either electrochemically nobler or less noble than the material base metal alone. If the coating metal behaves less noble, it acts as a sacrificial anode in the corrosive medium in the sense of cathodic protection against the base metal. Although this is associated with the formation of corrosion products of the coating metal protection function is indeed desirable, but the corrosion products of the coating often lead even to undesirable decorative and often to functional impairments of the workpiece. In order to reduce the corrosion of the coating metal or to prevent as long as possible, so-called conversion layers are often used especially on cathodically protective base coating metals such as zinc and its alloys. These are reaction products of the base metal which are insoluble in aqueous media over a wide pH range with the reaction solution. Examples of these so-called conversion layers are, for example, so-called phosphating and chromating. In the case of phosphating, the layer to be protected is dipped in an acidic solution containing phosphate ions. The acidic medium leads to the partial dissolution of zinc from the coating. In principle, the liberated Zn 2+ cations form a sparingly soluble zinc phosphate layer on the surface with the phosphate ions of the reaction solution. Since zinc phosphate coatings themselves form only a comparatively bad corrosion protection, but an excellent primer for this On applied paints and paints, their main application is in the function of a primer for coatings and paints.
Im Falle von Chromatierungen wird die zu behandelnde Oberfläche in eine saure, Chrom(VI)-lonen enthaltende Lösung getaucht. Handelt es sich beispielsweise um eine Zink-Oberfläche, so löst sich ein Teil des Zinks auf. Unter den hierbei herrschenden reduzierenden Bedingungen wird Chrom(VI) zu Chrom(lll) reduziert, das in dem durch die Wasserstoffentwicklung alkalischeren Oberflächenfilm u.a. als Chrom(lll)- hydroxid bzw. als schwerlöslicher μ-Oxo- oder μ-Hydroxo-verbrückter Chrom(lll) — Komplex abgeschieden wird. Parallel wird schwerlösliches Zinkchromat(VI) gebildet. Insgesamt entsteht ein dicht geschlossener, sehr gut vor dem Korrosionsangriff durch Elektrolyte schützender Konversions-Überzug auf der Zinkoberfläche.In the case of chromating, the surface to be treated is dipped in an acidic solution containing chromium (VI) ions. For example, if it is a zinc surface, some of the zinc will dissolve. Under the reducing conditions prevailing here, chromium (VI) is reduced to chromium (III), which in the hydrogenation more alkaline surface film i.a. as chromium (III) - hydroxide or as sparingly soluble μ-oxo or μ-hydroxo-bridged chromium (III) - complex is deposited. In parallel, sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well protects against corrosion attack by electrolytes conversion coating on the zinc surface.
Chrom(VI)-Verbindungen zeichnen sich neben ihrer akuten Toxizität durch ihr hohes karzinogenes Potential aus, so dass ein Ersatz der mit diesen Verbindungen einhergehenden Verfahren notwendig ist. Als Ersatz für Chromatierungsverfahren mit sechswertigen Chromverbindungen haben sich mittlerweile eine Vielzahl von Verfahren etabliert, die unterschiedliche Komplexe dreiwertiger Chromverbindungen verwenden. Ein entscheidender Schritt im Laufe der Abscheidung besteht in einer Reaktion, durch die der pH-Wert an der Grenzfläche der Zinkoberfläche oder zinkhaltigen Oberfläche zur Lösung soweit ansteigt, dass die Abscheidung der Konversionsschicht erfolgt.In addition to their acute toxicity, chromium (VI) compounds are distinguished by their high carcinogenic potential, so that it is necessary to replace the processes associated with these compounds. As a substitute for chromating processes with hexavalent chromium compounds, a large number of processes have now been established which use different complexes of trivalent chromium compounds. A decisive step in the course of the deposition is a reaction by which the pH at the interface of the zinc surface or zinc-containing surface to the solution increases to such an extent that the deposition of the conversion layer takes place.
Chrom(lll) eignet sich nicht im oben beschriebenen Sinne als Oxidationsmittel für Zink. Eine Reduktion zu Chrom(ll) ist zwar aufgrund der Redoxpotentiale möglich, führt aber nicht zum Anstieg des pH-Wertes an der Grenzfläche. Es ist daher erforderlich, zum Aufbau einer Konversionsschicht aus einer wässrigen sauren Lösung von Chrom(lll)-Ionen zusätzlich ein geeignetes Oxidationsmittel zuzugeben, das an der Grenzfläche Zink- bzw. Zinklegierung-Lösung die Konzentration von Zinkionen wie auch den pH-Wert soweit erhöht, dass die beim pH-Wert im Lösungsinneren löslichen Komponenten der Konversionsschicht auf der Metalloberfläche in eine schwerlösliche Hydrolyseform überführt werden.Chromium (III) is not suitable in the sense described above as an oxidizing agent for zinc. Reduction to chromium (II) is possible due to redox potential, but does not increase the pH at the interface. It is therefore necessary, in order to build up a conversion layer from an aqueous acidic solution of chromium (III) ions, to additionally add a suitable oxidizing agent which increases the concentration of zinc ions as well as the pH at the zinc or zinc alloy interface in that the components of the conversion layer which are soluble in the inside of the solution in solution on the metal surface are converted into a sparingly soluble hydrolysis form.
Um Chrom(VI)-freie Behandlungslösungen zu realisieren, wurden Peroxide wie Wasserstoffperoxid oder Peroxodisulfate als Oxidationsmittel vorgeschlagen
(US 4,384,902, US 4,349,392). Wasserstoffperoxid ist bei den sauren pH-Werten kein hinreichend starkes Oxidationsmittel um Chrom(lll) zu Chrom(VI) zu oxidieren.In order to realize chromium (VI) -free treatment solutions, peroxides such as hydrogen peroxide or peroxodisulfates have been proposed as oxidizing agents (US 4,384,902, US 4,349,392). Hydrogen peroxide is not a sufficiently strong oxidant at the acidic pH values to oxidize chromium (III) to chromium (VI).
Breite Anwendung als Oxidationsmittel, das Zink oxidiert, zur Anhebung des pH- Wertes beiträgt und Chrom(lll) unter den Bedingungen der Behandlungslösungen nicht oxidiert, hat Nitrat gefunden (EP 0 907 762 B1 , EP 1 318 214 A1 , WO 2004/072325 A1 ).Widely used as an oxidizing agent which oxidizes zinc, contributes to raising the pH and does not oxidize chromium (III) under the conditions of the treatment solutions, has found nitrate (EP 0 907 762 B1, EP 1 318 214 A1, WO 2004/072325 A1 ).
Nitrat wird unter den üblichen Reaktionsbedingungen der Behandlungslösungen zunächst zum Nitrit reduziert.Nitrate is first reduced to nitrite under the usual reaction conditions of the treatment solutions.
NO3 " + Zn + 2 H3O+ τ± NO2 " + Zn2+ + 3 H2ONO 3 " + Zn + 2H 3 O + τ ± NO 2 " + Zn 2+ + 3H 2 O
bzw. das so gebildete Nitrit als aktiveres Oxidationsmittel weiter entsprechendor the nitrite thus formed further as a more active oxidizing agent
2 NO2 " + 4 H3O+ + Zn Ϊ± 2 NOt + 6 H2O + Zn2+ 2NO 2 " + 4H 3 O + + Zn Ϊ ± 2NOt + 6H 2 O + Zn 2+
zum Stickstoffmonoxid.to nitric oxide.
2 NO3 " + 3 Zn + 8 H3O+ τ± 2 NOt + 3 Zn2+ + 12 H2O2NO 3 " + 3Zn + 8H 3 O + τ ± 2NOt + 3Zn 2+ + 12H 2 O
Weiterhin ist Nitrit im sauren Milieu der Behandlungslösungen, der pH-Wert liegt üblicherweise zwischen pH 1 und pH 3.5, nicht stabil sondern neigt zur Disproportionie- rung in Nitrat und Stickstoffmonoxid:Furthermore, nitrite is in the acidic medium of the treatment solutions, the pH is usually between pH 1 and pH 3.5, not stable but tends to disproportionation in nitrate and nitrogen monoxide:
3 NO2 " + 2 H3O+ τ± NO3 " + 2 NOt + 3 H2O3 NO 2 "+ 2 H 3 O + τ ± NO 3" + 2 + 3 H 2 O NOt
Sowohl die Reduktion von Nitrit wie auch die Disproportionierung von Nitrit in der sauren Lösung führt damit zur Freisetzung von Stickstoffmonoxid. Stickstoffoxide sind toxische Gase und müssen unbedingt oberhalb der Lösungsoberfläche abgesaugt werden.Both the reduction of nitrite and the disproportionation of nitrite in the acidic solution thus lead to the release of nitric oxide. Nitrogen oxides are toxic gases and must be extracted by suction above the surface of the solution.
Die Patentschrift EP 1 816 234 A1 beschreibt eine wässrige Reaktionslösung und ein Verfahren zur Passivierung von Zink und Zinklegierungen. Die Reaktionslösungen enthalten Nicotinsäure, deren Salze oder deren Derivate. Aus derartigen Reaktionslösungen werden farbige Passivierungsschichten auf Zink und Zinklegierungen erzeugt.
Nicotinsäure ist nicht als Oxidationsmittel in Chrom(lll)-haltigen Behandlungslösungen zur Erzeugung von Konversionsschichten auf Zink-haltigen Oberflächen geeignet.Patent EP 1 816 234 A1 describes an aqueous reaction solution and a process for the passivation of zinc and zinc alloys. The reaction solutions contain nicotinic acid, its salts or their derivatives. From such reaction solutions, colored passivation layers are produced on zinc and zinc alloys. Nicotinic acid is not suitable as an oxidizing agent in chromium (III) -containing treatment solutions for producing conversion coatings on zinc-containing surfaces.
Die Patentschrift EP 1 970 470 A1 beschreibt Chrom(VI)-freie Schwarzpassivierungen für Zink-haltige Oberflächen, die als Komplexbildner Carbonsäurederivate des Pyri- dins enthalten können. Derartige Carbonsäurederivate des Pyridins können in solchen Lösungen nicht als Oxidationsmittel wirken.The patent specification EP 1 970 470 A1 describes chromium (VI) -free black passivations for zinc-containing surfaces, which as complexing agents may contain carboxylic acid derivatives of pyridine. Such carboxylic acid derivatives of pyridine can not act as oxidizing agents in such solutions.
Die Patentschriften EP 1 005 578 B1 und GB 715,607 beschreiben Verfahren zur Erzeugung von Phosphatierungsschichten. Als Beschleuniger kommen hier organische Nitroverbindungen und organische N-Oxide zur Anwendung. Die hier beschriebenen Phosphatierungsschichten sind porös und bieten deshalb keinen Korrosionsschutz.The patents EP 1 005 578 B1 and GB 715,607 describe processes for the production of phosphating layers. The accelerators used here are organic nitro compounds and organic N-oxides. The phosphating layers described here are porous and therefore offer no corrosion protection.
Beschreibung der ErfindungDescription of the invention
Es ist Aufgabe der vorliegenden Erfindung, ein Oxidationsmittel zur Verfügung zu stellen, das die oben dargelegten Kriterien bezüglich Zinkoxidation, Oxoniumionen- verbrauch sowie Reaktivität gegenüber Chrom(lll) erfüllt, nicht aber zur Bildung toxischer Gase führt. Diese Kriterien werden durch die erfindungsgemäßen organischen Oxidationsmittel, ausgewählt aus aliphatischen Nitroverbindungen, aromatischen Nitroverbindungen, N-Oxiden und Chinonen erfüllt. Der Ersatz von Nitraten durch wasserlösliche, organische Oxidationsmittel führt nicht zu gasförmigen, toxischen Reaktionsprodukten.It is an object of the present invention to provide an oxidizing agent which meets the above-mentioned criteria with regard to zinc oxidation, oxonium ion consumption and reactivity with respect to chromium (III), but does not lead to the formation of toxic gases. These criteria are met by the organic oxidizing agents of the invention selected from aliphatic nitro compounds, aromatic nitro compounds, N-oxides and quinones. Substitution of nitrates by water-soluble, organic oxidants does not result in gaseous, toxic reaction products.
In geringer Konzentration können Nitrationen in der Lösung vorliegen, ohne dass die negativen Eigenschaften problematisch sind. Bevorzugt enthält die Lösung jedoch kein Nitrat.In low concentrations nitrate ions can be present in the solution without the negative properties being problematic. Preferably, however, the solution does not contain nitrate.
Diese Aufgabe wird durch eine wässrige Behandlungslösung zur Erzeugung von im wesentlichen Chrom(VI)-freien schwarzen Konversionsschichten auf Zink- oder Zinklegierungsschichten, gelöst, die unter anderem die folgenden Komponenten enthält:This object is achieved by an aqueous treatment solution for producing substantially chromium (VI) -free black conversion layers on zinc or zinc alloy layers, which contains, inter alia, the following components:
- mindestens eine Cr3+-lonen Quelle undat least one Cr 3+ ion source and
- mindestens eine organische Verbindung ausgewählt aus der Gruppe enthaltend
- containing at least one organic compound selected from the group
IV. V.IV. V.
wobei R1 bis R5 unabhängig voneinanderwhere R 1 to R 5 are independent of one another
a) ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, linear oder verzweigt odera) a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, linear or branched or
b) eine -NR2, -NO2, -COOR, -OR, -SO3R Gruppe mit R = -H oder Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, darstellen, wobei Methlyl-, Ethyl-, n-Propyl- und Isopropyl besonders bevorzugt sindb) a -NR 2 , -NO 2 , -COOR, -OR, -SO 3 R group with R = -H or alkyl group having 1 to 5 carbon atoms, linear or branched, where methyl, ethyl, n- Propyl and isopropyl are particularly preferred
mit der Maßgabe, dass O bis 2 Reste R1 bis R5 ausgewählt sind aus der Gruppe b).with the proviso that O to 2 radicals R 1 to R 5 are selected from the group b).
Bevorzugte organische Verbindungen werden aus der Gruppe bestehend aus Verbindungen gemäß den Formeln I., III., IV. und V. ausgewählt wobei R1 bis R5 unabhängig voneinanderPreferred organic compounds are selected from the group consisting of compounds according to formulas I, III, IV and V where R 1 to R 5 are independently of one another
a) ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, linear oder verzweigt odera) a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, linear or branched or
b) eine -NR2, -NO2, -COOR, -OR, -SO3R Gruppe mit R = -H oder Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, darstellen, wobei Methlyl-, Ethyl-, n-Propyl- und Isopropyl besonders bevorzugt sind
mit der Maßgabe, dass O bis 2 Reste R1 bis R5 ausgewählt sind aus der Gruppe b).b) a -NR 2 , -NO 2 , -COOR, -OR, -SO 3 R group with R = -H or alkyl group having 1 to 5 carbon atoms, linear or branched, where methyl, ethyl, n- Propyl and isopropyl are particularly preferred with the proviso that O to 2 radicals R 1 to R 5 are selected from the group b).
Besonders bevorzugte organische Verbindungen werden aus der Gruppe bestehend aus Verbindungen gemäß Formel I. ausgewählt, wobei R1 bis R5 unabhängig voneinanderParticularly preferred organic compounds are selected from the group consisting of compounds of the formula I., wherein R 1 to R 5 independently
a) ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, linear oder verzweigt odera) a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, linear or branched or
b) eine -NR2, -NO2, -COOR, -OR, -SO3R Gruppe mit R = -H oder Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, darstellen, wobei Methlyl-, Ethyl-, n-Propyl- und Isopropyl besonders bevorzugt sindb) a -NR 2 , -NO 2 , -COOR, -OR, -SO 3 R group with R = -H or alkyl group having 1 to 5 carbon atoms, linear or branched, where methyl, ethyl, n- Propyl and isopropyl are particularly preferred
mit der Maßgabe, dass 0 bis 2 Reste R1 bis R5 ausgewählt sind aus der Gruppe b).with the proviso that 0 to 2 radicals R 1 to R 5 are selected from the group b).
Beispiele für geeignete Verbindungsklassen sind z.B. Nitrobenzoesäuren, Nitrosali- cylsäuren, Nitrophenole, Dinitrophenole, Trinitrophenole, Nitropropionsäure, Pyridin- N-oxide, Morpholin-N-oxide sowie Benzochinone. Geeignete Verbindungen im Sinne der Erfindung sind daher z.B. m-Nitrobenzoesäure, 2-Hydroxy-5-nitrobenzoesäure, 3,5-Dinitrosalicylsäure, 2,4-Dinitrophenol, m-Nitrobenzolsulfonsäure, N-Methyl- morpholin-N-oxid, Pyridin-N-oxid sowie p-Benzochinon.Examples of suitable classes of compounds are e.g. Nitrobenzoic acids, nitrosalicylic acids, nitrophenols, dinitrophenols, trinitrophenols, nitropropionic acid, pyridine-N-oxides, morpholine-N-oxides and benzoquinones. Suitable compounds in the meaning of the invention are therefore, e.g. m-nitrobenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3,5-dinitrosalicylic acid, 2,4-dinitrophenol, m-nitrobenzenesulfonic acid, N-methylmorpholine N-oxide, pyridine N-oxide and p-benzoquinone.
Überraschenderweise stellte sich weiterhin heraus, dass bei Verwendung organischer Oxidationsmittel wie Chinonen, N-Oxiden sowie aromatischer Nitroverbindungen wie Nitrobenzoesäuren, Nitrophenolen, insbesondere Nitrobenzolsulfonsäuren wie z.B. m-Nitrobenzolsulfonsäure der Korrosionsschutz der erzeugten Konversionsschichten signifikant über dem liegt, der durch entsprechende nitrathaltige Passivierungen erreicht werden kann. Dies gilt insbesondere für Konversionsschichten, die durch Einbau von Metallpartikeln von Eisen, Cobalt oder Nickel oder Partikeln schwarzer bzw. schwärzender Metallverbindungen von Verbindungen der genannten Metalle schwarz bzw. dunkel pigmentiert sind.Surprisingly, it has also been found that when using organic oxidants such as quinones, N-oxides and aromatic nitro compounds such as nitrobenzoic acids, nitrophenols, in particular nitrobenzenesulfonic such. m-nitrobenzenesulfonic the corrosion protection of the conversion layers is significantly above that which can be achieved by corresponding nitrate-containing passivations. This applies in particular to conversion layers which are pigmented black or dark by incorporation of metal particles of iron, cobalt or nickel or particles of black or blackening metal compounds of compounds of the metals mentioned.
Höchstwahrscheinlich ist dies neben einer anderen Kinetik der Zinkoxidation und damit des Konversionsschichtwachstums auch auf korrosionsinhibierende Eigen-
Schäften der in der Passivierungsschicht mit abgeschiedenen bzw. adsorbierten Reduktionsprodukte der organischen Oxidationsmittel, die ihrerseits gute Reduktionsmittel sind, zurückzuführen. Beispiele für mögliche Reduktionsreaktionen sind in Gleichung 1 angegeben.This is most likely not only due to a different kinetics of the zinc oxidation and thus of the conversion layer growth but also to corrosion-inhibiting properties. Shafts of the passivation layer with deposited or adsorbed reduction products of organic oxidants, which in turn are good reducing agents, due. Examples of possible reduction reactions are given in Equation 1.
Gleichung 1. Beispiele für Reduktionsreaktionen geeigneter organischer Oxidationsmittel im sauren Milieu.Equation 1. Examples of reduction reactions of suitable organic oxidants in an acidic medium.
Ein weiterer Vorteil der erfindungsgemäßen Komponenten besteht darin, dass sie keine freies Nitrat aufweisen und damit in Lösungen zur Erzeugung von Konversionsschichten eingesetzt werden können, die Farbstoffe mit Aminogruppen enthalten. Der Nachteil der im Stand der Technik bekannten Verwendung von Nitrationen zur Erzeugung der Konversionsschicht besteht darin, dass das Nitrat zu Nitrit reduziert wird. Dieses Nitrit kann in der stark sauren Lösung zur Bildung der Konversionsschicht mit aminohaltigen Farbstoffen Diazotierungsreaktionen eingehen, die zu Undefinierten Farbstoffprodukten reagieren, die nicht mehr die gewünschte Oberflächenfarbe der Konversionsschicht ergeben. Solche Reaktionen gehen organisch gebundene NO-Gruppen gemäß der Formeln I. - III. nicht ein.
Erfindungsgemäße wässrige Behandlungslösungen enthalten zwischen 0.2 g/l und 20 g/l Chrom(lll), bevorzugt zwischen 0.5 g/l und 15 g/l Chrom(lll)-Ionen und besonders bevorzugt zwischen 1 g/l und 5 g/l Chrom(lll)-Ionen. Zu der Lösung werden keine Cr(VI)-Salze gegeben. Als Anionen können beispielsweise Methansulfonat, Sulfat, Hydrogensulfat, Borate, sowie die Anionen saurer Borsäureester, Phosphat, Hydro- genphosphat, Dihydrogenphosphat, Nitrat, Nitrit, Chlorid, lodid, Fluorid, Hexafluorosi- likat, Hexafluorotitanat, Tetrafluoroborat, Hexafluoroantimonat, Hexafluorphosphat, Phosphat, Hydrogenphosphat, Dihydrogenphosphat bzw. entsprechende Anionen von Estern der Phosphorsäure enthalten. Chrom(lll) kann den Lösungen entweder in Form eines Chrom(lll)-Salzes wie z.B. basisches Chrom(lll)-sulfat, Chrom(lll)- hydroxid, Chrom(lll)-dihydrogenphosphat, Chrom(lll)-chlohd, Kaliumchrom(lll)-sulfat oder Chrom(lll)-Salzen organischer Säuren wie z.B. Chrom(lll)-methansulfonat, Chrom(lll)-citrat zugegeben werden.Another advantage of the components of the invention is that they have no free nitrate and thus can be used in solutions for the production of conversion layers containing dyes with amino groups. The disadvantage of the use of nitrate ions known in the art for producing the conversion layer is that the nitrate is reduced to nitrite. This nitrite can undergo diazotization reactions in the strongly acidic solution to form the conversion layer with amino-containing dyes, which react to Undefined dye products, which no longer give the desired surface color of the conversion layer. Such reactions go organically bound NO groups according to the formulas I. - III. not a. Aqueous treatment solutions according to the invention contain between 0.2 g / l and 20 g / l chromium (III), preferably between 0.5 g / l and 15 g / l chromium (III) ions and more preferably between 1 g / l and 5 g / l chromium (III) ions. To the solution, no Cr (VI) salts are added. Examples of suitable anions are methanesulfonate, sulfate, hydrogensulfate, borates and the anions of acidic boric esters, phosphate, hydrogenphosphate, dihydrogenphosphate, nitrate, nitrite, chloride, iodide, fluoride, hexafluorosilicate, hexafluorotitanate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, phosphate, Hydrogen phosphate, dihydrogen phosphate or corresponding anions of esters of phosphoric acid. Chromium (III) may be added to the solutions either in the form of a chromium (III) salt such as basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chlorite, potassium chromium ( III) sulfate or chromium (III) salts of organic acids such as chromium (III) methanesulfonate, chromium (III) citrate.
Daneben können Komplexbildner eingesetzt werden wie z.B. Polycarbonsäuren, Hydroxycarbonsäuren, Hydroxypolycarbonsäuren, Aminocarbonsäuren oder Hydro- xyphosphonsäuren. Beispiele für mögliche Carbonsäuren sind Oxalsäure, Malonsäu- re, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebazinsäure, Maleinsäure, Phthalsäure, Terephthalsäure, Weinsäure, Citronensäu- re, Äpfelsäure, Ascorbinsäure, Ethylendinithlotetraessigsäure, Tetrahydrofuran-2- carbonsäure, Maleinsäure, Ethylendiamintetraessigsäure, Diethylendiaminpentaes- sigsäure, Nithlotriessigsäure, Milchsäure, Adipinsäure, 4-Aminohippursäure, 4- Aminobezoesäure, 5-Aminoisophthalsäure, L-Asparaginsäure, L-Glutamin, L- Glutaminsäure, Alanin, beta-Alanin, L-Arginin, L-Asparagin, L- Alanin, N,N-Bis(2- hydroxyethyl)-glycin, L-Cystein, L-Cystin, Glutathion, Glycin, Glycylglycin, L-Histidin, L-Hydroxyprolin, L-Isoleucin, L-Leucin, L-Lysin, L-Methionin, L-Ornithin, L- Phenylalanin, L-Prolin, L-Serin, L-Tyrosin, L-Tryptophan, L-Threonin, L-VaNn, N- [Ths(hydroxymethyl)-methyl]-glycin, L-Citrullin, N-Acetyl-L-cystein, N-(2-Acetamindo)- iminodiessigsäure, 1 ,2-Cyclohexeylen-dinithlotetraessigsäure, D(+)-Biotin, L- Norleucin, 5-Aminolävulinsäure, DL-Methionin, 3-Aminobenzoesäure, 6- Aminohexansäure, Acetylendicarbonsäure, Pyhdin-2,3-dicarbonsäure, (-)-Chinasäure, 4-Amino-2-hydroxybenzoesäure, Pyridin-2,6-dicarbonsäure, Pyridin-2-carbonsäure, Pyrazin-2,3-dicarbonsäure, Pyrazin-2-carbonsäure, Pyhdin-4-carbonsäure, 3,5- Diyhdroxybenzoesäure, 2,4-Dihydroxybenzoesäure, Sebacinsäure, Benzol-1 ,3,5-
tricarbonsäure, Furan-2-carbonsäure, Methylenbernsteinsäure, DL-Mandelsäure, DL- alpha-Aminophenylessigsäure, DL-Tropasäure, 2,2'-Thiodiessigsäure, 3,3'- Thiodipropionsäure, 3-(2-Furyl)-acrylsäure, Piperidin-4-carbonsäure, 4- Guanidinobenzoesäure, L-Homoserin, trans-Propen-1 ,2,3-tricarbonsäure, (R)-(-)- Citramalsäure, (3-Hydroxyphenyl)-essigsäure, 4-Hydroxychinolin-2-carbonsäure, N- Acetyl-L-glutaminsäure, N-Acetyl-DL-valin, 4-Aminohippursäure, 2,6-In addition, complexing agents can be used, such as, for example, polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids. Examples of possible carboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, tartaric acid, citric acid, malic acid, ascorbic acid, ethylenedinithlotetraacetic acid, tetrahydrofuran-2-carboxylic acid, maleic acid , Ethylenediaminetetraacetic acid, diethylenediaminopentaacetic acid, nithlotriacetic acid, lactic acid, adipic acid, 4-aminohippuric acid, 4-aminobenzoic acid, 5-aminoisophthalic acid, L-aspartic acid, L-glutamine, L-glutamic acid, alanine, beta-alanine, L-arginine, L-asparagine , L-alanine, N, N-bis (2-hydroxyethyl) glycine, L-cysteine, L-cystine, glutathione, glycine, glycylglycine, L-histidine, L-hydroxyproline, L-isoleucine, L-leucine, L- Lysine, L-methionine, L-ornithine, L-phenylalanine, L-proline, L-serine, L-tyrosine, L-tryptophan, L-threonine, L-VaNn, N- [ths (hydroxymethyl) -methyl] -glycine , L-citrulline, N-acetyl-L-cysteine, N- (2-acetamido) -iminodies acetic acid, 1,2-cyclohexylene-dinithlotetraacetic acid, D (+) - biotin, L-norleucine, 5-aminolevulinic acid, DL-methionine, 3-aminobenzoic acid, 6-aminohexanoic acid, acetylenedicarboxylic acid, pyhdine-2,3-dicarboxylic acid, (-) Quinic acid, 4-amino-2-hydroxybenzoic acid, pyridine-2,6-dicarboxylic acid, pyridine-2-carboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2-carboxylic acid, pyhdine-4-carboxylic acid, 3,5-dihydroxybenzoic acid , 2,4-Dihydroxybenzoic acid, sebacic acid, benzene-1, 3,5- tricarboxylic acid, furan-2-carboxylic acid, methylenesuccinic acid, DL-mandelic acid, DL-alpha-aminophenylacetic acid, DL-tropic acid, 2,2'-thiodiacetic acid, 3,3'-thiodipropionic acid, 3- (2-furyl) -acrylic acid, piperidine 4-carboxylic acid, 4-guanidinobenzoic acid, L-homoserine, trans-propene-1, 2,3-tricarboxylic acid, (R) - (-) - citramalic acid, (3-hydroxyphenyl) -acetic acid, 4-hydroxyquinoline-2-carboxylic acid, N-acetyl-L-glutamic acid, N-acetyl-DL-valine, 4-amino-hippuric acid, 2,6-
Dihydroxybenzoesäure, 4-(Dimethylamino)-benzoesäure, Glucuronsäure, Citrazinsäu- re, lndol-3-carbonsäure, lndol-5-carbonsäure, Butan-1 ,2,3,4-tetracarbonsäure, DL- Leucin, 2,2-Bis-(hydroxymethyl)-propionsäure, Chinlin-2,4-dicarbonsäure, 2- Aminopyridin-3-carbonsäure, 5-Amino-2-hydroxybenzoesäure, Anthranilsäure, Ben- zol-1 ,2,4-tricarbonsäure, 3,5-Diaminobenzoesäure, 4,8-Dihydroxychinolin-2- carbonsäure, 3,3-Dimethylglutarsäure, trans,trans-2,4-Haxadiensäure, 3- Hydroxybuttersäure, o-Hydroxyhippursäure, (4-Hydroxyphenyl)-essigsäure, Imidazol- 4-acrylsäure, lndol-2-carbonsäure, lndol-3-propionsäure, Mercaptobernsteinsäure, 3- Oxoglutarsäure, Pyhdin-2,4-dicarbonsäure, Pyhdin-3,5-dicarbonsäure, 2- Methylalanin, 2-Sulfobenzoesäure, Pyhdin-2,5-dicarbonsäure, Gluconsäure, 4- Aminobenzoesäure, (-)-Shikiminsäure, Chinaldinsäure, 5-Hydroxyisophthalsäure, Pyrazol-3,5-dicarbonsäuren, Pyhdin-3,4-dicarbonsäure, 1 ,2-Diaminopropan- tetraessigsäure, 2-Pyridylessigsäure,D-Norvalin, 2-Methylglutarsäure, 2,3- Dibrombernsteinsäure, 3-Methylglutarsäure, (2-Hydroxyphenyl)essigsäure, 3,4- Dihydroxybenzoesäure, Diglycolsäure, Propan-1 ,2,3-tricarbonsäure, 2,3- Dimethylaminopropionsäure, 2,5-Dihydroxybenzoesäure, 2-Hydroxyisobuttersäure, Phenylbernsteinsäure, N-Phenylglycin, I -Aminocylcohexancarbonsäure, Sarcosin, Tropasäure, Azelainsäure, Brenzschleimsäure, sowie Schleimsäure. Es können neben den Säuren auch alle Anhydride, Salze, Nitrile u.a. Verbindungen, die im sauren Milieu als Quelle für die Carbonsäuren fungieren können eingesetzt werden. Beispiele chiraler Verbindungen sind nicht auf die angegebene Konfiguration beschränkt; es können auch Diasteromere, Enantiomere oder Racemate der angegebenen Verbindungen eingesetzt werden.Dihydroxybenzoic acid, 4- (dimethylamino) benzoic acid, glucuronic acid, citrazinic acid, indole-3-carboxylic acid, indole-5-carboxylic acid, butane-1, 2,3,4-tetracarboxylic acid, DL-leucine, 2,2-bis- (hydroxymethyl) propionic acid, quinoline-2,4-dicarboxylic acid, 2-aminopyridine-3-carboxylic acid, 5-amino-2-hydroxybenzoic acid, anthranilic acid, benzene-1, 2,4-tricarboxylic acid, 3,5-diaminobenzoic acid, 4,8-dihydroxyquinoline-2-carboxylic acid, 3,3-dimethylglutaric acid, trans, trans-2,4-haxadienoic acid, 3-hydroxybutyric acid, o-hydroxyhippuric acid, (4-hydroxyphenyl) -acetic acid, imidazole-4-acrylic acid, indole 2-carboxylic acid, indole-3-propionic acid, mercaptosuccinic acid, 3-oxoglutaric acid, pyhdine-2,4-dicarboxylic acid, pyhdine-3,5-dicarboxylic acid, 2-methylalanine, 2-sulfobenzoic acid, pyhdine-2,5-dicarboxylic acid, gluconic acid, 4-aminobenzoic acid, (-) - shikimic acid, quinaldic acid, 5-hydroxyisophthalic acid, pyrazole-3,5-dicarboxylic acids, pyhdine-3,4-dicarboxylic acid, 1, 2-diaminopropane-tetraacetic acid, 2-pyridyl-acetic acid acid, D-norvaline, 2-methylglutaric acid, 2,3-dibromosuccinic acid, 3-methylglutaric acid, (2-hydroxyphenyl) acetic acid, 3,4-dihydroxybenzoic acid, diglycolic acid, propane-1,2,3-tricarboxylic acid, 2,3-dimethylaminopropionic acid , 2,5-dihydroxybenzoic acid, 2-hydroxyisobutyric acid, phenylsuccinic acid, N-phenylglycine, 1-aminocyclohexanecarboxylic acid, sarcosine, tropic acid, azelaic acid, pyruvic acid, as well as mucic acid. In addition to the acids, all anhydrides, salts, nitriles and the like may also be used. Compounds that can act as a source of the carboxylic acids in an acidic medium can be used. Examples of chiral compounds are not limited to the specified configuration; it is also possible to use diastereomers, enantiomers or racemates of the compounds indicated.
Diese Aufzählung möglicher Komplexbildner gibt lediglich Beispiele für geeignete Verbindungen, begrenzt die Gruppe der erfindungsgemäß einsetzbaren Substanzen aber nicht auf die genannten Substanzen. Die Konzentration der Komplexbildner in
den Behandlungslösungen kann zwischen 0.05 g/l und der Löslichkeitsgrenze der Komplexbildner liegen.This list of possible complexing agents merely gives examples of suitable compounds, but does not limit the group of substances which can be used according to the invention to the substances mentioned. The concentration of complexing agents in The treatment solutions may be between 0.05 g / l and the solubility limit of the complexing agents.
Die Behandlungslösungen können ferner weiterhin eine oder mehrere oberflächenaktive Substanzen wie z.B. Oxo-alkoholethoxylate (z.B. Lugalvan ON110, BASF), Fet- talkoholethoxylate (z.B. Ethylan CPG 660, Julius Hoesch GmbH), oder Tenside mit fluorierten Resten (z.B. Novec FC-4432, 3M) und zwischen 0.01 g/l und 10 g/l eines weiteren Metallions oder Metalloidion wie z.B. Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, AI, Si, P enthalten.The treatment solutions may further comprise one or more surfactants such as e.g. Oxo alcohol ethoxylates (eg Lugalvan ON110, BASF), fatty alcohol ethoxylates (eg Ethylan CPG 660, Julius Hoesch GmbH), or surfactants with fluorinated radicals (eg Novec FC-4432, 3M) and between 0.01 g / l and 10 g / l another metal ion or metalloidion such as Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P.
BeispieleExamples
Allgemeine VersuchsvorschriftGeneral test procedure
Es wird eine wässrige Behandlungslösung angesetzt, die 3.0 g/l Cr3+ (aus Chrom(lll)- chlorid Hexahydrat), 2 g/l Co2+ (aus Cobaltsulfat Heptahydrat) sowie 8 g/l PO4 3" (aus ortho-Phosphorsäure) und 2.5 g/l Fe2+ (aus Eisen(lll)-sulfat Heptahydrat) sowie eine erfindungsgemäße Verbindung bzw. Nitrat gemäß Vergleichsbeispiel gemäß Tabelle 1 enthält. Die Behandlungslösung wird mit Salpetersäure / Natriumhydroxid auf einen pH-Wert von 1.6 eingestellt. In einem alkalischen Verzinkungsverfahren (Protolux 3000, Atotech Deutschland GmbH) wird ein Blech aus niedriglegiertem Stahl mit 10 μm Zink beschichtet. Das Blech wird in 0.3 Gew.%iger Salpetersäure für 10 s aktiviert, dreifach mit demin. Wasser gespült und für 60 s in die oben beschriebene Behandlungslösung getaucht. Die Lösung wird hierbei gerührt. Nach Entnehmen des Bleches wird dieses mit demin. Wasser dreifach gespült und bei 80 0C für 10 min im Umluftofen getrocknet. Das schwarze Blech zeigt im neutralen Salzsprühnebeltest nach DIN EN ISO 9227 nach 6 h erste Ansätze zur Zinkkorrosion. Ein analog hergestelltes Blech wird mit einer organisch-silikatischen Versiegelung (z.B. Corrosil Plus 501 , Atotech Deutschland GmbH) behandelt und im Umluftofen bei 80 0C für 10 min getrocknet. Das Blech wird im neutralen Salzsprühnebeltest nach DIN EN ISO 9227 geprüft. Die Zeitdauer in h, bis erste Anzeichen von Zinkkorrosion erkennbar sind, ist in Tabelle 1 wiedergegeben.
Tabelle 1 : Versuche mit KonversionsschichtenAn aqueous treatment solution is prepared which contains 3.0 g / l Cr 3+ (from chromium (III) chloride hexahydrate), 2 g / l Co 2+ (from cobalt sulfate heptahydrate) and 8 g / l PO 4 3 " (from ortho Phosphoric acid) and 2.5 g / l Fe 2+ (from iron (III) sulfate heptahydrate) and a compound according to the invention or nitrate according to the comparative example according to Table 1. The treatment solution is adjusted to a pH of 1.6 with nitric acid / sodium hydroxide In an alkaline galvanizing process (Protolux 3000, Atotech Deutschland GmbH), a sheet of low-alloy steel is coated with 10 μm zinc The sheet is activated in 0.3% by weight nitric acid for 10 s, washed three times with demineralized water and left for 60 s immersed in the above-described treatment solution. the solution is stirred in this case. After removal of the plate, this is rinsed three times with demin. water at 80 0 C for 10 min in a circulating air oven. the black sheet is in the neutral salt spray according to DIN EN ISO 9227 after 6 h initial approaches to zinc corrosion. A analogously prepared sheet is treated with an organic-silicate sealant (eg Corrosil Plus 501, Atotech Germany GmbH) and dried in a circulating air oven at 80 0 C for 10 min. The sheet is tested in the neutral salt spray test according to DIN EN ISO 9227. The time in h, until the first signs of zinc corrosion are visible, is shown in Table 1. Table 1: Experiments with conversion coatings
Claims
1. Wässrige Behandlungslösung zur Erzeugung von im wesentlichen Chrom(VI)- freien Konversionsschichten auf Zink- oder Zinklegierungsschichten, wobei die Lösung enthält:An aqueous treatment solution for the production of essentially chromium (VI) -free conversion layers on zinc or zinc alloy layers, the solution comprising:
- mindestens eine Cr3+-lonen Quelle undat least one Cr 3+ ion source and
- mindestens eine organische Verbindung ausgewählt aus der Gruppe enthaltend- containing at least one organic compound selected from the group
IV. V.IV. V.
wobei R1 bis R5 unabhängig voneinanderwhere R 1 to R 5 are independent of one another
a) ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, linear oder verzweigt odera) a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, linear or branched or
b) eine -NR2, -NO2, -COOR, -OR, -SO3R Gruppe mit R = -H oder Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, darstellen,b) a -NR 2 , -NO 2 , -COOR, -OR, -SO 3 R group with R = -H or alkyl group having 1 to 5 carbon atoms, linear or branched,
und der Maßgabe, dass O bis 2 Reste R1 bis R5 ausgewählt sind aus der Gruppe b). and with the proviso that O to 2 radicals R 1 to R 5 are selected from the group b).
2. Wässrige Behandlungslösung nach Anspruch 1 , dadurch gekennzeichnet, dass die organische Verbindung ausgewählt ist aus der Gruppe umfassend2. Aqueous treatment solution according to claim 1, characterized in that the organic compound is selected from the group comprising
IV. V.IV. V.
wobei R1 bis R5 unabhängig voneinanderwhere R 1 to R 5 are independent of one another
a) ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, linear oder verzweigt odera) a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, linear or branched or
b) eine -NR2, -NO2, -COOR, -OR, -SO3R Gruppe mit R = -H oder Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, darstellen,b) a -NR 2 , -NO 2 , -COOR, -OR, -SO 3 R group with R = -H or alkyl group having 1 to 5 carbon atoms, linear or branched,
und der Maßgabe, dass 0 bis 2 Reste R1 bis R5 ausgewählt sind aus der Gruppe b).and with the proviso that 0 to 2 radicals R 1 to R 5 are selected from the group b).
3. Wässrige Behandlungslösung nach anspruch 1 , dadurch gekennzeichnet, dass die organische Verbindung ausgewählt ist aus der Gruppe umfassend3. Aqueous treatment solution according to claim 1, characterized in that the organic compound is selected from the group comprising
wobei R1 bis R5 unabhängig voneinander where R 1 to R 5 are independent of one another
a) ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, linear oder verzweigt odera) a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, linear or branched or
b) eine -NR2, -NO2, -COOR, -OR, -SO3R Gruppe mit R = -H oder Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, linear oder verzweigt, darstellen,b) a -NR 2 , -NO 2 , -COOR, -OR, -SO 3 R group with R = -H or alkyl group having 1 to 5 carbon atoms, linear or branched,
und der Maßgabe, dass 0 bis 2 Reste R1 bis R5 ausgewählt sind aus der Gruppe b).and with the proviso that 0 to 2 radicals R 1 to R 5 are selected from the group b).
4. Wässrige Behandlungslösung nach Anspruch 1 , dadurch gekennzeichnet, dass die organische Verbindung ausgewählt ist aus der Gruppe enthaltend m- Nitrobenzoesäure, 2-Hydroxy-5-nitrobenzoesäure, 3,5-Dinitrosalicylsäure, 2,4- Dinitrophenol, m-Nitrobenzolsulfonsäure, N-Methylmorpholin-N-oxid, Pyridin-N- oxid, und p-Benzochinon.4. Aqueous treatment solution according to claim 1, characterized in that the organic compound is selected from the group comprising m-nitrobenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3,5-dinitrosalicylic acid, 2,4-dinitrophenol, m-nitrobenzenesulfonic acid, N Methylmorpholine N-oxide, pyridine N-oxide, and p-benzoquinone.
5. Wässrige Behandlungslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Konzentration der organischen Verbindungen I. - V. zwischen 30 mg/l und 30 g/l der Substanz liegen.5. Aqueous treatment solution according to one of the preceding claims, characterized in that the concentration of the organic compounds I.V. lies between 30 mg / l and 30 g / l of the substance.
6. Wässrige Behandlungslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Behandlungslösung zwischen 0.2 g/l und 20 g/l Chrom(lll)-Ionen enthält.6. An aqueous treatment solution according to any one of the preceding claims, characterized in that the treatment solution contains between 0.2 g / l and 20 g / l chromium (III) ions.
7. Wässrige Behandlungslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Behandlungslösung mindestens ein Anion ausgewählt aus der Gruppe enthaltend Methansulfonat, Sulfat, Hydrogensulfat, Borat, saure Borsäureester, Phosphat, Hydrogenphosphat, Dihydrogenphosphat, Chlorid,7. Aqueous treatment solution according to any one of the preceding claims, characterized in that the treatment solution at least one anion selected from the group consisting of methanesulfonate, sulfate, hydrogen sulfate, borate, acidic boric acid esters, phosphate, hydrogen phosphate, dihydrogen phosphate, chloride,
lodid, Fluorid, Nitrat, Hexafluorosilikat, Hexafluorotitanat, Tetrafluoroborat, He- xafluoroantimonat, Hexafluorphosphat, Phosphat, Hydrogenphosphat, Dihydrogenphosphat und Anionen von Estern der Phosphorsäure enthalten.iodide, fluoride, nitrate, hexafluorosilicate, hexafluorotitanate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, phosphate, hydrogen phosphate, dihydrogen phosphate and anions of esters of phosphoric acid.
8. Wässrige Behandlungslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Behandlungslösung weiterhin mindestens ein Metall oder Metalloid ausgewählt aus der Gruppe enthaltend Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, AI, Si, P in einer Konzentration zwischen 0.01 und 10 g/l enthält.8. Aqueous treatment solution according to one of the preceding claims, characterized in that the treatment solution further comprises at least one metal or metalloid selected from the group consisting of Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P in a concentration between 0.01 and 10 g / l.
9. Wässrige Behandlungslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Behandlungslösung zwischen 0.05 g/l 20 g/l mindestens einen Komplexbildner ausgewählt aus der Gruppe enthaltend Polycarbon- säuren, Hydroxycarbonsäuren, Hydroxypolycarbonsäure, Aminocarbonsäuren oder Hydroxyphosphonsäuren enthält.9. Aqueous treatment solution according to any one of the preceding claims, characterized in that the treatment solution contains between 0.05 g / l 20 g / l at least one complexing agent selected from the group containing polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acid, aminocarboxylic acids or hydroxyphosphonic acids.
10. Wässrige Behandlungslösung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Behandlungslösung einen pH-Wert zwischen pH 0.1 und pH 7 aufweist.10. An aqueous treatment solution according to any one of the preceding claims, characterized in that the treatment solution has a pH value between pH 0.1 and pH 7.
11. Verfahren zur Behandlung einer eine Konversionsschicht aufweisende Oberfläche, dadurch gekennzeichnet, dass die zu behandelnde Oberfläche in eine Behandlungslösung gemäß einem der Ansprüche 1-10 eingetaucht wird.11. A method for treating a conversion layer having a surface, characterized in that the surface to be treated is immersed in a treatment solution according to any one of claims 1-10.
12. Verfahren nach Anspruch 11 dadurch gekennzeichnet, dass die Behandlungsdauer in der Behandlungslösung zwischen 0.5 s und 180 s liegt.12. The method according to claim 11, characterized in that the treatment time in the treatment solution is between 0.5 s and 180 s.
13. Verfahren nach den Ansprüchen 11 und 12, dadurch gekennzeichnet, dass die Behandlungslösung eine Temperatur zwischen 10 0C und 90 0C aufweist. 13. The method according to claims 11 and 12, characterized in that the treatment solution has a temperature between 10 0 C and 90 0 C.
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| PL09760833T PL2358922T3 (en) | 2008-11-27 | 2009-11-23 | Conversion layers for surfaces containing zinc |
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| DE102008044143A DE102008044143B4 (en) | 2008-11-27 | 2008-11-27 | Aqueous treatment solution and method for producing conversion layers for zinc-containing surfaces |
| PCT/EP2009/065646 WO2010060883A1 (en) | 2008-11-27 | 2009-11-23 | Conversion layers for surfaces containing zinc |
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| EP09760833.5A Not-in-force EP2358922B1 (en) | 2008-11-27 | 2009-11-23 | Conversion layers for surfaces containing zinc |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20110217476A1 (en) |
| EP (1) | EP2358922B1 (en) |
| JP (1) | JP5562347B2 (en) |
| KR (1) | KR20110089304A (en) |
| CN (1) | CN102227516B (en) |
| DE (1) | DE102008044143B4 (en) |
| ES (1) | ES2565839T3 (en) |
| PL (1) | PL2358922T3 (en) |
| WO (1) | WO2010060883A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2617865A4 (en) * | 2010-09-14 | 2014-12-31 | Yuken Kogyo Co Ltd | Chemical film finishing agent and method for producing same |
| US11008659B2 (en) * | 2014-12-26 | 2021-05-18 | Dipsol Chemicals Co., Ltd. | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film |
| US20160348245A1 (en) * | 2015-05-28 | 2016-12-01 | Macdermid, Incorporated | Method of Pretreatment for Electroless Plating |
| EP3156518A1 (en) * | 2015-10-14 | 2017-04-19 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Corrosion inhibitor composition for magnesium or magnesium alloys |
| CN105937031B (en) * | 2016-06-29 | 2018-10-30 | 周少霞 | A kind of preparation method of heat zinc coating plate passivating solution |
| KR101998606B1 (en) * | 2018-11-21 | 2019-07-10 | 주식회사 지에스켐텍 | trivalent chromate black corrosion-resistant enhancer agent for Zinc-Nickel plating and Surface treatment of Zinc-Nickel plating layer using the same |
| CN114592186B (en) * | 2022-04-27 | 2024-03-12 | 上海库曜新材料有限公司 | Chromium-free passivation method for zinc powder |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB715607A (en) * | 1948-07-23 | 1954-09-15 | Pyrene Co Ltd | Improvements in or relating to the coating of ferrous surfaces |
| DE1933013C3 (en) * | 1969-06-28 | 1978-09-21 | Gerhard Collardin Gmbh, 5000 Koeln | Process for the production of protective layers on aluminum, iron and zinc by means of solutions containing complex fluorides |
| US4384902A (en) | 1981-06-15 | 1983-05-24 | Occidental Chemical Corporation | Trivalent chromium passivate composition and process |
| US4349392A (en) | 1981-05-20 | 1982-09-14 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
| DE19615664A1 (en) | 1996-04-19 | 1997-10-23 | Surtec Produkte Und Systeme Fu | Chromium (VI) free chromate layer and process for its production |
| WO1999007916A1 (en) * | 1997-08-06 | 1999-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Phosphating method accelerated by n-oxides |
| JP3332373B1 (en) | 2001-11-30 | 2002-10-07 | ディップソール株式会社 | A treatment solution for forming a hexavalent chromium-free rust preventive film on zinc and zinc alloy plating, a hexavalent chromium-free rust preventive film, and a method for forming the same. |
| WO2004072325A1 (en) | 2003-02-07 | 2004-08-26 | Pavco, Inc. | Black trivalent chromium chromate conversion coating |
| DE102005025830B4 (en) * | 2005-06-02 | 2010-04-08 | Walter Hillebrand Gmbh & Co. Kg Galvanotechnik | Zinc-nickel black passivation and passivation process |
| JP5198727B2 (en) * | 2005-10-07 | 2013-05-15 | ディップソール株式会社 | Treatment solution for forming black hexavalent chromium-free conversion coating on zinc or zinc alloy |
| ATE431442T1 (en) * | 2006-01-31 | 2009-05-15 | Atotech Deutschland Gmbh | AQUEOUS REACTION SOLUTION AND METHOD FOR PASSIVATION OF ZINC AND ZINC ALLOYS |
| ES2361361T3 (en) * | 2007-03-05 | 2011-06-16 | Atotech Deutschland Gmbh | PASSIVATION IN BLACK EXEMPT FROM CHROME (VI) FOR SURFACES CONTAINING ZINC. |
| JP5584922B2 (en) * | 2007-12-19 | 2014-09-10 | ディップソール株式会社 | Trivalent chromium chemical conversion treatment solution for forming a trivalent chromium chemical conversion coating on zinc or zinc alloy plating |
| DE102008000600B4 (en) * | 2008-03-11 | 2010-05-12 | Chemetall Gmbh | Process for coating metallic surfaces with a passivating agent, the passivating agent, the coating produced therewith and their use |
-
2008
- 2008-11-27 DE DE102008044143A patent/DE102008044143B4/en not_active Expired - Fee Related
-
2009
- 2009-11-23 US US13/125,357 patent/US20110217476A1/en not_active Abandoned
- 2009-11-23 WO PCT/EP2009/065646 patent/WO2010060883A1/en active Application Filing
- 2009-11-23 PL PL09760833T patent/PL2358922T3/en unknown
- 2009-11-23 CN CN200980147454.9A patent/CN102227516B/en not_active Expired - Fee Related
- 2009-11-23 ES ES09760833.5T patent/ES2565839T3/en active Active
- 2009-11-23 EP EP09760833.5A patent/EP2358922B1/en not_active Not-in-force
- 2009-11-23 KR KR1020117011981A patent/KR20110089304A/en not_active Application Discontinuation
- 2009-11-23 JP JP2011537953A patent/JP5562347B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2010060883A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| PL2358922T3 (en) | 2016-07-29 |
| WO2010060883A1 (en) | 2010-06-03 |
| DE102008044143A1 (en) | 2010-06-02 |
| JP5562347B2 (en) | 2014-07-30 |
| EP2358922B1 (en) | 2016-01-27 |
| CN102227516A (en) | 2011-10-26 |
| CN102227516B (en) | 2015-07-22 |
| US20110217476A1 (en) | 2011-09-08 |
| KR20110089304A (en) | 2011-08-05 |
| DE102008044143B4 (en) | 2011-01-13 |
| JP2012509994A (en) | 2012-04-26 |
| ES2565839T3 (en) | 2016-04-07 |
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