EP3093370A1 - Pre-treatment of zinc surfaces before zinc phosphating - Google Patents
Pre-treatment of zinc surfaces before zinc phosphating Download PDFInfo
- Publication number
- EP3093370A1 EP3093370A1 EP16175371.0A EP16175371A EP3093370A1 EP 3093370 A1 EP3093370 A1 EP 3093370A1 EP 16175371 A EP16175371 A EP 16175371A EP 3093370 A1 EP3093370 A1 EP 3093370A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- acid
- zinc
- component
- soluble
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 62
- 239000011701 zinc Substances 0.000 title claims abstract description 62
- 238000002203 pretreatment Methods 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 229910052742 iron Inorganic materials 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- -1 iron ions Chemical class 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 30
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 28
- 239000008397 galvanized steel Substances 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 20
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 150000004715 keto acids Chemical class 0.000 claims abstract description 11
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 53
- 230000008569 process Effects 0.000 claims description 26
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001371 alpha-amino acids Chemical class 0.000 claims description 5
- 235000008206 alpha-amino acids Nutrition 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000018977 lysine Nutrition 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Substances 0.000 claims description 2
- KCTSXBFNNAXQFG-UHFFFAOYSA-N [hydroxy(oxido)phosphaniumyl]phosphinic acid Chemical compound OP(=O)P(O)=O KCTSXBFNNAXQFG-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 2
- 150000008040 ionic compounds Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 235000004400 serine Nutrition 0.000 claims description 2
- 235000008521 threonine Nutrition 0.000 claims description 2
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 claims 1
- BUIMWOLDCCGZKZ-UHFFFAOYSA-N n-hydroxynitramide Chemical compound ON[N+]([O-])=O BUIMWOLDCCGZKZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 30
- 230000007797 corrosion Effects 0.000 abstract description 30
- 238000005260 corrosion Methods 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 23
- 239000003973 paint Substances 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract description 8
- 238000007739 conversion coating Methods 0.000 abstract description 7
- 230000008595 infiltration Effects 0.000 abstract description 7
- 238000001764 infiltration Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000005520 cutting process Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000004922 lacquer Substances 0.000 abstract description 3
- 239000011253 protective coating Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 24
- 229910000831 Steel Inorganic materials 0.000 description 20
- 239000010959 steel Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000002161 passivation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 3
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229960002989 glutamic acid Drugs 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241001499740 Plantago alpina Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 2
- 235000004554 glutamine Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 1
- 208000013016 Hypoglycemia Diseases 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N Isohexonic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 229930182816 L-glutamine Natural products 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FATUQANACHZLRT-KMRXSBRUSA-L calcium glucoheptonate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O FATUQANACHZLRT-KMRXSBRUSA-L 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 235000013924 ferrous gluconate Nutrition 0.000 description 1
- 239000004222 ferrous gluconate Substances 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- 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
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
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- 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
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- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- 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
- C23C22/78—Pretreatment of the material to be coated
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
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- 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
Definitions
- the present invention relates to a wet-chemical pretreatment of zinc surfaces prior to the application of a corrosion-protective coating.
- the wet-chemical pretreatment causes the deposition of a thin inorganic coating consisting essentially of oxidic and / or metallic iron.
- a layer of iron applied according to the invention - referred to below as icing - requires an improvement in the achievable corrosion protection of wet-chemical conversion coatings known from the prior art on zinc surfaces.
- the icing causes both a reduction in the contact corrosion of assembled metallic components which have zinc and iron surfaces and a reduction of the corrosive paint infiltration at cutting edges of galvanized steel strip with lacquer layer structure.
- the invention relates to an alkaline composition for icing containing a source of iron ions, a reducing agent based on oxo acids of the elements nitrogen and phosphorus and water-soluble organic carboxylic acids having an amino group in ⁇ -, ⁇ -, or ⁇ -position to the acid group and / or their water-soluble salts.
- car bodies consist of a large number of sheet-metal parts which are joined together by spot welding.
- the metallic zinc coatings which are applied to the steel strip either electrolytically or by hot dip coating, impart a cathodic protective effect which permits active dissolution of the nobler core material by mechanically causing injuries to the material Zinc coating effectively prevented.
- the steel strip producers are increasingly turning to the integration of surface finishing with metallic coatings, the application of inorganic and / or organic protective layers, in particular the application of organic primers in the belt system.
- surface-finished strip steels whose predisposition to Thomaskanten- and bimetallic corrosion is only slightly pronounced, so that even after the production of the products, the punching, cutting, forming and / or joining the strip steel comprises, and a subsequent paint layer structure further good corrosion protection and a good paint adhesion can be ensured.
- there is a need for the surfaces of products composed of different metallic strip materials To pretreat that the preferred delamination of subsequently applied paint layers is leveled at cut edges and bimetallic contacts.
- the prior art describes various pretreatments that address the problem of edge protection.
- An essential strategy is to improve the paint adhesion of the organic barrier layer on the surface-treated steel strip.
- the German Offenlegungsschrift teaches DE 197 33 972 A1 a process for the alkaline passivating pretreatment of galvanized and alloy-galvanized steel surfaces in strip lines.
- the surface-treated steel strip is brought into contact with an alkaline treatment agent containing magnesium ions, iron (III) ions and a complexing agent.
- the zinc surface is passivated thereby forming the corrosion protection layer.
- Such a passivated surface offers according to the teaching of DE19733972 already a paint adhesion, which is comparable to nickel and cobalt-containing processes.
- this pretreatment can be followed by further treatment steps such as chromium-free post-passivation to improve the corrosion protection before the paint system is applied.
- the alkaline passivation serves primarily to improve the corrosion protection of chromium-free conversion coatings.
- the aim is to achieve an alkaline cleaning step that leads to alkaline passivation and subsequent acidic passivation to provide a coating base which is comparable to zinc phosphating and protects against corrosion.
- the pursued DE 10 2007 021 364 A1 the goal by means of electroless metal cations without electroless deposition to realize a thin metallic coating layer on galvanized steel surfaces, which together with a subsequent passivation to significantly reduce corrosion at cut edges and bimetallic contacts of cut and assembled surface-coated strip steel should make.
- the icing and tinning of galvanized and alloy-galvanized steel strip is proposed to improve the edge protection.
- the icing preferably acidic compositions containing iron ions, a complexing agent with oxygen and / or nitrogen ligands and phosphinic acid are used as the reducing agent.
- the object of the present invention is to further develop the icing of metallic components having zinc surfaces such that, in conjunction with subsequent wet-chemical conversion coatings, improved corrosion protection and paint adhesion on the zinc surfaces results, in particular the edge protection at cut edges of galvanized steel surfaces is to be improved ,
- Water solubility in the context of the present invention means that the solubility of the compound at a temperature of 25 ° C and a pressure of 1 bar in deionized water with a conductivity of less than 1 ⁇ Scm -1 is greater than 1 g / l.
- oxidation level is meant, according to the invention, the hypothetical charge of an atom resulting from the number of electrons of the atom compared to its atomic number that the corresponding atom hypothesizes when electrons are attributed due to the electronegativity of the elements forming the molecule or salt with the higher electronegativity element combining all the electrons it shares with the elements of lower electronegativity, while the electrons be shared by the same elements, each half be awarded to the one and the other half to the other atom.
- surfaces of galvanized steel and alloy-galvanized steel are considered as zinc surfaces in addition to surfaces of metallic zinc if the zinc coating is at least 5 g / m 2 based on the element zinc and the proportion of zinc in the zinc layer on the steel is at least 40 at% ,
- the source of iron ions dissolved in water are all compounds which release iron ions in water.
- one or more water-soluble salts of di- or trivalent iron in a composition according to the invention serve as a source of iron ions dissolved in water, wherein the use of water-soluble salts of divalent iron ions is preferred, such as, for example, iron (II) nitrate or iron (II) sulfate.
- Particularly suitable water-soluble compounds are the corresponding salts of the ⁇ -hydroxycarboxylic acids having not more than 8 carbon atoms, which in turn are preferably selected from salts of polyhydroxymonocarboxylic acid, polyhydroxydicarboxylic acid each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or ⁇ -hydroxybutyric acid.
- compositions according to the invention for a sufficiently fast kinetics of icing from aqueous solution, preference is given to compositions according to the invention in which at least 0.1 g / l, preferably at least 1 g / l, particularly preferably at least 2 g / l, of iron ions dissolved in the aqueous phase are included.
- additional amounts of dissolved iron ions initially cause a further increase in the deposition kinetics, so that, depending on the duration of the application process-related application, a different minimum amount of iron ions in the composition of the invention is opportune.
- the composition preferably contains at least 3 g / l of iron ions.
- the upper limit for the amount of iron ions is primarily determined by the stability of the composition and is preferably 50 g / l for a composition according to the invention.
- the amounts with respect to the iron ions in a composition according to the invention of course relate to the amount of iron ions available for the icing and thus to the amount of iron ions dissolved in the aqueous phase, for example in hydrated and / or complexed form. Iron ions in non-freezing form, ie for example, bound in undissolved iron salts do not contribute to the proportion of iron ions in the composition of the invention.
- the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is not greater than 2: 1. Above this molar ratio, the accelerating effect of the organic carboxylic acids according to component b) decreases Icing already noticeable. Particular preference is therefore given to compositions according to the invention in which the abovementioned molar ratio is not greater than 1: 1. Conversely, a reduction of the aforementioned molar ratio below 1:12 with the same amount of iron ions, ie a further increase in the proportion of component b), causes no appreciable additional acceleration in the icing of zinc surfaces. Therefore, such compositions according to the invention are preferred in which the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is at least 1: 12, preferably at least 1: 8.
- compositions according to the invention are particularly suitable for producing uniform and adequate iron coating layers on zinc surfaces in a time interval typical for wet-chemical pretreatment.
- those compositions are preferred according to the invention in which the organic carboxylic acids and / or their salts according to component b) are selected from water-soluble ⁇ -amino acids and their water-soluble salts, in particular from ⁇ -amino acids and their water-soluble salts, in addition to amino and carboxyl Groups have exclusively hydroxyl groups and / or carboxamide groups, wherein the ⁇ -amino acids preferably have not more than 7 carbon atoms.
- a composition according to the invention contains as component b) lysine, serine, threonine, alanine, glycine, aspartic acid, glutamic acid, glutamine and / or their water-soluble salts, particularly preferably lysine, glycine, glutamic acid, glutamine and / or their water-soluble salts, especially preferred is glycine and / or its water-soluble salts.
- an alkaline composition for the pretreatment of metallic surfaces having zinc surfaces is preferred according to the invention, for which the proportion of glycine and / or its water-soluble salts of water-soluble organic carboxylic acids according to component b) and / or their water-soluble salts at least 50 wt .-%, more preferably at least 80 wt .-%, particularly preferably at least 90 wt .-% is.
- compositions according to the invention have reducing properties and thus bring about rapid and homogeneous icing of the zinc surfaces brought into contact with the composition according to the invention.
- compositions according to the invention are used for the icing, which contain at least one oxo acid of phosphorus with at least one phosphorus atom in a middle oxidation state and their water-soluble salts as component c).
- the molar ratio of iron ions to oxo acids of phosphorus or nitrogen according to component c) and their water-soluble salts is for economic reasons at least 1:10, preferably at least 1: 6.
- the relative proportion of these compounds should be Component c) be sufficiently large for a sufficient icing of the zinc surfaces.
- the aforementioned molar ratio in a composition according to the invention is not greater than 3: 1, more preferably not greater than 2: 1. It is further preferred if the proportion of oxo acids of phosphorus in a composition according to the invention based on the total amount of Components c) at least 50 mol .-%, particularly preferably at least 80 mol .-% is.
- the compounds according to component c) of a composition according to the invention are preferably selected from hyposalphurous acid, hypos nitric acid, nitrous acid, hypophosphoric acid, hypodiphosphonic acid, diphosphoric (III, V) acid, phosphonic acid, diphosphonic acid and phosphinic acid and their water-soluble salts, phosphinic acid and their water-soluble salts are particularly preferred.
- composition according to the invention therefore preferably additionally contains chelating complexing agents with oxygen and / or nitrogen ligands which do not contain water-soluble carboxylic acids according to component b) of the invention Compositions are.
- Particularly preferred in this context are compositions according to the invention which contain as additional component d) one or more such complexing agents which are selected from water-soluble ⁇ -hydroxycarboxylic acids which have at least one hydroxyl and one carboxyl group and no water-soluble organic carboxylic acids according to component b ), as well as from their water-soluble salts.
- the water-soluble ⁇ -hydroxycarboxylic acids according to component d) preferably have not more than 8 carbon atoms and are in particular selected from polyhydroxymonocarboxylic acids and / or polyhydroxydicarboxylic acids each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or ⁇ -hydroxybutyric acid and from their water-soluble salts, most preferably selected from lactic acid and / or 2,3,4,5,6-pentahydroxyhexanoic acid and from their water-soluble salts.
- a particularly effective formulation of the inventive composition with the aforementioned complexing agents according to component d) has a molar ratio of iron ions to water-soluble ⁇ -hydroxycarboxylic acids and their water-soluble salts of at least 1: 4, preferably of at least 1: 3, but not greater than 2: 1, preferably not greater than 1: 1.
- reducing accelerators can be used, which are known to those skilled in the art in the phosphating. These include hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid and reducing sugars.
- the pH of the alkaline composition according to the invention is preferably not greater than 11.0, more preferably preferably not greater than 10.5, particularly preferably not greater than 10.0.
- compositions according to the invention may additionally contain surface-active compounds, preferably nonionic surfactants, in order to bring about additional purification and activation of the metal surfaces, so that homogeneous icing on the zinc surfaces is additionally promoted.
- the nonionic surfactants are preferably selected from one or more ethoxylated and / or propoxylated C 10 -C 18 fatty alcohols having a total of at least two but not more than 12 alkoxy groups, more preferably ethoxy and / or propoxy, some with an alkyl radical, more preferably with a Methyl, ethyl, propyl, butyl radical end-capped can.
- the proportion of nonionic surfactants in a composition according to the invention is preferably at least 0.01 g / l, more preferably at least 0.1 g / l, for sufficient cleaning and activation of the metal surfaces, and for economic reasons preferably not more than 10 g / l nonionic surfactants are included.
- compositions according to the invention do not contain zinc ions in an amount for which the ratio of the total molar fraction of zinc ions and iron ions to the total molar fraction of water-soluble organic carboxylic acids according to component b) and water-soluble organic ⁇ -hydroxycarboxylic acids according to component d) and their respective water-soluble salts greater than 1: 1, more preferably greater than 2: 3.
- the present invention is further characterized in that no further heavy metals have to be added to a composition according to the invention in order to provide improved corrosion protection on the zinc surfaces as part of the icing in cooperation with a subsequent wet chemical conversion treatment.
- a composition according to the invention therefore preferably contains less than 50 ppm total of metal ions of the elements Ni, Co, Mo, Cr, Ce, V and / or Mn, particularly preferably less than 10 ppm, particularly preferably less than 1 ppm of these elements.
- composition according to the invention preferably contains less than 1 g / l of water-soluble or water-dispersible organic polymers, since carryover of polymeric constituents from the pretreatment for icing into subsequent baths for wet-chemical conversion treatment may adversely affect the formation of the conversion layer.
- water-soluble or water-dispersible polymers are understood as meaning organic compounds which remain in the retentate in an ultrafiltration with a nominal cutoff limit (NMWC) of 10,000 ⁇ .
- step ii) first of all, a coating layer consisting essentially of oxidic and / or metallic iron is produced on the zinc surfaces ("icing").
- the metallic component which may be, for example, surfaces of iron, steel and / or aluminum, such an inorganic layer is not detectable.
- the specific deposition of the passive layer on the zinc surfaces leads in the process according to the invention, in which the icing a passivating wet chemical conversion treatment, surprisingly to a significant improvement in paint adhesion properties of these surfaces and effectively prevents the corrosion of cut edges of galvanized steel and the contact corrosion of the zinc surfaces connected ferrous metals.
- a passivating wet-chemical conversion treatment is a standard procedure in the steel and automotive industry for pre-treatment before an organic topcoat composition.
- the metallic component has galvanized steel surfaces.
- the method in the treatment of galvanized steel strip as it provides excellent edge corrosion protection, and of components consisting of mixed composite and / or assembled metallic components made of galvanized steel, iron and / or steel and possibly aluminum, as it the contact corrosion is greatly reduced.
- the alkaline cleaning step i) in the process according to the invention is optional and necessary when the surfaces of zinc have impurities in the form of salts and fats, for example drawing fats and corrosion protection oils.
- step ii) of the process according to the invention wherein the manner of bringing into contact with the alkaline composition according to the invention is not restricted in terms of process technology to a particular method.
- the zinc surfaces are contacted by dipping or spraying with the composition according to the invention for freezing.
- the metallic component is for at least 3 seconds, but not more than 4 minutes at a temperature of at least 30 ° C, more preferably at least 40 ° C, but not more than 70 ° C, more preferably not more than 60 ° C brought into contact with an alkaline composition according to the invention.
- the compositions according to the invention cause an icing of the zinc surfaces.
- the formation of icing is self-limiting, ie with increasing icing of the zinc surfaces, the deposition rate of iron decreases.
- the preferred treatment or contact times should be selected in the method according to the invention so that the layer of iron is at least 20 mg / m 2 based on the element iron.
- the treatment and contact times for the realization of such a minimum layer coverage vary depending on the type of application and depend in particular on the flow of the aqueous fluids acting on the metal surface to be treated.
- the formation of icing in processes in which the composition is applied by spraying faster than in immersion applications.
- the coating compositions according to the invention do not produce any layer deposits on iron significantly above 300 mg / m 2, based on the element iron, due to the self-limiting freezing.
- a sufficient layer formation and an optimal edge protection in the treatment of galvanized steel surfaces immediately after the icing in step ii) with or without subsequent rinsing layer coatings of iron preferably at least 20 mg / m 2 , more preferably at least 50 mg / m 2 , in particular preferably more than 100 mg / m 2 . but preferably not more than 250 mg / m 2 in each case based on the element iron realized realized.
- the coating of iron on the zinc surfaces can be determined after dissolution of the coating by means of a spectroscopic method which is described in the examples of the present invention.
- step ii) of the method according to the invention is preferably carried out without external current, ie without applying an external voltage source to the metallic component.
- a passivating wet-chemical conversion treatment takes place subsequently to step ii) with or without an intermediate rinsing step.
- Wet-chemical conversion treatment is understood according to the invention as bringing into contact at least the zinc surfaces of the metallic component with an aqueous composition which produces a passivating and substantially inorganic conversion coating on the treated zinc surfaces.
- a conversion coating is any inorganic coating on the metallic zinc substrate which does not represent an oxide or hydroxide coating whose cationogenic main constituent is zinc ions.
- a conversion coating may therefore be a zinc phosphate layer.
- a passivating wet chemical conversion treatment is carried out in step iii) by bringing into contact with an acidic aqueous composition which has a total of at least 5 ppm but not more than 1500 ppm total of water-soluble inorganic compounds of the elements Zr, Ti , Si and / or Hf based on the aforementioned elements, and preferably water-soluble inorganic compounds which release fluoride ions, for example, fluorocomplexes, hydrofluoric acid and / or metal fluorides.
- step iii) of the process according to the invention which contain as water-soluble compounds of the elements zirconium, titanium and / or hafnium only water-soluble compounds of the elements zirconium and / or titanium, more preferably water-soluble compounds of the element zirconium.
- both compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements titanium and / or zirconium for example H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium compounds, as well as fluorine-free compounds of the elements zirconium and / or titanium, for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ), in acidic aqueous compositions used in step iii) of the method according to the invention.
- fluorine-free compounds of the elements zirconium and / or titanium for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ), in acidic aqueous compositions used in step iii) of the method according to the invention.
- the acidic aqueous composition containing a total of at least 5 ppm but not more than 1500 ppm total of water-soluble inorganic compounds of the elements Zr, Ti, Si and / or Hf with respect to the aforementioned elements is preferred chromium-free, ie it contains less than 10 ppm, preferably less than 1 ppm of chromium, in particular no chromium (VI).
- a zinc phosphating is carried out in step iii), wherein the presence of the heavy metals Ni and / or Cu in the zinc phosphating can largely be dispensed with due to the previous icing of the zinc surfaces of the metallic component in step ii).
- the icing of the zinc surfaces thus provides for subsequent zinc phosphating the unexpected advantage that results for such phosphated zinc surfaces corrosion protection and paint adhesion, which is comparable to the Zinkphosphatleiter of iron or steel surfaces.
- the pretreated metallic components which have surfaces of zinc directly resulting from a method according to the invention, are then preferably provided with an organic covering layer, with or without an intermediate rinsing and / or drying step.
- the first cover layer in the pretreatment of already cut, formed and assembled components is usually an electrodeposition paint, more preferably a cathodic dip.
- organic primer coatings are preferably applied as the first organic cover layer in the anticorrosive or decorative coating of galvanized steel strip following the inventive method.
- metallic components having surfaces of zinc find use in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
- compositions (C1-C4) thin coatings of oxidic and / or metallic iron on the zinc surfaces ("icing") are obtained with all inventive compositions (C1-C4), but particularly homogeneous coatings are formed specifically by compositions (C1; C5) according to the invention comprising glycine.
- concentration of the active components in a composition according to the invention has an immediate effect on the deposition rate, so that dilute compositions must be brought into contact with the galvanized steel surface for a longer time in order to obtain a homogeneously coated zinc surface (see C1 in comparison to C5).
- Table 2 shows the corrosive infiltration of an immersion paint on electrolytically galvanized steel after the respective process chain for corrosion-protective pretreatment in
- Fixodine® 50CF Henkel Remaining deionized water ( ⁇ ⁇ 1 ⁇ SCM -1 ) Duration of treatment at 20 ° C: 60 seconds E1.
- Acid passivation 0.34 g / L H 2 Zr F 6 0.12 g / L Ammonium 0.08 g / L Cu (NO 3 ) 2 . 3H 2 O Remaining deionized water ( ⁇ ⁇ 1 ⁇ SCM -1 ) pH 4
- Nickel-free phosphating 0.13% by weight zinc 0.09% by weight manganese 0.12% by weight nitrate 1.63% by weight phosphate 0.25% by weight Hydroxylamine 0.02% by weight Ammonium 0.10% by weight H 2 SiF 6 Remaining deionized water ( ⁇ ⁇ 1 ⁇ SCM -1 )
- Free fluoride 40 mg / L Free acid: 1.3 points (pH 3.6) Total acidity: 26 points (pH 8.5) Treatment time at 50 ° C: 180 seconds E3.
- Nickel-containing phosphating (trication-phosphating): 0.13% by weight zinc 0.09% by weight manganese 0.10% by weight nickel 0.32% by weight nitrate 1.63% by weight phosphate 0.25% by weight Hydroxylamine 0.02% by weight Ammonium 0.10% by weight H 2 SiF 6 Remaining deionized water ( ⁇ ⁇ 1 ⁇ SCM -1 ) Free fluoride: 40 mg / L Free acid: 1.3 points (pH 3.6) Total acid: 26.5 points (pH 8.5) Treatment time at 50 ° C: 180 seconds F. Coating structure: EV2007 (PPG): layer thickness 17-19 ⁇ m
- the coating weight of zinc phosphate results from the multiplication of the area-related amount of phosphorus with a factor of 6.23. 3 quantitative determination of the amount of iron (III) ions by UV photometer (WTW, PhotoFlex®) in 300 .mu.l sample volume of a 5 wt .-% nitric acid solution, which immediately after the process step "C" using a measuring cell ring (Fa Helmut-Fischer) was pipetted onto a defined area of the 1.33 cm 2 galvanized sheet and, after 30 seconds of action at a temperature of 25 ° C., picked up by the same pipette and placed in the UV measuring cuvette in which 5 ml of a 1, 0% sodium thiocyanate solution were submitted, to determine the absorption at a wavelength of 517 nm and temperature of 25 ° C was transferred.
- WTW UV photometer
- the calibration was carried out in a two-point method by determining the absorption values of identical volumes (300 ⁇ l) of two standard solutions of ferric nitrate in 5% strength by weight nitric acid, which was used to determine the absorption values at 25 ° C. in the measuring cuvette containing 5 ml of a 1.0% sodium thiocyanate solution.
Abstract
Die vorliegende Erfindung betrifft eine nasschemische Vorbehandlung von Zinkoberflächen vor der Aufbringung einer korrosionsschützenden Beschichtung. Die nasschemische Vorbehandlung bewirkt die Abscheidung einer dünnen anorganischen Beschichtung, die im Wesentlichen aus oxidischem und/oder metallischem Eisen besteht. Eine erfindungsgemäß aufgebrachte Schichtauflage an Eisen - nachstehend Vereisenung genannt - bedingt eine Verbesserung des erreichbaren Korrosionsschutzes von im Stand der Technik bekannten nasschemischen Konversionsbeschichtungen auf Zinkoberflächen. Des Weiteren bewirkt die Vereisenung sowohl eine Verminderung der Kontaktkorrosion von zusammengefügten metallischen Bauteilen die Zink- und Eisenoberflächen aufweisen als auch eine Verminderung der korrosiven Lackunterwanderung an Schnittkanten von verzinktem Bandstahl mit Lackschichtaufbau. Die Erfindung betrifft insbesondere eine alkalische Zusammensetzung zur Vereisenung enthaltend eine Quelle für Eisen-Ionen, ein Reduktionsmittel auf Basis von Oxosäuren der Elemente Stickstoff und Phosphor sowie wasserlösliche organische Carbonsäuren mit einer Amino-Gruppe in a-, ²-, oder ³-Stellung zur Säuregruppe und/oder deren wasserlösliche Salze.The present invention relates to a wet-chemical pretreatment of zinc surfaces prior to the application of a corrosion-protective coating. The wet-chemical pretreatment causes the deposition of a thin inorganic coating consisting essentially of oxidic and / or metallic iron. A layer of iron applied according to the invention - referred to below as icing - requires an improvement in the achievable corrosion protection of wet-chemical conversion coatings known from the prior art on zinc surfaces. Furthermore, the icing causes both a reduction in the contact corrosion of assembled metallic components which have zinc and iron surfaces and a reduction of the corrosive paint infiltration at cutting edges of galvanized steel strip with lacquer layer structure. The invention particularly relates to an alkaline composition for icing containing a source of iron ions, a reducing agent based on oxo acids of the elements nitrogen and phosphorus and water-soluble organic carboxylic acids having an amino group in a, ²-, or ³-position to the acid group and / or their water-soluble salts.
Description
Die vorliegende Erfindung betrifft eine nasschemische Vorbehandlung von Zinkoberflächen vor der Aufbringung einer korrosionsschützenden Beschichtung. Die nasschemische Vorbehandlung bewirkt die Abscheidung einer dünnen anorganischen Beschichtung, die im Wesentlichen aus oxidischem und/oder metallischem Eisen besteht. Eine erfindungsgemäß aufgebrachte Schichtauflage an Eisen - nachstehend Vereisenung genannt - bedingt eine Verbesserung des erreichbaren Korrosionsschutzes von im Stand der Technik bekannten nasschemischen Konversionsbeschichtungen auf Zinkoberflächen. Des Weiteren bewirkt die Vereisenung sowohl eine Verminderung der Kontaktkorrosion von zusammengefügten metallischen Bauteilen die Zink- und Eisenoberflächen aufweisen als auch eine Verminderung der korrosiven Lackunterwanderung an Schnittkanten von verzinktem Bandstahl mit Lackschichtaufbau. Die Erfindung betrifft insbesondere eine alkalische Zusammensetzung zur Vereisenung enthaltend eine Quelle für Eisen-Ionen, ein Reduktionsmittel auf Basis von Oxosäuren der Elemente Stickstoff und Phosphor sowie wasserlösliche organische Carbonsäuren mit einer Amino-Gruppe in α-, β-, oder γ-Stellung zur Säuregruppe und/oder deren wasserlösliche Salze.The present invention relates to a wet-chemical pretreatment of zinc surfaces prior to the application of a corrosion-protective coating. The wet-chemical pretreatment causes the deposition of a thin inorganic coating consisting essentially of oxidic and / or metallic iron. A layer of iron applied according to the invention - referred to below as icing - requires an improvement in the achievable corrosion protection of wet-chemical conversion coatings known from the prior art on zinc surfaces. Furthermore, the icing causes both a reduction in the contact corrosion of assembled metallic components which have zinc and iron surfaces and a reduction of the corrosive paint infiltration at cutting edges of galvanized steel strip with lacquer layer structure. More particularly, the invention relates to an alkaline composition for icing containing a source of iron ions, a reducing agent based on oxo acids of the elements nitrogen and phosphorus and water-soluble organic carboxylic acids having an amino group in α-, β-, or γ-position to the acid group and / or their water-soluble salts.
In der Stahlindustrie wird eine Vielzahl oberflächenveredelter Stahlwerkstoffe hergestellt, wobei oberflächenveredelte Ausführungen zur Gewährleistung eines möglichst nachhaltigen Schutzes vor Korrosion stark nachgefragt werden. Für die Produktion von Erzeugnissen, beispielsweise Automobilkarosserien, werden insbesondere Feinblechprodukte aus unterschiedlichen metallischen Materialien und mit unterschiedlicher Oberflächenvergütung weiterverarbeitet. Für die Fertigung der Erzeugnisse werden die oberflächenveredelten Bandstähle zugeschnitten, umgeformt und mittels Schweiß- oder Klebeverfahren mit anderen metallischen Bauteilen zusammengefügt. In diesen Erzeugnissen liegen daher verschiedenste Kombinationen von metallischem Grund- und Oberflächenmaterial realisiert vor. Diese Fertigungsart ist im hohen Maße typisch für den Karosseriebau in der Automobilindustrie und wird häufig als Multimetallbauweise bezeichnet. Im Karosseriebau wird hauptsächlich verzinkter Bandstahl weiterverarbeitet und beispielsweise mit unverzinktem Bandstahl und/oder Bandaluminium zusammengefügt. So bestehen Autokarosserien aus einer Vielzahl von Blechteilen, die durch Punktschweißen miteinander verbunden werden.
Die metallischen Zinküberzüge, die elektrolytisch oder im Schmelztauchverfahren auf das Stahlband aufgebracht werden, verleihen eine kathodische Schutzwirkung, die eine aktive Auflösung des edleren Kernmaterials durch mechanisch hervorgerufene Verletzungen des Zinküberzuges effektiv verhindert. Jedoch besteht ein wirtschaftliches Interesse die Korrosionsrate insgesamt zu minimieren, um die kathodische Schutzwirkung des unedleren Metallüberzugs möglichst nachhaltig aufrecht zu erhalten. Zu diesem Zweck werden beim Bandstahlhersteller oder vor einer Lackierung im Paint-Shop der Fertigungsstrasse von Karosserien beim Automobilhersteller Passivierungsschichten, die rein anorganischer oder gemischt organisch-anorganischer Natur sind, und/oder organische Primer als Barriereschicht zur weiteren Minimierung der Korrosion aufgebracht, die zudem als Lackhaftgrund für eine spätere Decklackierung des Erzeugnisses dienen.
Aus der heute üblichen Kombinationsvielfalt von metallischen Bandmaterialien in einem Erzeugnis und der vornehmlichen Verwendung von oberflächenveredelten Bandstählen ergeben sich in den beschriebenen Fertigungsprozessen als besondere Korrosionsphänomene die Schnittkanten- und Bimetallkorrosion. An Schnittkanten und an durch die Bearbeitung oder sonstige Einflüsse auftretenden Verletzungen an der Zinkauflage bewirkt die galvanische Kopplung zwischen Kernmaterial und metallischem Überzug eine lokale Auflösung des Überzugsmaterials, die wiederum die korrosive Unterwanderung der organischen Barriereschichten an diesen Stellen zur Folge haben kann. Das Phänomen der Lackenthaftung oder des "Blistering" wird daher speziell an den Schnittkanten der Bleche beobachtet. Gleiches gilt prinzipiell für die Stellen eines Bauteils, an denen unterschiedliche metallische Materialien durch Fügetechniken unmittelbar miteinander verbundenen sind und Bimetallkorrosion die Folge ist. Die lokale Aktivierung eines solchen "Defektes" (Schnittkante, Verletzung im metallischen Überzug, Punktschweißstelle) und damit die korrosive Lackenthaftung, die von diesen "Defekten" ausgeht, ist umso ausgeprägter je größer der elektrische Potentialunterschied zwischen den Metallen im unmittelbaren Kontakt ist. Entsprechend gute Ergebnisse bezüglich der Lackhaftung an Schnittkanten bietet Bandstahl mit Zinküberzügen, die mit edleren Metallen legiert sind, z.B. eisenlegierte Zinküberzüge (Galvannealed Steel). Die Bandstahlproduzenten gehen verstärkt dazu über, neben der Oberflächenveredelung mit metallischen Überzügen die Applikation von anorganischen und/oder organischen Schutzschichten, insbesondere die Applikation von organischen Primern, in der Bandanlage zu integrieren. Diesbezüglich besteht in der weiterverarbeitenden Industrie ein großes wirtschaftliches Interesse darin, solche oberflächenveredelten Bandstähle zu erhalten, deren Prädisposition zur Schnittkanten- und Bimetallkorrosion nur gering ausgeprägt ist, so dass auch nach der Fertigung der Erzeugnisse, die das Stanzen, Schneiden, Umformen und/oder Fügen der Bandstähle umfasst, und einem nachfolgenden Lackschichtaufbau weiterhin ein guter Korrosionsschutz und eine gute Lackhaftung gewährleistet werden kann. Gleichermaßen besteht in der weiterverarbeitenden Industrie ein Bedarf die Oberflächen von aus unterschiedlichen metallischen Bandmaterialien zusammengesetzten Erzeugnissen derart vorzubehandeln, dass die bevorzugte Enthaftung von nachträglich aufgebrachten Lackschichten an Schnittkanten und Bimetallkontakten nivelliert wird.In the steel industry, a large number of surface-refined steel materials are produced, with surface-refined versions being in great demand to ensure the most sustainable possible protection against corrosion. For the production of products, such as automobile bodies, in particular thin sheet products made of different metallic materials and with different surface finish are processed. For the production of the products, the surface-treated steel strip is cut to size, formed and joined by welding or gluing process with other metallic components. In these products, therefore, a variety of combinations of metallic base and surface material are realized. This type of production is highly typical of the body shop in the automotive industry and is often referred to as multi-metal construction. In the body shop mainly galvanized steel strip is processed and joined together, for example, with non-galvanized steel strip and / or strip aluminum. Thus, car bodies consist of a large number of sheet-metal parts which are joined together by spot welding.
The metallic zinc coatings, which are applied to the steel strip either electrolytically or by hot dip coating, impart a cathodic protective effect which permits active dissolution of the nobler core material by mechanically causing injuries to the material Zinc coating effectively prevented. However, there is an economic interest in minimizing the overall corrosion rate in order to sustain the cathodic protection of the less noble metal coating as sustainably as possible. For this purpose, at the strip steel manufacturer or before painting in the paint shop of the production line of bodies at the car manufacturer Passivierungsschichten that are purely inorganic or mixed organic-inorganic nature, and / or organic primer applied as a barrier layer to further minimize the corrosion, which also Lackhaftgrund serve for a subsequent topcoat of the product.
From today's usual combination of variety of metallic strip materials in a product and the primary use of surface-coated strip steel results in the described manufacturing processes as special corrosion phenomena Schnittkanten- and bimetallic corrosion. At cutting edges and at the zinc coating caused by machining or other influences, the galvanic coupling between the core material and the metallic coating causes a local dissolution of the coating material, which in turn may result in corrosive infiltration of the organic barrier layers at these locations. The phenomenon of Lackenthaftung or "blistering" is therefore observed especially at the cut edges of the sheets. The same applies in principle to the locations of a component on which different metallic materials are directly connected by joining techniques and bimetal corrosion is the result. The local activation of such a "defect" (cut edge, damage in the metallic coating, spot welding point) and thus the corrosive paint release resulting from these "defects" is all the more pronounced the greater the electrical potential difference between the metals in direct contact. Correspondingly, good results with regard to paint adhesion at cut edges are offered by steel strips with zinc coatings alloyed with nobler metals, eg iron-alloyed zinc coatings (galvannealed steel). The steel strip producers are increasingly turning to the integration of surface finishing with metallic coatings, the application of inorganic and / or organic protective layers, in particular the application of organic primers in the belt system. In this regard, in the processing industry, there is great economic interest in obtaining such surface-finished strip steels, whose predisposition to Schnittkanten- and bimetallic corrosion is only slightly pronounced, so that even after the production of the products, the punching, cutting, forming and / or joining the strip steel comprises, and a subsequent paint layer structure further good corrosion protection and a good paint adhesion can be ensured. Similarly, in the processing industry, there is a need for the surfaces of products composed of different metallic strip materials To pretreat that the preferred delamination of subsequently applied paint layers is leveled at cut edges and bimetallic contacts.
Im Stand der Technik sind verschiedene Vorbehandlungen beschrieben, die das Problem des Kantensschutzes adressieren. Als wesentliche Strategie wird dabei die Verbesserung der Lackhaftung der organischen Barriereschicht auf dem oberflächenveredelten Bandstahl verfolgt. Beispielsweise lehrt die deutsche Offenlegungsschrift
Ebenso verfolgt die
Demgegenüber verfolgt die
Aufgabe der vorliegenden Erfindung ist es, die Vereisenung von metallischen Bauteilen, die Zinkoberflächen aufweisen, dahingehend weiter zu entwickeln, dass im Zusammenwirken mit nachfolgenden nasschemischen Konversionsbeschichtungen ein verbesserter Korrosionsschutz und Lackhaftgrund auf den Zinkoberflächen resultiert, insbesondere soll der Kantenschutz an Schnittkanten von verzinkten Stahloberflächen verbessert werden.The object of the present invention is to further develop the icing of metallic components having zinc surfaces such that, in conjunction with subsequent wet-chemical conversion coatings, improved corrosion protection and paint adhesion on the zinc surfaces results, in particular the edge protection at cut edges of galvanized steel surfaces is to be improved ,
Überraschenderweise konnte gezeigt werden, dass bei Verwendung von organischen Carbonsäuren mit einer Amino-Gruppe in α-, β-, oder γ-Stellung zur Säuregruppe und/oder deren wasserlöslichen Salze in alkalischen Zusammensetzungen zur Vereisenung auf Zinkoberflächen äußerst homogene dünne Schichtauflagen bestehend im Wesentlichen aus oxidischem und/oder metallischem Eisen erzeugt werden ("Vereisenung"), die im Zusammenwirken mit einer nachfolgenden nasschemischen Konversionsbehandlung einen verbesserten Korrosionsschutz, insbesondere an Schnittkanten von verzinkten Stahloberflächen, und einen hervorragenden Lackhaftgrund bereitstellen.Surprisingly, it has been possible to demonstrate that, when organic carboxylic acids containing an amino group in the α, β or γ position to the acid group and / or their water-soluble salts in alkaline compositions for freezing on zinc surfaces are used, extremely thin film coatings consist essentially of oxidic and / or metallic iron ("icing") which, in conjunction with a subsequent wet chemical conversion treatment, provide improved corrosion protection, in particular at cut edges of galvanized steel surfaces, and an excellent lacquer adhesion.
Die vorliegende Erfindung betrifft daher in einem ersten Aspekt eine alkalische Zusammensetzung zur Vorbehandlung von metallischen Bauteilen, die Zinkoberflächen aufweisen, mit einem pH-Wert von zumindest 8,5 enthaltend
- a) zumindest 0,01 g/l an Eisen-Ionen,
- b) ein oder mehrere wasserlösliche organische Carbonsäuren, die zumindest eine Amino-Gruppe in α-, β-, oder γ-Stellung zur Säuregruppe aufweisen, sowie deren wasserlösliche Salze,
- c) ein oder mehrere Oxosäuren von Phosphor oder Stickstoff sowie deren wasserlösliche Salze, wobei mindestens ein Phosphoratom oder Stickstoffatom in einer mittleren Oxidationsstufe vorliegt.
- a) at least 0.01 g / l of iron ions,
- b) one or more water-soluble organic carboxylic acids which have at least one amino group in α, β or γ position to the acid group, and their water-soluble salts,
- c) one or more oxo acids of phosphorus or nitrogen and their water-soluble salts, wherein at least one phosphorus atom or nitrogen atom is present in a middle oxidation state.
Wasserlöslichkeit im Rahmen der vorliegenden Erfindung bedeutet, dass die Löslichkeit der Verbindung bei einer Temperatur von 25 °C und einem Druck von 1 bar in entionisiertem Wasser mit einer Leitfähigkeit von weniger als 1µScm-1 größer als 1 g/l ist.Water solubility in the context of the present invention means that the solubility of the compound at a temperature of 25 ° C and a pressure of 1 bar in deionized water with a conductivity of less than 1μScm -1 is greater than 1 g / l.
Unter Oxidationsstufe wird erfindungsgemäß die hypothetische Ladung eines Atoms bezeichnet, die sich aus derjenigen Anzahl der Elektronen des Atoms im Vergleich zu seiner Kernladungszahl ergibt, die das entsprechende Atom hypothetisch hat, wenn Elektronen aufgrund der Elektronegativität der Elemente, die das Molekül oder Salz bilden, zugesprochen werden, wobei das Element mit der höheren Elektronegativität sämtliche Elektronen auf sich vereint, die es mit den Elementen niedrigerer Elektronegativität teilt, während Elektronen, die von gleichen Elementen geteilt werden, jeweils zur Hälfte dem einen und zur anderen Hälfte dem anderen Atom zugesprochen werden.By oxidation level is meant, according to the invention, the hypothetical charge of an atom resulting from the number of electrons of the atom compared to its atomic number that the corresponding atom hypothesizes when electrons are attributed due to the electronegativity of the elements forming the molecule or salt with the higher electronegativity element combining all the electrons it shares with the elements of lower electronegativity, while the electrons be shared by the same elements, each half be awarded to the one and the other half to the other atom.
Als Zinkoberflächen gelten erfindungsgemäß neben Oberflächen von metallischem Zink auch Oberflächen von verzinktem Stahl und legierungsverzinktem Stahl, wenn die Zinkauflage zumindest 5 g/m2 bezogen auf das Element Zink und der Anteil an Zink in der Zinkauflage auf dem Stahl zumindest 40 At.-% beträgt.According to the invention, surfaces of galvanized steel and alloy-galvanized steel are considered as zinc surfaces in addition to surfaces of metallic zinc if the zinc coating is at least 5 g / m 2 based on the element zinc and the proportion of zinc in the zinc layer on the steel is at least 40 at% ,
Als Quelle für in Wasser gelöste Eisen-Ionen kommen sämtliche Verbindungen in Betracht, die in Wasser Eisen-Ionen freisetzen. Vorzugsweise können ein oder mehrere wasserlösliche Salze von zwei- oder dreiwertigem Eisen in einer erfindungsgemäßen Zusammensetzung als Quelle für in Wasser gelöste Eisen-Ionen dienen, wobei der Einsatz von wasserlöslichen Salzen zweiwertiger Eisen-Ionen bevorzugt ist, wie bspw. Eisen(II)nitrat oder Eisen(II)sulfat. Besonders geeignete wasserlösliche Verbindungen sind die entsprechenden Salze der α-Hydroxycarbonsäuren mit nicht mehr als 8 Kohlenstoffatomen, die wiederum vorzugsweise ausgewählt sind aus Salzen der Polyhydroxymonocarbonsäure, Polyhydroxydicarbonsäure mit jeweils zumindest 4 Kohlenstoffatomen, Tartronsäure, Glykolsäure, Milchsäure und/oder α-Hydroxybuttersäure.The source of iron ions dissolved in water are all compounds which release iron ions in water. Preferably, one or more water-soluble salts of di- or trivalent iron in a composition according to the invention serve as a source of iron ions dissolved in water, wherein the use of water-soluble salts of divalent iron ions is preferred, such as, for example, iron (II) nitrate or iron (II) sulfate. Particularly suitable water-soluble compounds are the corresponding salts of the α-hydroxycarboxylic acids having not more than 8 carbon atoms, which in turn are preferably selected from salts of polyhydroxymonocarboxylic acid, polyhydroxydicarboxylic acid each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or α-hydroxybutyric acid.
Für eine hinreichend schnelle Kinetik der Vereisenung aus wässriger Lösung sind solche erfindungsgemäßen Zusammensetzungen bevorzugt, in denen zumindest 0,1 g/l, vorzugsweise zumindest 1 g/l, besonders bevorzugt zumindest 2 g/l, von in der wässrigen Phase gelösten Eisen-Ionen enthalten sind. Grundsätzlich bewirken zusätzliche Mengen an gelösten Eisen-Ionen zunächst eine weitere Erhöhung der Abscheidekinetik, so dass je nach der verfahrenstechnisch bedingten Applikationsdauer eine andere Mindestmenge an Eisen-Ionen in der erfindungsgemäßen Zusammensetzung opportun ist. Wenn die Vereisenung verfahrenstechnisch bedingt innerhalb weniger Sekunden durchzuführen ist, wie es beispielsweise bei der Vorbehandlung von verzinktem Bandstahl in einer Bandbeschichtungsanlage der Fall ist, so enthält die Zusammensetzung vorzugsweise zumindest 3 g/l an Eisen-Ionen. Die Obergrenze für die Menge an Eisen-Ionen wird vornehmlich durch die Stabilität der Zusammensetzung bestimmt und liegt für eine erfindungsgemäße Zusammensetzung vorzugsweise bei 50 g/l. Die Mengenangaben bezüglich der Eisen-Ionen in einer erfindungsgemäßen Zusammensetzung beziehen sich selbstverständlich auf die Menge von für die Vereisenung verfügbaren Eisen-Ionen und damit auf die Menge der in der wässrigen Phase gelösten Eisen-Ionen, bspw. in hydratisierter und/oder komplexierter Form. Eisen-Ionen in für die Vereisenung nicht verfügbarer Form, also beispielsweise gebunden in ungelösten Eisen-Salzen, tragen nicht zum Anteil an Eisen-Ionen in der erfindungsgemäßen Zusammensetzung bei.For a sufficiently fast kinetics of icing from aqueous solution, preference is given to compositions according to the invention in which at least 0.1 g / l, preferably at least 1 g / l, particularly preferably at least 2 g / l, of iron ions dissolved in the aqueous phase are included. In principle, additional amounts of dissolved iron ions initially cause a further increase in the deposition kinetics, so that, depending on the duration of the application process-related application, a different minimum amount of iron ions in the composition of the invention is opportune. If the icing process procedural is to be carried out within a few seconds, as is the case for example in the pretreatment of galvanized steel strip in a coil coating plant, the composition preferably contains at least 3 g / l of iron ions. The upper limit for the amount of iron ions is primarily determined by the stability of the composition and is preferably 50 g / l for a composition according to the invention. The amounts with respect to the iron ions in a composition according to the invention of course relate to the amount of iron ions available for the icing and thus to the amount of iron ions dissolved in the aqueous phase, for example in hydrated and / or complexed form. Iron ions in non-freezing form, ie for example, bound in undissolved iron salts do not contribute to the proportion of iron ions in the composition of the invention.
In einer bevorzugten erfindungsgemäßen Zusammensetzung ist das molare Verhältnis von Eisen-Ionen zu wasserlöslichen organischen Carbonsäuren gemäß Komponente b) und deren wasserlöslichen Salzen nicht größer als 2 : 1. Oberhalb dieses molaren Verhältnisses verringert sich die beschleunigende Wirkung der organischen Carbonsäuren gemäß Komponente b) auf die Vereisenung bereits merklich. Besonders bevorzugt sind daher erfindungsgemäße Zusammensetzungen, in denen das zuvor genannte molare Verhältnis nicht größer als 1 : 1 ist. Umgekehrt bewirkt eine Absenkung des zuvor genannten molaren Verhältnisses unterhalb von 1 : 12 bei gleich bleibender Menge an Eisen-Ionen, also eine weitergehende Erhöhung des Anteils an der Komponente b), keine nennenswerte zusätzliche Beschleunigung in der Vereisenung von Zinkoberflächen. Es sind daher solche erfindungsgemäßen Zusammensetzungen bevorzugt, in denen das molare Verhältnis von Eisen-Ionen zu wasserlöslichen organischen Carbonsäuren gemäß Komponente b) und deren wasserlöslichen Salzen zumindest 1 : 12, vorzugsweise zumindest 1 : 8 beträgt.In a preferred composition according to the invention, the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is not greater than 2: 1. Above this molar ratio, the accelerating effect of the organic carboxylic acids according to component b) decreases Icing already noticeable. Particular preference is therefore given to compositions according to the invention in which the abovementioned molar ratio is not greater than 1: 1. Conversely, a reduction of the aforementioned molar ratio below 1:12 with the same amount of iron ions, ie a further increase in the proportion of component b), causes no appreciable additional acceleration in the icing of zinc surfaces. Therefore, such compositions according to the invention are preferred in which the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is at least 1: 12, preferably at least 1: 8.
Des Weiteren hat sich herausgestellt, dass bestimmte organische Carbonsäuren und/oder deren Salze gemäß der Komponente b) in erfindungsgemäßen Zusammensetzungen besonders geeignet sind, gleichmäßige und hinreichende Schichtauflagen an Eisen auf Zinkoberflächen in einem für die nasschemische Vorbehandlung typischen Zeitintervall zu erzeugen. So sind solche Zusammensetzungen erfindungsgemäß bevorzugt, in denen die organischen Carbonsäuren und/oder deren Salze gemäß der Komponente b) ausgewählt sind aus wasserlöslichen α-Aminosäuren und deren wasserlösliche Salze, insbesondere aus α-Aminosäuren und deren wasserlösliche Salze, die neben Amino- und Carboxyl-Gruppen ausschließlich Hydroxyl-Gruppen und/oder Carbonsäureamid-Gruppen aufweisen, wobei die α-Aminosäuren vorzugsweise nicht mehr als 7 Kohlenstoffatome aufweisen. In einer bevorzugten Ausführungsform enthält eine erfindungsgemäße Zusammensetzung als Komponente b) Lysin, Serin, Threonin, Alanin, Glycin, Asparaginsäure, Glutaminsäure, Glutamin und/oder deren wasserlösliche Salze, besonders bevorzugt Lysin, Glycin, Glutaminsäure, Glutamin und/oder deren wasserlösliche Salze, insbesondere bevorzugt Glycin und/oder seine wasserlöslichen Salze.Furthermore, it has been found that certain organic carboxylic acids and / or their salts according to component b) in compositions according to the invention are particularly suitable for producing uniform and adequate iron coating layers on zinc surfaces in a time interval typical for wet-chemical pretreatment. Thus, those compositions are preferred according to the invention in which the organic carboxylic acids and / or their salts according to component b) are selected from water-soluble α-amino acids and their water-soluble salts, in particular from α-amino acids and their water-soluble salts, in addition to amino and carboxyl Groups have exclusively hydroxyl groups and / or carboxamide groups, wherein the α-amino acids preferably have not more than 7 carbon atoms. In a preferred embodiment, a composition according to the invention contains as component b) lysine, serine, threonine, alanine, glycine, aspartic acid, glutamic acid, glutamine and / or their water-soluble salts, particularly preferably lysine, glycine, glutamic acid, glutamine and / or their water-soluble salts, especially preferred is glycine and / or its water-soluble salts.
In diesem Zusammenhang ist eine alkalische Zusammensetzung zur Vorbehandlung metallischer Oberflächen, die Zinkoberflächen aufweisen, erfindungsgemäß bevorzugt, für die der Anteil von Glycin und/oder seinen wasserlöslichen Salzen an wasserlöslichen organischen Carbonsäuren gemäß Komponente b) und/oder deren wasserlöslichen Salzen zumindest 50 Gew.-%, besonders bevorzugt zumindest 80 Gew.-%, insbesondere bevorzugt zumindest 90 Gew.-% beträgt.In this connection, an alkaline composition for the pretreatment of metallic surfaces having zinc surfaces is preferred according to the invention, for which the proportion of glycine and / or its water-soluble salts of water-soluble organic carboxylic acids according to component b) and / or their water-soluble salts at least 50 wt .-%, more preferably at least 80 wt .-%, particularly preferably at least 90 wt .-% is.
Die Oxosäuren von Phosphor oder Stickstoff gemäß Komponente c) der erfindungsgemäßen Zusammensetzung haben reduzierende Eigenschaften und bewirken so eine schnelle und homogene Vereisenung der mit der erfindungsgemäßen Zusammensetzung in Kontakt gebrachten Zinkoberflächen. Bevorzugt werden dabei solche erfindungsgemäßen Zusammensetzungen für die Vereisenung eingesetzt, die zumindest eine Oxosäure von Phosphor mit zumindest einem Phosphoratom in einer mittleren Oxidationsstufe sowie deren wasserlöslichen Salze als Komponente c) enthalten.The oxo acids of phosphorus or nitrogen according to component c) of the composition according to the invention have reducing properties and thus bring about rapid and homogeneous icing of the zinc surfaces brought into contact with the composition according to the invention. Preferably, such compositions according to the invention are used for the icing, which contain at least one oxo acid of phosphorus with at least one phosphorus atom in a middle oxidation state and their water-soluble salts as component c).
In einer bevorzugten erfindungsgemäßen Zusammensetzung beträgt das molare Verhältnis von Eisen-Ionen zu Oxosäuren von Phosphor oder Stickstoff gemäß Komponente c) und deren wasserlöslichen Salzen aus wirtschaftlichen Gründen zumindest 1 : 10, vorzugsweise zumindest 1 : 6. Andererseits sollte der relative Anteil an diesen Verbindungen gemäß Komponente c) für eine ausreichende Vereisenung der Zinkoberflächen hinreichend groß sein. Vorzugsweise ist daher das zuvor genannte molare Verhältnis in einer erfindungsgemäßen Zusammensetzung nicht größer als 3 : 1, besonders bevorzugt nicht größer als 2 : 1. Hierbei ist es weiterhin bevorzugt, wenn der Anteil an Oxosäuren von Phosphor in einer erfindungsgemäßen Zusammensetzung bezogen auf den Gesamtanteil an Komponenten c) zumindest 50 Mol.-%, besonders bevorzugt zumindest 80 Mol.-% beträgt.In a preferred composition according to the invention, the molar ratio of iron ions to oxo acids of phosphorus or nitrogen according to component c) and their water-soluble salts is for economic reasons at least 1:10, preferably at least 1: 6. On the other hand, the relative proportion of these compounds should be Component c) be sufficiently large for a sufficient icing of the zinc surfaces. Preferably, therefore, the aforementioned molar ratio in a composition according to the invention is not greater than 3: 1, more preferably not greater than 2: 1. It is further preferred if the proportion of oxo acids of phosphorus in a composition according to the invention based on the total amount of Components c) at least 50 mol .-%, particularly preferably at least 80 mol .-% is.
Zur Erhöhung der Abscheidungsrate sind die Verbindungen gemäß Komponente c) einer erfindungsgemäßen Zusammensetzung vorzugsweise ausgewählt aus Hyposalpetriger Säure, Hyposalpetersäure, Salpetriger Säure, Hypophosphorsäure, Hypodiphosphonsäure, Diphosphor(III, V)-säure, Phosphonsäure, Diphosphonsäure und Phosphinsäure sowie deren wasserlöslichen Salze, wobei Phosphinsäure sowie deren wasserlöslichen Salze besonders bevorzugt sind.To increase the deposition rate, the compounds according to component c) of a composition according to the invention are preferably selected from hyposalphurous acid, hypos nitric acid, nitrous acid, hypophosphoric acid, hypodiphosphonic acid, diphosphoric (III, V) acid, phosphonic acid, diphosphonic acid and phosphinic acid and their water-soluble salts, phosphinic acid and their water-soluble salts are particularly preferred.
Für eine hinreichende Stabilität der erfindungsgemäßen Zusammensetzung enthaltend Eisen-Ionen ist es zudem vorteilhaft bestimmte Komplexbildner einzusetzen, um das Ausfällen von Eisenhydroxiden zu unterbinden und einen möglichst hohen Anteil an Eisen-Ionen in der wässrigen Phase in hydratisiserter und/oder komplexierter Form aufrecht zu erhalten.For a sufficient stability of the inventive composition containing iron ions, it is also advantageous to use certain complexing agents to prevent the precipitation of iron hydroxides and to maintain the highest possible proportion of iron ions in the aqueous phase in a hydrated and / or complexed form.
Die erfindungsgemäße Zusammensetzung enthält daher zur Stabilisierung vorzugsweise zusätzlich chelatisierende Komplexbildner mit Sauerstoff- und/oder Stickstoff-Liganden, die keine wasserlöslichen Carbonsäuren gemäß der Komponente b) der erfindungsgemäßen Zusammensetzungen sind. Insbesondere bevorzugt sind in diesem Zusammenhang erfindungsgemäße Zusammensetzungen, die als zusätzliche Komponente d) ein oder mehrere solcher Komplexbildner enthalten, die ausgewählt sind aus wasserlöslichen α-Hydroxycarbonsäuren, die zumindest eine Hydroxyl- und eine Carboxyl-Gruppe aufweisen und keine wasserlöslichen organischen Carbonsäuren gemäß Komponente b) sind, sowie aus deren wasserlöslichen Salze. Weiterhin besitzen die wasserlöslichen α-Hydroxycarbonsäuren gemäß Komponente d) vorzugsweise nicht mehr als 8 Kohlenstoffatome und sind insbesondere ausgewählt aus Polyhydroxymonocarbonsäuren und/oder Polyhydroxydicarbonsäuren mit jeweils zumindest 4 Kohlenstoffatomen, Tartronsäure, Glykolsäure, Milchsäure und/oder α-Hydroxybuttersäure sowie aus deren wasserlöslichen Salze, ganz besonders bevorzugt ausgewählt aus Milchsäure und/oder 2,3,4,5,6-pentahydroxyhexansäure sowie aus deren wasserlöslichen Salzen.The composition according to the invention therefore preferably additionally contains chelating complexing agents with oxygen and / or nitrogen ligands which do not contain water-soluble carboxylic acids according to component b) of the invention Compositions are. Particularly preferred in this context are compositions according to the invention which contain as additional component d) one or more such complexing agents which are selected from water-soluble α-hydroxycarboxylic acids which have at least one hydroxyl and one carboxyl group and no water-soluble organic carboxylic acids according to component b ), as well as from their water-soluble salts. Furthermore, the water-soluble α-hydroxycarboxylic acids according to component d) preferably have not more than 8 carbon atoms and are in particular selected from polyhydroxymonocarboxylic acids and / or polyhydroxydicarboxylic acids each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or α-hydroxybutyric acid and from their water-soluble salts, most preferably selected from lactic acid and / or 2,3,4,5,6-pentahydroxyhexanoic acid and from their water-soluble salts.
Eine besonders effektive Formulierung der erfindungsgemäßen Zusammensetzung mit vorstehend genannten Komplexbildnern gemäß Komponente d) weist ein molares Verhältnis von Eisen-Ionen zu wasserlöslichen α-Hydroxycarbonsäuren und deren wasserlöslichen Salzen von zumindest 1 : 4, vorzugsweise von zumindest 1 : 3, jedoch von nicht größer als 2 : 1, vorzugsweise von nicht größer als 1 : 1 auf.A particularly effective formulation of the inventive composition with the aforementioned complexing agents according to component d) has a molar ratio of iron ions to water-soluble α-hydroxycarboxylic acids and their water-soluble salts of at least 1: 4, preferably of at least 1: 3, but not greater than 2: 1, preferably not greater than 1: 1.
Des Weiteren können in einer erfindungsgemäßen Zusammensetzung als optionale Komponente e) reduzierende Beschleuniger eingesetzt werden, die dem Fachmann aus dem Stand der Technik in der Phosphatierung bekannt sind. Hierzu gehören Hydrazin, Hydroxylamin, Nitroguanidin, N-Methylmorpholin-N-oxid, Glucoheptonat, Ascorbinsäure und reduzierende Zucker.Furthermore, in a composition according to the invention as an optional component e) reducing accelerators can be used, which are known to those skilled in the art in the phosphating. These include hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid and reducing sugars.
Der pH-Wert der erfindungsgemäßen alkalischen Zusammensetzung ist vorzugsweise nicht größer als 11,0, besonders bevorzugt vorzugsweise nicht größer als 10,5, insbesondere bevorzugt nicht größer als 10,0.The pH of the alkaline composition according to the invention is preferably not greater than 11.0, more preferably preferably not greater than 10.5, particularly preferably not greater than 10.0.
Die erfindungsgemäßen Zusammensetzungen können zudem oberflächenaktive Verbindungen, vorzugsweise nichtionische Tenside, enthalten, um eine zusätzliche Reinigung und Aktivierung der Metalloberflächen zu bewirken, so dass eine homogene Vereisenung auf den Zinkoberflächen zusätzlich begünstigt wird. Die nichtionischen Tenside sind dabei vorzugsweise ausgewählt aus einem oder mehreren ethoxylierten und/oder propoxylierten C10-C18 Fettalkoholen mit insgesamt zumindest zwei aber nicht mehr als 12 Alkoxygruppen, besonders bevorzugt Ethoxy- und/oder Propoxygruppen, die teilweise mit einem Alkylrest, besonders bevorzugt mit einem Methyl-, Ethyl-, Propyl-, Butyl-Rest endgrupppenverschlossen vorliegen können. Der Anteil an nichtionischen Tensiden in einer erfindungsgemäßen Zusammensetzung beträgt für eine hinreichende Reinigung und Aktivierung der Metalloberflächen vorzugsweise zumindest 0,01 g/l, besonders bevorzugt zumindest 0,1 g/l, wobei aus wirtschaftlichen Gründen vorzugsweise nicht mehr als 10 g/l an nichtionischen Tensiden enthalten sind.The compositions according to the invention may additionally contain surface-active compounds, preferably nonionic surfactants, in order to bring about additional purification and activation of the metal surfaces, so that homogeneous icing on the zinc surfaces is additionally promoted. The nonionic surfactants are preferably selected from one or more ethoxylated and / or propoxylated C 10 -C 18 fatty alcohols having a total of at least two but not more than 12 alkoxy groups, more preferably ethoxy and / or propoxy, some with an alkyl radical, more preferably with a Methyl, ethyl, propyl, butyl radical end-capped can. The proportion of nonionic surfactants in a composition according to the invention is preferably at least 0.01 g / l, more preferably at least 0.1 g / l, for sufficient cleaning and activation of the metal surfaces, and for economic reasons preferably not more than 10 g / l nonionic surfactants are included.
Zur Unterbindung von Ausfällungen ist es weiterhin bevorzugt, dass erfindungsgemäße Zusammensetzungen Zink-Ionen nicht in einer solchen Menge enthalten, für die das Verhältnis des molaren Gesamtanteils an Zink-Ionen und Eisen-Ionen zum molaren Gesamtanteil an wasserlöslichen organischen Carbonsäuren gemäß Komponente b) und wasserlöslichen organischen α-Hydroxycarbonsäuren gemäß Komponente d) und deren jeweiligen wasserlöslichen Salzen größer als 1 : 1, besonders bevorzugt größer als 2 : 3 ist.To prevent precipitation, it is further preferred that compositions according to the invention do not contain zinc ions in an amount for which the ratio of the total molar fraction of zinc ions and iron ions to the total molar fraction of water-soluble organic carboxylic acids according to component b) and water-soluble organic α-hydroxycarboxylic acids according to component d) and their respective water-soluble salts greater than 1: 1, more preferably greater than 2: 3.
Die vorliegende Erfindung zeichnet sich ferner darin aus, dass einer erfindungsgemäßen Zusammensetzung keine weiteren Schwermetalle hinzugesetzt werden müssen, um auf den Zinkoberflächen als Bestandteil der Vereisenung im Zusammenwirken mit einer nachfolgenden nasschemischen Konversionsbehandlung einen verbesserten Korrosionsschutz bereitzustellen. Eine erfindungsgemäße Zusammensetzung enthält daher vorzugsweise insgesamt weniger als 50 ppm von Metall-Ionen der Elemente Ni, Co, Mo, Cr, Ce, V und/oder Mn, besonders bevorzugt jeweils weniger als 10 ppm, insbesondere bevorzugt jeweils weniger als 1 ppm an diesen Elementen.The present invention is further characterized in that no further heavy metals have to be added to a composition according to the invention in order to provide improved corrosion protection on the zinc surfaces as part of the icing in cooperation with a subsequent wet chemical conversion treatment. A composition according to the invention therefore preferably contains less than 50 ppm total of metal ions of the elements Ni, Co, Mo, Cr, Ce, V and / or Mn, particularly preferably less than 10 ppm, particularly preferably less than 1 ppm of these elements.
Des Weiteren enthält die erfindungsgemäße Zusammensetzung vorzugsweise weniger als 1 g/l an wasserlöslichen oder wasserdispergierbaren organischen Polymeren, da sich eine Verschleppung von polymeren Bestandteilen aus der Vorbehandlung zur Vereisenung in nachfolgende Bäder zur nasschemischen Konversionsbehandlung nachteilig auf die Ausbildung der Konversionsschicht auswirken kann. Unter wasserlöslichen oder wasserdispergierbaren Polymeren werden erfindungsgemäß organische Verbindungen verstanden, die bei einer Ultrafiltration mit einer nominellen Ausschlussgrenze (NMWC "Nominal Molecular Weight Cut-Off") von 10.000 u im Retentat verbleiben.Furthermore, the composition according to the invention preferably contains less than 1 g / l of water-soluble or water-dispersible organic polymers, since carryover of polymeric constituents from the pretreatment for icing into subsequent baths for wet-chemical conversion treatment may adversely affect the formation of the conversion layer. According to the invention, water-soluble or water-dispersible polymers are understood as meaning organic compounds which remain in the retentate in an ultrafiltration with a nominal cutoff limit (NMWC) of 10,000 μ.
Die vorliegende Erfindung umfasst auch ein Konzentrat, das durch Verdünnung um den Faktor 5-50 eine zuvor beschriebene erfindungsgemäße alkalische Zusammensetzung liefert. Ein erfindungsgemäßes Konzentrat hat einen pH-Wert oberhalb von 8,5 und enthält vorzugsweise
- a) 5-100 g/l an Eisen-Ionen,
- b) 15-200 g/l an wasserlöslichen organischem Carbonsäuren, die zumindest eine Amino-Gruppe in α-, β-, oder γ-Stellung zur Säuregruppe aufweisen, sowie deren wasserlösliche Salze,
- c) 20-300 g/l an Oxosäuren von Phosphor oder Stickstoff sowie deren wasserlösliche Salze, wobei mindestens ein Phosphoratom oder Stickstoffatom in einer mittleren Oxidationsstufe vorliegt.
- a) 5-100 g / l of iron ions,
- b) 15-200 g / l of water-soluble organic carboxylic acids which have at least one amino group in α-, β-, or γ-position to the acid group, as well as their water-soluble salts,
- c) 20-300 g / l of oxo acids of phosphorus or nitrogen and their water-soluble salts, wherein at least one phosphorus atom or nitrogen atom is present in a middle oxidation state.
In einem zweiten Aspekt betrifft die vorliegende Erfindung ein Verfahren zur Vorbehandlung ("Vereisenung") von metallischen Bauteilen, die Zinkoberflächen aufweisen, wobei zumindest die Zinkoberflächen des Bauteils
- i) ggf. zunächst mit einem alkalischen Reiniger gereinigt und entfettet,
- ii) mit einer zuvor beschriebenen erfindungsgemäßen alkalischen Zusammensetzung in Kontakt gebracht, und
- iii) anschließend einer passivierenden nasschemischen Konversionsbehandlung unterzogen werden.
- i) if necessary, first cleaned and degreased with an alkaline cleaner,
- ii) contacted with a previously described inventive alkaline composition, and
- iii) subsequently subjected to a passivating wet chemical conversion treatment.
Im erfindungsgemäßen Verfahren wird im Schritt ii) zunächst eine Schichtauflage bestehend im Wesentlichen aus oxidischem und/oder metallischem Eisen auf den Zinkoberflächen erzeugt ("Vereisenung"). Auf den übrigen Oberflächen des metallischen Bauteils, die bspw. Oberflächen von Eisen, Stahl und/oder Aluminium sein können, ist eine derartige anorganische Schicht nicht nachweisbar. Die spezifische Abscheidung der Passivschicht auf den Zinkoberflächen führt im erfindungsgemäßen Verfahren, bei dem sich der Vereisenung eine passivierende nasschemische Konversionsbehandlung anschließt, überraschenderweise zu einer deutlichen Verbesserung der Lackhaftungseigenschaften dieser Oberflächen und unterbindet effektiv die Korrosion an Schnittkanten von verzinktem Stahl und die Kontaktkorrosion von mit den Zinkoberflächen verbundenen Eisenmetallen. Eine passivierende nasschemische Konversionsbehandlung ist eine in der Stahl- und Automobilindustrie übliche Maßnahme zur Vorbehandlung vor einem organischen Decklackaufbau.In the process according to the invention, in step ii), first of all, a coating layer consisting essentially of oxidic and / or metallic iron is produced on the zinc surfaces ("icing"). On the other surfaces of the metallic component, which may be, for example, surfaces of iron, steel and / or aluminum, such an inorganic layer is not detectable. The specific deposition of the passive layer on the zinc surfaces leads in the process according to the invention, in which the icing a passivating wet chemical conversion treatment, surprisingly to a significant improvement in paint adhesion properties of these surfaces and effectively prevents the corrosion of cut edges of galvanized steel and the contact corrosion of the zinc surfaces connected ferrous metals. A passivating wet-chemical conversion treatment is a standard procedure in the steel and automotive industry for pre-treatment before an organic topcoat composition.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens weist das metallische Bauteil verzinkte Stahloberflächen auf. Insbesondere vorteilhaft ist das Verfahren bei der Behandlung von verzinktem Bandstahl, da es einen hervorragenden Kantenkorrosionsschutz liefert, und von Bauteilen bestehend aus von in Mischbauweise zusammengesetzten und/oder zusammengefügten metallischen Bauelementen aus verzinktem Stahl, Eisen und/oder Stahl und ggf. Aluminium, da es die Kontaktkorrosion stark reduziert.In a preferred embodiment of the method according to the invention, the metallic component has galvanized steel surfaces. Particularly advantageous is the method in the treatment of galvanized steel strip, as it provides excellent edge corrosion protection, and of components consisting of mixed composite and / or assembled metallic components made of galvanized steel, iron and / or steel and possibly aluminum, as it the contact corrosion is greatly reduced.
Der alkalische Reinigungsschritt i) im erfindungsgemäßen Verfahren ist optional und dann erforderlich, wenn die Oberflächen von Zink Verunreinigungen in Form von Salzen und Fetten, beispielsweise Ziehfette und Korrosionsschutzöle, aufweisen.The alkaline cleaning step i) in the process according to the invention is optional and necessary when the surfaces of zinc have impurities in the form of salts and fats, for example drawing fats and corrosion protection oils.
Die Vereisenung erfolgt im Schritt ii) des erfindungsgemäßen Verfahrens, wobei die Art des In-Kontakt-bringens mit der erfindungsgemäßen alkalischen Zusammensetzung verfahrenstechnisch nicht auf eine bestimmte Methode beschränkt ist. Vorzugsweise werden die Zinkoberflächen durch Tauchen oder Spritzen mit der erfindungsgemäßen Zusammensetzung zur Vereisenung in Kontakt gebracht.The icing takes place in step ii) of the process according to the invention, wherein the manner of bringing into contact with the alkaline composition according to the invention is not restricted in terms of process technology to a particular method. Preferably, the zinc surfaces are contacted by dipping or spraying with the composition according to the invention for freezing.
In einer bevorzugten Ausführungsform des Verfahrens wird das metallische Bauteil für zumindest 3 Sekunden, aber nicht mehr als 4 Minuten bei einer Temperatur von zumindest 30°C, besonders bevorzugt zumindest 40°C, aber nicht mehr als 70°C, besonders bevorzugt nicht mehr als 60°C mit einer erfindungsgemäßen alkalischen Zusammensetzung in Kontakt gebracht. Die erfindungsgemäßen Zusammensetzungen bewirken, wie bereits geschildert, eine Vereisenung der Zinkoberflächen. Die Ausbildung der Vereisenung erfolgt dabei selbst-limitierend, d.h. mit zunehmender Vereisenung der Zinkoberflächen nimmt die Abscheiderate an Eisen ab. Die bevorzugten Behandlungs- bzw. Kontaktzeiten sollten im erfindungsgemäßen Verfahren so gewählt sein, dass die Schichtauflage an Eisen zumindest 20 mg/m2 bezogen auf das Element Eisen beträgt. Die Behandlungs- und Kontaktzeiten für die Realisierung einer solchen Mindestschichtauflage variieren je nach Applikationsart und hängen insbesondere von der auf die zu behandelnde Metalloberfläche einwirkenden Strömung der wässrigen Fluids ab. So erfolgt die Ausbildung der Vereisenung in Verfahren, bei denen die Zusammensetzung durch Spritzen aufgebracht wird, rascher als in Tauchapplikationen. Unabhängig von der Applikationsart werden durch die erfindungsgemäßen Zusammensetzungen aufgrund des selbst-limitierenden Vereisenung keine Schichtauflagen an Eisen deutlich oberhalb von 300 mg/m2 bezogen auf das Element Eisen erzielt.
Für eine hinreichende Schichtausbildung und einen optimalen Kantenschutz bei der Behandlung von verzinkten Stahloberflächen sollten unmittelbar nach der Vereisenung im Schritt ii) mit oder ohne nachfolgendem Spülschritt Schichtauflagen an Eisen von vorzugsweise zumindest 20 mg/m2, besonders bevorzugt zumindest 50 mg/m2, insbesondere bevorzugt mehr als 100 mg/m2. aber vorzugsweise nicht mehr als 250 mg/m2 jeweils bezogen auf das Element Eisen realisiert vorliegen.
Die Schichtauflage an Eisen auf den Zinkoberflächen kann nach Auflösen der Beschichtung mittels eines spektroskopischen Verfahrens ermittelt werden, dass im Beispielteil der vorliegenden Erfindung beschrieben wird.In a preferred embodiment of the method, the metallic component is for at least 3 seconds, but not more than 4 minutes at a temperature of at least 30 ° C, more preferably at least 40 ° C, but not more than 70 ° C, more preferably not more than 60 ° C brought into contact with an alkaline composition according to the invention. As already described, the compositions according to the invention cause an icing of the zinc surfaces. The formation of icing is self-limiting, ie with increasing icing of the zinc surfaces, the deposition rate of iron decreases. The preferred treatment or contact times should be selected in the method according to the invention so that the layer of iron is at least 20 mg / m 2 based on the element iron. The treatment and contact times for the realization of such a minimum layer coverage vary depending on the type of application and depend in particular on the flow of the aqueous fluids acting on the metal surface to be treated. Thus, the formation of icing in processes in which the composition is applied by spraying, faster than in immersion applications. Irrespective of the mode of application, the coating compositions according to the invention do not produce any layer deposits on iron significantly above 300 mg / m 2, based on the element iron, due to the self-limiting freezing.
For a sufficient layer formation and an optimal edge protection in the treatment of galvanized steel surfaces immediately after the icing in step ii) with or without subsequent rinsing layer coatings of iron preferably at least 20 mg / m 2 , more preferably at least 50 mg / m 2 , in particular preferably more than 100 mg / m 2 . but preferably not more than 250 mg / m 2 in each case based on the element iron realized realized.
The coating of iron on the zinc surfaces can be determined after dissolution of the coating by means of a spectroscopic method which is described in the examples of the present invention.
Die Vereisenung im Schritt ii) des erfindungsgemäßen Verfahrens wird vorzugsweise außenstromlos durchgeführt, d.h. ohne Anlegen einer äußeren Spannungsquelle an das metallische Bauteil.The icing in step ii) of the method according to the invention is preferably carried out without external current, ie without applying an external voltage source to the metallic component.
Im Schritt iii) des erfindungsgemäßen Verfahrens erfolgt nachfolgend dem Schritt ii) mit oder ohne dazwischenliegendem Spülschritt eine passivierende nasschemische Konversionsbehandlung. Unter nasschemischer Konversionsbehandlung versteht man erfindungsgemäß das In-Kontakt-bringen zumindest der Zinkoberflächen des metallischen Bauteils mit einer wässrigen Zusammensetzung, die eine passivierende und im Wesentlichen anorganische Konversionsbeschichtung auf den behandelten Zinkoberflächen erzeugt. Eine Konversionsbeschichtung ist dabei jede anorganische Beschichtung auf dem metallischen Zinksubstrat, die keine oxidische oder hydroxidische Beschichtung darstellt, deren kationogener Hauptbestandteil Zink-Ionen sind. Eine Konversionsbeschichtung kann daher eine Zinkphosphatschicht sein.In step iii) of the process according to the invention, a passivating wet-chemical conversion treatment takes place subsequently to step ii) with or without an intermediate rinsing step. Wet-chemical conversion treatment is understood according to the invention as bringing into contact at least the zinc surfaces of the metallic component with an aqueous composition which produces a passivating and substantially inorganic conversion coating on the treated zinc surfaces. In this case, a conversion coating is any inorganic coating on the metallic zinc substrate which does not represent an oxide or hydroxide coating whose cationogenic main constituent is zinc ions. A conversion coating may therefore be a zinc phosphate layer.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt im Schritt iii) eine passivierende nasschemische Konversionsbehandlung durch In-Kontakt-bringen mit einer sauren wässrigen Zusammensetzung, die insgesamt zumindest 5 ppm, jedoch insgesamt nicht mehr als 1500 ppm an wasserlöslichen anorganischen Verbindungen der Elemente Zr, Ti, Si und/oder Hf bezogen auf die vorgenannten Elemente und vorzugsweise wasserlösliche anorganische Verbindungen, die Fluorid-Ionen freisetzen, beispielsweise Fluorokomplexe, Flusssäure und/oder Metallfluoride, enthält.In a preferred embodiment of the process according to the invention, a passivating wet chemical conversion treatment is carried out in step iii) by bringing into contact with an acidic aqueous composition which has a total of at least 5 ppm but not more than 1500 ppm total of water-soluble inorganic compounds of the elements Zr, Ti , Si and / or Hf based on the aforementioned elements, and preferably water-soluble inorganic compounds which release fluoride ions, for example, fluorocomplexes, hydrofluoric acid and / or metal fluorides.
Diesbezüglich bevorzugt sind solche sauren wässrigen Zusammensetzungen im Schritt iii) des erfindungsgemäßen Verfahrens, die als wasserlösliche Verbindungen der Elemente Zirconium, Titan und/oder Hafnium lediglich wasserlösliche Verbindungen der Elemente Zirconium und/oder Titan, besonders bevorzugt wasserlösliche Verbindungen des Elements Zirconium enthalten. Als wasserlösliche Verbindungen der Elemente Zirconium und/oder Titan können sowohl Verbindungen, die in wässriger Lösung in Anionen von Fluorokomplexen der Elemente Titan und/oder Zirconium dissozieren, beispielsweise H2ZrF6, K2ZrF6, Na2ZrF6 und (NH4)2ZrF6 und die analogen Titan-Verbindungen, als auch fluorfreie Verbindungen der Elemente Zirconium und/oder Titan, beispielsweise (NH4)2Zr(OH)2(CO3)2 oder TiO(SO4), in sauren wässrigen Zusammensetzungen im Schritt iii) des erfindungsgemäßen Verfahrens eingesetzt werden.Preferred in this regard are those acidic aqueous compositions in step iii) of the process according to the invention which contain as water-soluble compounds of the elements zirconium, titanium and / or hafnium only water-soluble compounds of the elements zirconium and / or titanium, more preferably water-soluble compounds of the element zirconium. As water-soluble compounds of the elements zirconium and / or titanium, both compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements titanium and / or zirconium, for example H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium compounds, as well as fluorine-free compounds of the elements zirconium and / or titanium, for example (NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 or TiO (SO 4 ), in acidic aqueous compositions used in step iii) of the method according to the invention.
Im Schritt iii) des bevorzugten erfindungsgemäßen Verfahrens ist die saure wässrige Zusammensetzung, die insgesamt zumindest 5 ppm, jedoch insgesamt nicht mehr als 1500 ppm an wasserlöslichen anorganischen Verbindungen der Elemente Zr, Ti, Si und/oder Hf bezogen auf die vorgenannten Elemente enthält, vorzugsweise chromfrei, d.h. sie enthält weniger als 10 ppm, vorzugsweise weniger als 1 ppm Chrom, insbesondere kein Chrom(VI).In step iii) of the preferred process according to the invention, the acidic aqueous composition containing a total of at least 5 ppm but not more than 1500 ppm total of water-soluble inorganic compounds of the elements Zr, Ti, Si and / or Hf with respect to the aforementioned elements is preferred chromium-free, ie it contains less than 10 ppm, preferably less than 1 ppm of chromium, in particular no chromium (VI).
In einer alternativ bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt im Schritt iii) eine Zinkphosphatierung, wobei in der Zinkphosphatierung auf die Anwesenheit der Schwermetalle Ni und/oder Cu aufgrund der vorherigen Vereisenung der Zinkoberflächen des metallischen Bauteils im Schritt ii) weitgehend verzichtet werden kann. Die Vereisenung der Zinkoberflächen erbringt für eine nachfolgende Zinkphosphatierung also den unerwarteten Vorteil, dass für derart phosphatierte Zinkoberflächen ein Korrosionsschutz und eine Lackhaftung resultiert, die mit der Zinkphosphatierung von Eisen- oder Stahloberflächen vergleichbar ist.In an alternative preferred embodiment of the process according to the invention, a zinc phosphating is carried out in step iii), wherein the presence of the heavy metals Ni and / or Cu in the zinc phosphating can largely be dispensed with due to the previous icing of the zinc surfaces of the metallic component in step ii). The icing of the zinc surfaces thus provides for subsequent zinc phosphating the unexpected advantage that results for such phosphated zinc surfaces corrosion protection and paint adhesion, which is comparable to the Zinkphosphatierung of iron or steel surfaces.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens besteht die passivierende nasschemische Konversionsbehandlung im Schritt iii) darin, dass die im Schritt ii) vorbehandelten verzinkten Stahloberflächen mit einer sauren wässrigen Zusammensetzung in Kontakt gebracht werden, die einen pH-Wert im Bereich von 2,5-3,6 aufweist und
- a) 0,2 bis 3,0 g/L Zink(II)-lonen,
- b) 5,0 bis 30 g/L Phosphat-Ionen berechnet als P2O5, und
- c) vorzugsweise jeweils weniger als 0,1 g/L an ionischen Verbindungen der Metalle Nickel und Cobalt jeweils bezogen auf das metallische Element enthält.
- a) 0.2 to 3.0 g / L zinc (II) ions,
- b) 5.0 to 30 g / L of phosphate ions calculated as P 2 O 5 , and
- c) preferably each less than 0.1 g / L of ionic compounds of the metals nickel and cobalt in each case based on the metallic element.
Die aus einem erfindungsgemäßen Verfahren unmittelbar hervorgehenden vorbehandelten metallischen Bauteile, die Oberflächen von Zink aufweisen, werden sodann mit oder ohne dazwischenliegendem Spül- und/oder Trocknungsschritt vorzugsweise mit einer organischen Deckschicht versehen. Die erste Deckschicht bei der Vorbehandlung von bereits zugeschnitten, umgeformten und zusammengefügten Bauelementen ist üblicherweise ein Elektrotauchlack, besonders bevorzugt ein kathodischer Tauchlack ist. Demgegenüber werden organische Primerbeschichtungen vorzugsweise als erste organische Deckschicht bei der korrosionsschützenden oder dekorativen Beschichtung von verzinktem Bandstahl im Anschluss an das erfindungsgemäße Verfahren aufgebracht.The pretreated metallic components, which have surfaces of zinc directly resulting from a method according to the invention, are then preferably provided with an organic covering layer, with or without an intermediate rinsing and / or drying step. The first cover layer in the pretreatment of already cut, formed and assembled components is usually an electrodeposition paint, more preferably a cathodic dip. In contrast, organic primer coatings are preferably applied as the first organic cover layer in the anticorrosive or decorative coating of galvanized steel strip following the inventive method.
Die in einem erfindungsgemäßen Verfahren behandelten metallischen Bauteile, die Oberflächen von Zink aufweisen, finden Verwendung im Karosseriebau bei der automobilen Fertigung, im Schiffsbau, im Baugewerbe sowie für die Herstellung Weißer Ware.The treated in a process according to the invention metallic components having surfaces of zinc, find use in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
Der Einfluss verschiedener α-Aminosäuren hinsichtlich der Homogenität der Vereisenung nach dem In-Kontakt-bringen von erfindungsgemäßen Zusammensetzungen mit elektrolytisch verzinktem Stahl durch Tauchen ist in Tabelle 1 wiedergegeben.The influence of various α-amino acids with respect to the homogeneity of the icing after contacting of inventive compositions with electrolytically galvanized steel by dipping is reproduced in Table 1.
Zunächst erhält man mit allen erfindungsgemäßen Zusammensetzungen (C1-C4) dünne Überzüge aus oxidischem und/oder metallischem Eisen auf den Zinkoberflächen ("Vereisenung"), wobei jedoch besonders homogene Beschichtungen speziell von erfindungsgemäßen Zusammensetzungen (C1; C5) enthaltend Glycin gebildet werden.
Die Konzentration der Aktivkomponenten in einer erfindungsgemäßen Zusammensetzung wirkt sich unmittelbar auf die Abscheiderate aus, so dass verdünnte Zusammensetzungen entsprechend länger mit der verzinkten Stahloberfläche in Kontakt gebracht werden müssen, um eine homogen beschichtete Zinkoberfläche zu erhalten (siehe C1 im Vergleich zu C5).The concentration of the active components in a composition according to the invention has an immediate effect on the deposition rate, so that dilute compositions must be brought into contact with the galvanized steel surface for a longer time in order to obtain a homogeneously coated zinc surface (see C1 in comparison to C5).
Im Folgenden soll die Wirkung der Vereisenung bei Verwendung erfindungsgemäßer Zusammensetzungen anhand von Prozessketten zur korrosionsschützenden Vorbehandlung von Zinkoberflächen dargestellt werden. Tabelle 2 gibt die korrosive Unterwanderung eines Tauchlackes auf elektrolytisch verzinktem Stahl nach der jeweiligen Prozesskette zur korrosionsschützenden Vorbehandlung im Wechselklimatest und Steinschlagtest wieder.In the following, the effect of icing when using compositions according to the invention on the basis of process chains for the corrosion-protective pretreatment of zinc surfaces will be illustrated. Table 2 shows the corrosive infiltration of an immersion paint on electrolytically galvanized steel after the respective process chain for corrosion-protective pretreatment in Wechselklimatest and stone impact test again.
Es folgen die einzelnen Verfahrensschritte der in Tabelle 2 aufgeführten Prozessketten zur korrosionsschützenden Behandlung einzelner verzinkter Stahlbleche (Gardobond® MBZE7):
A. Alkalische Reinigung (pH 11):
B. Spülen mit vollentsalztem Wasser (κ<1 µSCM-1)
C. Vereisenung unter Verwendung einer Zusammensetzung gemäß Tabelle 1: Behandlungsdauer bei 50 °C: 60 Sekunden
D. Aktivierung:
Behandlungsdauer bei 20 °C: 60 Sekunden
E1. Saure Passivierung:
pH-Wert 4
Behandlungsdauer bei 30 °C: 120 Sekunden
E2. Nickelfreie Phosphatierung:
Freies Fluorid: 40 mg/L
Freie Säure: 1,3 Punkte (pH 3,6)
Gesamtsäure : 26 Punkte (pH 8,5)
Behandlungsdauer bei 50 °C: 180 Sekunden
E3. Nickelhaltige Phosphatierung (Trikationen-Phosphatierung):
Freies Fluorid: 40 mg/L
Freie Säure: 1,3 Punkte (pH 3,6)
Gesamtsäure : 26,5 Punkte (pH 8,5)
Behandlungsdauer bei 50 °C : 180 Sekunden
F. Lackaufbau: EV2007 (Fa. PPG): Schichtdicke 17 - 19 µmThe individual process steps of the process chains listed in Table 2 for the corrosion-protective treatment of individual galvanized steel sheets (Gardobond® MBZE7) follow:
A. Alkaline Purification (pH 11):
B. Rinsing with demineralised water (κ <1 μSCM -1 )
C. Icing using a composition according to Table 1: Treatment time at 50 ° C: 60 seconds
D. Activation:
Duration of treatment at 20 ° C: 60 seconds
E1. Acid passivation:
pH 4
Treatment time at 30 ° C: 120 seconds
E2. Nickel-free phosphating:
Free fluoride: 40 mg / L
Free acid: 1.3 points (pH 3.6)
Total acidity: 26 points (pH 8.5)
Treatment time at 50 ° C: 180 seconds
E3. Nickel-containing phosphating (trication-phosphating):
Free fluoride: 40 mg / L
Free acid: 1.3 points (pH 3.6)
Total acid: 26.5 points (pH 8.5)
Treatment time at 50 ° C: 180 seconds
F. Coating structure: EV2007 (PPG): layer thickness 17-19 μm
Aus der Tabelle 2 geht deutlich hervor, dass die Vereisenung in einer erfindungsgemäßen Prozesskette, die die nasschemische Konversion mittels wässriger Zirconium-haltiger Passivierungslösungen (B1) im Vergleich zu einer analogen Prozesskette, in der auf die Vereisenung verzichtet wird (V1) einen verbesserten Korrosionsschutz bewirkt.
Gleiches kann für die Verbesserung des Korrosionsschutzes derjenigen verzinkten Stahlbleche festgestellt werden, die einer nickelfreien Zinkphosphatierung unterzogen wurden. Auch hier resultieren mit der vorausgehenden Vereisenung (B2) wesentlich verbesserte Korrosionswerte im Vergleich zur reinen Zinkphosphatierung (V2). Die mit der Vereisenung erzielten Korrosionsergebnisse (B2) sind sogar verbessert im Vergleich mit der im Stand der Technik zur korrosionsschützenden Vorbehandlung von in Mischbauweise gefertigten Bauteilen häufig eingesetzten Trikation-Phosphatierung (V3).
The same can be said for the improvement of the corrosion protection of those galvanized steel sheets subjected to nickel-free zinc phosphating. Here, too, the previous freezing (B2) results in significantly improved corrosion values compared to pure zinc phosphating (V2). The corrosion results (B2) achieved with the icing are even improved in comparison with the trication-phosphating (V3) frequently used in the prior art for the corrosion-protective pretreatment of components manufactured in mixed construction.
Claims (12)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL16175371T PL3093370T3 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before zinc phosphating |
| EP16175371.0A EP3093370B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before zinc phosphating |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12156863.8A EP2631333A1 (en) | 2012-02-24 | 2012-02-24 | Pre-treatment of zinc surfaces before passivation |
| EP13705479.7A EP2817434B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before passivation |
| EP16175371.0A EP3093370B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before zinc phosphating |
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| Application Number | Title | Priority Date | Filing Date |
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| EP13705479.7A Division EP2817434B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before passivation |
| EP13705479.7A Division-Into EP2817434B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before passivation |
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| EP3093370A1 true EP3093370A1 (en) | 2016-11-16 |
| EP3093370B1 EP3093370B1 (en) | 2018-01-17 |
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| EP16175371.0A Active EP3093370B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before zinc phosphating |
| EP13705479.7A Active EP2817434B1 (en) | 2012-02-24 | 2013-02-22 | Pre-treatment of zinc surfaces before passivation |
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| US (1) | US10227686B2 (en) |
| EP (3) | EP2631333A1 (en) |
| JP (1) | JP6526968B2 (en) |
| KR (1) | KR102095832B1 (en) |
| CN (1) | CN104185693B (en) |
| AU (1) | AU2013224115B2 (en) |
| CA (1) | CA2864467C (en) |
| ES (2) | ES2624195T3 (en) |
| HU (2) | HUE038740T2 (en) |
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| WO (1) | WO2013124400A1 (en) |
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| WO2016120671A1 (en) * | 2015-01-30 | 2016-08-04 | Arcelormittal | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve tribological properties |
| WO2016120669A1 (en) * | 2015-01-30 | 2016-08-04 | Arcelormittal | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve corrosion resistance |
| WO2016120670A1 (en) * | 2015-01-30 | 2016-08-04 | Arcelormittal | Method for the production of a coated metal sheet, comprising the application of an aqueous solution containing an amino acid, and associated use in order to improve compatibility with an adhesive |
| US10882771B2 (en) * | 2015-02-06 | 2021-01-05 | Baker Hughes, A Ge Company, Llc | Use of phosphino polymer and polyhydroxypolycarboxylic acid as corrosion inhibitor |
| WO2017109541A1 (en) | 2015-12-21 | 2017-06-29 | Arcelormittal | Method for producing a high strength coated steel sheet having improved ductility and formability, and obtained coated steel sheet |
| US10683576B2 (en) | 2017-03-27 | 2020-06-16 | Baker Hughes, A Ge Company, Llc | Corrosion inhibitors for passivation of galvanized coatings and carbon steel |
| US10655217B2 (en) * | 2018-05-01 | 2020-05-19 | Spts Technologies Limited | Method of forming a passivation layer on a substrate |
| EP3569734A1 (en) | 2018-05-18 | 2019-11-20 | Henkel AG & Co. KGaA | Passivation composition based on trivalent chromium |
| EP3663435B1 (en) | 2018-12-05 | 2024-03-13 | Henkel AG & Co. KGaA | Passivation composition based on mixtures of phosphoric and phosphonic acids |
| WO2021139955A1 (en) | 2020-01-06 | 2021-07-15 | Henkel Ag & Co. Kgaa | Passivation composition suitable for inner surfaces of zinc coated steel tanks storing hydrocarbons |
| CN116670236A (en) | 2021-01-06 | 2023-08-29 | 汉高股份有限及两合公司 | Cr (III) -based improved passivation for zinc-coated aluminum steels |
| GB2603194A (en) | 2021-02-01 | 2022-08-03 | Henkel Ag & Co Kgaa | Improved cr(iii) based dry-in-place coating composition for zinc coated steel |
| CN113913827B (en) * | 2021-09-09 | 2023-05-16 | 东风汽车集团股份有限公司 | Quenching and tempering state zinc-plated carbon steel metallographic corrosive agent and application thereof |
| EP4174211A1 (en) * | 2021-11-02 | 2023-05-03 | Henkel AG & Co. KGaA | Multistage treatment for activated zinc phosphating of metallic components with zinc surfaces |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1496683A (en) * | 1965-10-19 | 1967-09-29 | Parker Ste Continentale | Metal coating process |
| FR1538274A (en) * | 1967-10-02 | 1968-08-30 | Parker Ste Continentale | Method and composition for the treatment of metals |
| US3444007A (en) * | 1967-03-13 | 1969-05-13 | Hooker Chemical Corp | Process of forming paint-base coatings on zinc and zinc alloy surfaces |
| FR2352070A1 (en) * | 1975-05-21 | 1977-12-16 | Parker Ste Continentale | Pre-phosphating treatment for zinc alloys - with an aq soln contg metal ions, such as iron, antimony or manganese etc. |
| US5294266A (en) * | 1989-07-28 | 1994-03-15 | Metallgesellschaft Aktiengesellschaft | Process for a passivating postrinsing of conversion layers |
| DE19733972A1 (en) | 1997-08-06 | 1999-02-11 | Henkel Kgaa | Alkaline band passivation |
| DE102007021364A1 (en) | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallizing pretreatment of zinc surfaces |
| DE102010001686A1 (en) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4381203A (en) * | 1981-11-27 | 1983-04-26 | Amchem Products, Inc. | Coating solutions for zinc surfaces |
| JPS6220880A (en) * | 1985-07-19 | 1987-01-29 | Nippon Parkerizing Co Ltd | Surface treatment of zinc-aluminum alloy plated steel sheet |
| JP2901341B2 (en) * | 1990-11-29 | 1999-06-07 | 日本鋼管株式会社 | Pretreatment method for chromate treatment of zinc or zinc alloy |
| DE102006052919A1 (en) * | 2006-11-08 | 2008-05-15 | Henkel Kgaa | Zr / Ti-containing phosphating solution for the passivation of metal composite surfaces |
| MX365825B (en) * | 2009-12-28 | 2019-06-17 | Henkel Ag & Co Kgaa | Metal pretreatment composition containing zirconium, copper, zinc, and nitrate and related coatings on metal substrates. |
-
2012
- 2012-02-24 EP EP12156863.8A patent/EP2631333A1/en not_active Withdrawn
-
2013
- 2013-02-22 JP JP2014558113A patent/JP6526968B2/en active Active
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- 2013-02-22 CN CN201380010446.6A patent/CN104185693B/en active Active
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2014
- 2014-08-22 US US14/466,377 patent/US10227686B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1496683A (en) * | 1965-10-19 | 1967-09-29 | Parker Ste Continentale | Metal coating process |
| US3444007A (en) * | 1967-03-13 | 1969-05-13 | Hooker Chemical Corp | Process of forming paint-base coatings on zinc and zinc alloy surfaces |
| FR1538274A (en) * | 1967-10-02 | 1968-08-30 | Parker Ste Continentale | Method and composition for the treatment of metals |
| FR2352070A1 (en) * | 1975-05-21 | 1977-12-16 | Parker Ste Continentale | Pre-phosphating treatment for zinc alloys - with an aq soln contg metal ions, such as iron, antimony or manganese etc. |
| US5294266A (en) * | 1989-07-28 | 1994-03-15 | Metallgesellschaft Aktiengesellschaft | Process for a passivating postrinsing of conversion layers |
| DE19733972A1 (en) | 1997-08-06 | 1999-02-11 | Henkel Kgaa | Alkaline band passivation |
| DE102007021364A1 (en) | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallizing pretreatment of zinc surfaces |
| DE102010001686A1 (en) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2864467A1 (en) | 2013-08-29 |
| WO2013124400A1 (en) | 2013-08-29 |
| US20140360630A1 (en) | 2014-12-11 |
| JP6526968B2 (en) | 2019-06-12 |
| CN104185693B (en) | 2016-06-29 |
| HUE033958T2 (en) | 2018-01-29 |
| KR102095832B1 (en) | 2020-04-01 |
| ES2624195T3 (en) | 2017-07-13 |
| KR20140129238A (en) | 2014-11-06 |
| PL2817434T3 (en) | 2017-07-31 |
| EP2817434A1 (en) | 2014-12-31 |
| AU2013224115B2 (en) | 2017-02-02 |
| HUE038740T2 (en) | 2018-11-28 |
| CN104185693A (en) | 2014-12-03 |
| EP2817434B1 (en) | 2017-02-01 |
| PL3093370T3 (en) | 2018-07-31 |
| EP2631333A1 (en) | 2013-08-28 |
| US10227686B2 (en) | 2019-03-12 |
| ES2658337T3 (en) | 2018-03-09 |
| JP2015510550A (en) | 2015-04-09 |
| CA2864467C (en) | 2020-05-05 |
| AU2013224115A1 (en) | 2014-09-11 |
| EP3093370B1 (en) | 2018-01-17 |
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