EP1114206A1 - Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings - Google Patents
Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatingsInfo
- Publication number
- EP1114206A1 EP1114206A1 EP99936607A EP99936607A EP1114206A1 EP 1114206 A1 EP1114206 A1 EP 1114206A1 EP 99936607 A EP99936607 A EP 99936607A EP 99936607 A EP99936607 A EP 99936607A EP 1114206 A1 EP1114206 A1 EP 1114206A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- bath
- bath according
- amount
- coatings
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 71
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 21
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 hydroxide ions Chemical class 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003464 sulfur compounds Chemical class 0.000 claims description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 4
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000004902 Softening Agent Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003944 halohydrins Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- BCXBKOQDEOJNRH-UHFFFAOYSA-N NOP(O)=O Chemical class NOP(O)=O BCXBKOQDEOJNRH-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 claims 1
- 235000001968 nicotinic acid Nutrition 0.000 abstract description 8
- 239000011664 nicotinic acid Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 description 24
- 238000009826 distribution Methods 0.000 description 20
- 238000000151 deposition Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 7
- MACMNSLOLFMQKL-UHFFFAOYSA-N 1-sulfanyltriazole Chemical compound SN1C=CN=N1 MACMNSLOLFMQKL-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- AVWFAACIXBQMBF-UHFFFAOYSA-N 1-benzylpyridin-1-ium-3-carboxylate Chemical compound [O-]C(=O)C1=CC=C[N+](CC=2C=CC=CC=2)=C1 AVWFAACIXBQMBF-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- FCQPNTOQFPJCMF-UHFFFAOYSA-N 1,3-bis[3-(dimethylamino)propyl]urea Chemical compound CN(C)CCCNC(=O)NCCCN(C)C FCQPNTOQFPJCMF-UHFFFAOYSA-N 0.000 description 4
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000176 sodium gluconate Substances 0.000 description 4
- 235000012207 sodium gluconate Nutrition 0.000 description 4
- 229940005574 sodium gluconate Drugs 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- PHCDZUPEIPGYOG-UHFFFAOYSA-N [Fe].[Co].[Zn] Chemical compound [Fe].[Co].[Zn] PHCDZUPEIPGYOG-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 2
- LBKDGROORAKTLC-UHFFFAOYSA-N 1,5-dichloropentane Chemical compound ClCCCCCCl LBKDGROORAKTLC-UHFFFAOYSA-N 0.000 description 2
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 2
- DVDWDFLGEGWZFP-UHFFFAOYSA-N 1-[[4-[(3-carboxylatopyridin-1-ium-1-yl)methyl]phenyl]methyl]pyridin-1-ium-3-carboxylate Chemical compound [O-]C(=O)C1=CC=C[N+](CC=2C=CC(C[N+]=3C=C(C=CC=3)C([O-])=O)=CC=2)=C1 DVDWDFLGEGWZFP-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FPPBCGUXPMKUIM-UHFFFAOYSA-N 1,3-bis[3-(diethylamino)propyl]urea Chemical compound CCN(CC)CCCNC(=O)NCCCN(CC)CC FPPBCGUXPMKUIM-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- ZUSZPUNTECJHJZ-UHFFFAOYSA-N 2,3-dibromo-1,4-dimethylbenzene Chemical group CC1=CC=C(C)C(Br)=C1Br ZUSZPUNTECJHJZ-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- QJSFUOBKBXVTMN-UHFFFAOYSA-N C=C.P(O)(O)=O Chemical compound C=C.P(O)(O)=O QJSFUOBKBXVTMN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DUIOPKIIICUYRZ-NJFSPNSNSA-N aminourea Chemical group NN[14C](N)=O DUIOPKIIICUYRZ-NJFSPNSNSA-N 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
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 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
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000006636 nicotinic acid Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Definitions
- Cyanide-free zinc electrolyte baths can be divided into two bath types, namely weakly acidic zinc electrolytes (containing zinc chloride or zinc sulfate) and alkaline zincate electrolytes.
- a uniformly shiny zinc layer is deposited from weakly acidic zinc baths, so that this process could quickly assert a strong market share.
- this method has the disadvantage that its current efficiency is always 100% over a wide current density range.
- the ratio of zinc layer thickness in the high current density range to zinc layer thickness in the low current density range is called the layer thickness distribution and should ideally be 1.
- Zinc and zinc alloy baths have to meet ever higher demands. Accordingly, a zinc layer on the object to be coated should have the same layer thickness everywhere and have a high gloss.
- a good layer thickness distribution can be achieved by lowering the current efficiency in the high current density range, while maintaining the current efficiency in the low current density range.
- Alkaline zinc plating baths are generally based on an aqueous solution of zinc ions in sodium or potassium hydroxide. The use of these baths makes it possible to deposit zinc layers with a high gloss (DE 25 25 264, US 3 884 774), but these zinc layers do not have a uniform layer thickness distribution.
- No. 5,435,898 describes a similar compound with the trade name Mirapol WT as an additive for zinc and zinc alloy electroplating baths, which is also said to greatly improve the layer thickness distribution.
- DE 195 09 713 describes a diallylammonium sulfur dioxide copolymer as an additive for zinc and zinc alloy plating baths, which is intended to give the zinc layer a uniform layer thickness.
- US Pat. No. 4,030,987 likewise describes a diallylammonium-sulfur dioxide copolymer as an additive for zinc and zinc alloy electroplating baths, which is intended to give the zinc layer a uniform layer thickness.
- the invention is therefore based on the object of overcoming the shortcomings of the prior art and, in particular, of providing an aqueous cyanide-free alkaline bath for the electrodeposition of zinc and zinc alloy coatings, with which coatings of zinc or zinc alloys can be obtained, in which even after prolonged use Storage there is no tendency to form flaking.
- the advantages of these baths with regard to a uniform layer thickness, a high gloss and the uniformity of the alloy components in the coating are to be maintained over a wide range of current densities. It has now been found that the addition of a special type of quaternary ammonium polymer to aqueous alkaline cyanide-free zinc baths improves the layer thickness distribution of the coatings obtained and reduces the blistering of the coatings.
- the invention therefore relates to an aqueous alkaline, cyano-free bath for the galvanic deposition of zinc or zinc alloy coatings on substrate surfaces, which is characterized in that it
- n is 2 or 3
- n is at least 2
- R x , R 2 , R 3 and R which may be the same or different, each represent methyl, ethyl, hydroxyethyl
- p is in the range of 3 to 12 and X "stands for Cl “ , Br “ and / or I "
- the soluble polymer of the general formula A contained in the bath according to the invention can be obtained by reacting N, N'-bis [3- (Dialkylamino) alkyl] ureas with 1, ⁇ -Dihaiogenalkanen he will keep.
- This reaction can be represented by the following reaction scheme, where the radicals R ! -R 4 , X and m and n are as defined above:
- the reaction of the starting products can be carried out, for example, in aqueous solution and at temperatures of 20 to 100 ° C.
- the polymers of formula A used according to the invention can be obtained in which the amino urea units are connected by hydrocarbon bridges.
- the degree of polymerization of these polymers is 2-80.
- the starting materials of the general formulas D and E are known per se.
- the diaminoureas of the formula D are described, for example, in JP 04-198160.
- the other starting products for the preparation of the polymers used according to the invention are l, ⁇ -dihaloalkanes of the general formula E. Individual examples of these l, ⁇ -dihaloalkanes are 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-di- chloropentane, 1, 6-dichlorohexane.
- the polymer of formula A is contained in the bath according to the invention in an amount of 0.1 to 50 g / 1, preferably 0.25 to 10 g / 1.
- the degree of polymerization of polymer A plays no role in avoiding the formation of bubbles and improving the layer thickness distribution; only the required solubility of the polymer in the galvanic bath places an upper limit on the degree of polymerization.
- the bath contains as a further additive a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and / or a quaternary derivative of a pyridine-3-carboxylic acid of the formula C.
- R 6 is a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.
- the amount of this additional additive in the bath according to the invention is 0.005 to 0.5 g / l, preferably 0.01 to 0.2 g / l.
- the quaternary derivatives of a pyridine-3-carboxylic acid of Formula 3 or C are used as further additives in the inventive bath are compounds known per se and at ⁇ play, in BS James, M Phil Thesis, Aston University. 1979 or DE 40 38 721. These derivatives are generally prepared by reacting nicotinic acid with aliphatic, aromatic or araliphatic hydrogen halides.
- the baths according to the invention can also contain further polymers, such as, for example, the polymers mentioned in the abovementioned publications.
- the cyanide-free zinc baths according to the invention correspond to the customary aqueous alkaline cyanide-free baths, such as those used for the deposition of zinc or Zinc alloy coatings can be used on various substrates. Standard baths of this type are described, for example, in DE 25 25 264 and US 3,884,774.
- the baths according to the invention contain the usual sources of zinc ions, such as zinc metal, zinc salts and zinc oxide, but preference is given to zinc oxide which is present as zincate in alkaline solution.
- the concentration of the zinc in the baths according to the invention is in the range of 0.2 to 20 g / 1, preferably 5 to 20 g / 1, which is customary for such baths.
- the baths contain a source of additional metal ions.
- additional metal ions cobalt, nickel, manganese and / or iron ions are preferred.
- Salts of the corresponding metals, preferably of the metals described above, optionally also in a mixture, are preferably used as sources for these additional metal ions.
- Suitable salts are nickel sulfate, iron sulfate, cobalt sulfate and manganese chloride.
- the concentration of the metal ions in the baths according to the invention can vary within a wide range and is preferably 0.01 to 100 g / l. Since a different alloy content is required for different alloy types, for example to improve corrosion protection, this concentration differs from metal ion to metal ion.
- the baths preferably contain zinc in an amount of 0.2 to 20 g / 1, cobalt in an amount of 10 to 120 mg / 1, nickel in an amount of 0.3 to 3 g / 1, manganese in an amount of 10 up to 100 g / 1 and iron in an amount of 10 to 120 mg / 1. These concentrations relate to the amount of metal ions contained in the bath. Corresponding conversions provide the amounts of the salts of these metals to be used in each case.
- baths according to the invention contain the above-mentioned additional metal ions, then it is expedient to add complexing agents which are matched to these additional metal ions in order to control the deposition potentials and to enable a joint reduction with the zinc ions present.
- Chelating agents are preferred as such complexing agents.
- suitable chelating agents are hydroxycarboxylates, such as sodium gluconate, amino alcohols, such as triethanolamine, polyamines, such as polyethylene diamine, aminocarboxyates, such as ⁇ DTA, amine phosphonates, such as amino-tris (ethylene phosphonic acid), and polyhydric alcohols, such as sorbitol or sucrose.
- the chelating agent can be contained individually or as a mixture in the 3-baths according to the invention, the amount of which is preferably in the range from 2 to 200 g / l.
- the baths according to the invention like the corresponding baths of the prior art - contain a hydroxide ion source, preferably an alkali metal hydroxide.
- a hydroxide ion source preferably an alkali metal hydroxide.
- Sodium hydroxide is usually used in a concentration of 80 to 250 g / l; however, other alkali and alkaline earth metal hydroxides and mixtures thereof are also suitable for use in the bath according to the invention. So show by using e.g. Potassium hydroxide increases the gloss of the zinc layer.
- the baths according to the invention can contain known levelers, such as 3-mercapto-1,2,4,4-triazole and / or thiourea, thiourea being preferred.
- concentration of the leveler is the usual concentration of zinc baths and is, for example, 0.01 to 0.50 g / 1.
- Other additives for the baths according to the invention are aromatic aldehydes or their bisulfite adducts.
- Preferred aromatic aldehydes are selected from the group 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3, 4-dimethoxybenzaldehyde, 3, 4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures thereof.
- These additives the concentration of which is in the range from 0.005 to 1.0 g / 1, preferably from 0.01 to 0.50 g / 1, act in a manner known per se as brighteners.
- a particularly preferred example of such a brightener is vanillin.
- the bath according to the invention can also act as a brightener, such as substances selected from the group consisting of sulfur compounds, aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof.
- a brightener such as substances selected from the group consisting of sulfur compounds, aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof.
- the baths according to the invention can also contain water-softening agents, since such additives reduce the sensitivity of the bath according to the invention to foreign metal ions, in particular calcium and magnesium from tap water.
- water softening agents are EDTA, sodium silicates and tartaric acid.
- conventional conductive substrates made of metal can be provided with a coating of zinc or a zinc alloy.
- Another object of the invention is therefore a method for the galvanic deposition of zinc coatings or zinc alloy coatings on conventional substrates, which is characterized in that a bath with the above composition is used as the bath.
- the coatings are preferably deposited at a current density in the range from 0.01 to 10 A / dm and at a temperature in the range from 15 to 45 ° C.
- the method according to the invention can be carried out, for example, as a drum electroplating process and for deposition on larger workpieces as a rack electroplating process.
- Anodes are used that can be soluble, such as zinc anodes, which also serve as a source of zinc ions, so that the zinc deposited on the cathode is recovered by dissolving zinc at the anode.
- insoluble anodes such as, for example, iron anodes, can also be used, the zinc ions extracted from the electrolyte having to be added again in another way, for example using a zinc dissolving container.
- the process according to the invention can also be operated with air blowing in, with movement of goods or without movement, without this resulting in any disadvantages for the coatings obtained.
- Trilon D trisodium salt of hydroxyethylethylenediaminetriacetic acid; from BASF, 40% solution
- a coated Zn anode serves as the anode. It works with strong air injection (1 1 / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
- the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
- the bath should have a temperature of 20 ° C, as bubbles occur especially at low temperatures.
- the sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
- the cathode sheet is coated at 1A for 15 minutes.
- the bath should have a temperature of 28 ° C.
- the sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air.
- the layer thickness is measured at two points 3 cm from the bottom
- the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (icd).
- a bath with the following composition is used:
- the layer thickness measurement is carried out at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm).
- XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
- the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (Icd).
- Trilon D trisodium salt of hydroxyethylethylenediaminetriacetic acid; from BASF, 40% solution
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer.
- the electrolyte had the following composition: 10 g / 1 ZnO 120 g / 1 KOH
- a steel sheet (5 cm x 5 cm) was deposited at 2 A / dm and 30 ° C for 30 minutes.
- the steel sheet was rinsed and chromated in a commercially available blue chromating (Corrotriblue, Atotech).
- the chromated sheet had a standard commercially available.
- the zinc layer showed no tendency to form bubbles, even tempering in a circulating air cabinet at 220 ° C for 30 minutes and subsequent quenching in tap water at room temperature did not lead to flaking.
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer.
- the electrolyte had the following composition:
- the Hull cell sheet was rinsed and chromatized in a commercially available yellow chromation (Tridur Yellow Liquid, Atot ⁇ ch).
- the chromated sheet had a slight iridescence and standard commercially available.
- the layer thickness distribution was measured according to the test described above, it was 1.30.
- the zinc layer showed no signs of blistering, even after 30 minutes in the circulating air cabinet at 220 ° C. and subsequent quenching in tap water from room temperature.
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer.
- the electrolyte had the following composition:
- Steel screws were galvanized in a drum with a current density of 0.1 - 1 A / dm and room temperature.
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-nickel layer.
- the electrolyte had the following composition:
- a steel sheet (5 cm x 5 cm) was deposited at 3 A / dm 2 and 30 ° C for 30 minutes.
- a uniform, shiny zinc-nickel layer was deposited.
- the zinc-nickel layer showed no signs of blistering, even after 30 minutes of tempering in a circulating air cabinet at 220 ° C. and subsequent quenching in tap water at room temperature.
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-iron layer.
- the electrolyte had the following composition:
- a steel sheet (5 cm x 5 cm) was deposited at 2 A / dm "and room temperature for 30 minutes. A uniform, shiny zinc-iron-cobalt layer was deposited.
- the zinc-iron-cobalt layer showed no sign of blistering, even after 30 minutes of tempering in a circulating air cabinet at 220 ° C. and subsequent quenching in tap water at room temperature.
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-manganese layer.
- the electrolyte had the following composition:
- a Hullzellbl ⁇ ch was deposited at 1 ampere and room temperature for 15 minutes.
- the Hull cell sheet was rinsed and lightened in 0.3 vol% HN0 3 for 10 s.
- the layer thickness distribution was measured according to the test described above; it was 1.41.
- the manganese incorporation was measured with XRF at the same positions at which the layer thickness was also measured. at 60 mg / 1 iron (as FeSC 4 • 7 H 2 0) 25 g / 1 sodium gluconate
- a Hull cell sheet was deposited at 1 amp and room temperature for 15 minutes.
- the Hull cell sheet was rinsed and chromated in a commercially available black chromation for zinc-iron layers (Tridur Schwarz Liquid ZnFe, Atot ⁇ ch).
- the chromated sheet had a very good black color.
- the layer thickness distribution was measured according to the test described above, it was 1.50.
- the zinc-iron layer showed no signs of blistering, not even after 30 minutes' tempering in a circulating air cabinet at 220 ° C. and subsequent quenching in tap water at room temperature.
- aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-iron-cobalt layer.
- the electrolyte had the following composition:
- a bath with the following composition is used:
- the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm " ) and low current density (0.5 A / dm). Measurements are also taken XRF at four positions at the respective position in order to keep the measurement error as low as possible
- the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at higher (hcd) and lower current density (icd).
- a bath with the following composition is used:
- A.l's anode is a coated Zn anode. It will be at strong air injection (1 1 / min) worked, which flows out of an L-shaped plastic tube with 6 ki ⁇ in ⁇ n holes (3 on each side) below the inserted cathode.
- the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
- the bath should have a temperature of 20 ° C, since bubbles occur especially at low temperatures.
- the sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. Thereafter, the sheet is carefully straightened until it assumes an elongated shape and stored at room temperature. It must be examined daily for blisters.
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Abstract
An aqueous alkaline cyanide-free bath for the galvanic deposition of zinc or zinc alloy coatings on substrate surfaces is described, which contains in addition to a source of zinc ions and optionally a source of further metal ions, also hydroxide ions and a polymer of the general formula A that is soluble in the bathas well as optionally conventional additives. The bath may furthermore contain a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and/or a quaternary derivative of a pyridine-3-carboxylic acid of the formula CA process for the galvanic deposition of zinc coatings and zinc alloy coatings using the aforedescribed bath is also described.By using the baths according to the invention it is possible to produce coatings that exhibit a uniform layer thickness combined with a high gloss, and which do not exhibit any tendency to exfoliate.
Description
Beschreibung description
Wäßriges alkalisches cyanidfreies Bad zur galvanischen Abscheidung von Zink- oder ZinklegierungsuberzugenAqueous alkaline, cyanide-free bath for the galvanic deposition of zinc or zinc alloy coatings
Zinkabscheidungen aus cyanidischer, alkalischer Lösung dominieren seit vielen Jahren den industriellen Markt. Die immer höheren Auflagen an die Lohngalvaniken bezüglich der Entsorgung alter Zinkelektrolytbäder und die damit einhergehende strenge Kontrolle über das Abwasser führten zu einem verstärkten Interesse an den nicht toxischen, cyanidfreien Zink- elektrolytbädern. Cyanidfreie Zinkelektrolytbäder lassen sich in zwei Badtypen unterteilen, nämlich in schwach saure Zink- elektrolyte (enthaltend Zinkchlorid bzw. Zinksulfat) und alkalische Zinkatelektrolyte.Zinc deposits from cyanide, alkaline solution have dominated the industrial market for many years. The increasingly stringent requirements placed on contract electroplating with regard to the disposal of old zinc electrolyte baths and the associated strict control over the waste water led to an increased interest in the non-toxic, cyanide-free zinc electrolyte baths. Cyanide-free zinc electrolyte baths can be divided into two bath types, namely weakly acidic zinc electrolytes (containing zinc chloride or zinc sulfate) and alkaline zincate electrolytes.
Aus schwach sauren Zinkbädern wird eine gleichmäßig glänzende Zinkschicht abgeschieden, so daß dieses Verfahren schnell einen starken Marktanteil behaupten konnte. Dieses Verfahren hat jedoch den Nachteil, daß seine Stromausbeute über einen breiten Stromdichtebereich immer 100% beträgt.A uniformly shiny zinc layer is deposited from weakly acidic zinc baths, so that this process could quickly assert a strong market share. However, this method has the disadvantage that its current efficiency is always 100% over a wide current density range.
Bei Beschichtungsstücken, die eine einfache Form besitzen, mag dies positiv zu bewerten sein, da der Strom ausschließlich zur Abscheidung von Zink verbraucht wird. Doch führt dies bei Beschichtungsteilen, die eine kompliziertere Form besitzen, zu einer dicken Zinkschicht im Bereich hoher Stromdichten und zu sehr dünnen Zinkschichten im Bereich niedriger Stromdichten.In the case of coating pieces which have a simple shape, this may have to be assessed positively, since the electricity is used only for the deposition of zinc. However, in the case of coating parts which have a more complicated shape, this leads to a thick zinc layer in the area of high current densities and to very thin zinc layers in the area of low current densities.
Das Verhältnis von Zinkschichtdicke im hohem Stromdichtebereich zur Zinkschichtdicke im niedriσen Stromdichtebereich
wird als Schichtdickeverteilung bezeichnet und sollte im Idealfall 1 betragen. Zink- und Zinklegierungsbäder müssen immer höheren Ansprüchen genüge tun. Dementsprechend soll eine Zinkschicht auf dem zu beschichtenden Gegenstand überall die gleiche Schichtdicke besitzen und einen hohen Glanz aufweisen. Eine gute Schichtdickeverteilung kann erreicht werden durch das Senken der Stromausbeute im hohen Stromdichtebereich, während die Stromausbeute im niedrigen Stromdichtebereich aufrechterhalten bleibt .The ratio of zinc layer thickness in the high current density range to zinc layer thickness in the low current density range is called the layer thickness distribution and should ideally be 1. Zinc and zinc alloy baths have to meet ever higher demands. Accordingly, a zinc layer on the object to be coated should have the same layer thickness everywhere and have a high gloss. A good layer thickness distribution can be achieved by lowering the current efficiency in the high current density range, while maintaining the current efficiency in the low current density range.
Diese Art des Angleichens der Zinkschichtdicke über einen breiten Stromdichtebereich ist bisher nur durch die Abscheidung von Zink aus alkalischen, cyanidfreien Elektrolyten gelungen. Alkalische Zinkgalvanisierbäder sind allgemein auf der Basis einer wäßrigen Lösung von Zinkationen in Natriumoder Kaliumhydroxid aufgebaut . Durch die Verwendung dieser Bäder ist es möglich, Zinkschichten mit hohem Glanz abzuscheiden (DE 25 25 264, US 3 884 774), jedoch weisen diese Zinkschichten keine gleichmäßige Schichtdickeverteilung auf .This type of adjustment of the zinc layer thickness over a wide current density range has so far only been possible through the deposition of zinc from alkaline, cyanide-free electrolytes. Alkaline zinc plating baths are generally based on an aqueous solution of zinc ions in sodium or potassium hydroxide. The use of these baths makes it possible to deposit zinc layers with a high gloss (DE 25 25 264, US 3 884 774), but these zinc layers do not have a uniform layer thickness distribution.
Im Stand der Technik wurden schon zahlreiche Vorschläge gemacht, um die Schichrdickeverteilung der Zinkschichten durch Zugabe geeigneter Additive zu verbessern (US 5 405 523, US 5 435 898, DE 195 09 713, US 4 030 987).Numerous proposals have already been made in the prior art to improve the layer thickness distribution of the zinc layers by adding suitable additives (US Pat. No. 5,405,523, US Pat. No. 5,435,898, DE 195 09 713, US Pat. No. 4,030,987).
Bei den bislang vorgeschlagenen Additiven besteht nachteiligerweise jedoch die Neigung, daß die galvanisch erzeugten Zinkschichten abplatzen. Die Bildung von Zink- bzw. Zinkle- gierungsabplatzern von dem beschichteten Substrat, oft auch als Blasenbildung bezeichnet , stellt bei der Verwendung von cyanidfreien, alkalischen Bädern ein schwerwiegendes Problem dar, wobei noch keine gesicherten Erkenntnisse hinsichtlich dem Einfluß der jeweils verwendeten Zusätze auf die Blasenbildung vorliegen. Die Erscheinung der Blasenbildung wirkt sich als besonders nachteilig aus, weil sie oft erst nach Wochen auftritt und somiz häufig zu Reklamationen bei der Be- schichterindustrie führen kann.
In der US 5 405 523 wird als Zusatz in Zinklegierungsbädern eine Substanz mit dem Handelsnamen Mirapol A 15 und ähnliche Verbindungen beschrieben, die den Glanz von Zinklegierungen verbessern soll.In the case of the additives proposed hitherto, however, there is the disadvantage that the galvanically produced zinc layers flake off. The formation of flaked zinc or zinc alloy flakes from the coated substrate, often also called blistering, is a serious problem when using cyanide-free, alkaline baths, with no reliable knowledge regarding the influence of the additives used on the blistering available. The appearance of the blistering is particularly disadvantageous because it often only occurs after weeks and somiz can often lead to complaints in the coating industry. No. 5,405,523 describes a substance with the trade name Mirapol A 15 and similar compounds as an additive in zinc alloy baths which is said to improve the gloss of zinc alloys.
In der US 5 435 898 wird als Zusatz für Zink- und Zinklegierungsgalvanisierbäder eine ähnliche Verbindung mit dem Handelsnamen Mirapol WT beschrieben, die ebenfalls die Schicht- dickeverteilung stark verbessern soll.No. 5,435,898 describes a similar compound with the trade name Mirapol WT as an additive for zinc and zinc alloy electroplating baths, which is also said to greatly improve the layer thickness distribution.
In der DE 195 09 713 wird ein Diallylammonium-Schwefeldioxid- Copolymer als Zusatz für Zink- und Zinklegierungsgalvanisierbäder beschrieben, welches der Zinkschicht eine gleichmäßige Schichtdicke verleihen soll .DE 195 09 713 describes a diallylammonium sulfur dioxide copolymer as an additive for zinc and zinc alloy plating baths, which is intended to give the zinc layer a uniform layer thickness.
In der US 4 030 987 wird ebenfalls ein Diallylammonium-Schwe- feldioxid-Copolymer als Zusatz für Zink- und Zinklegierungs- galvanisierbäder beschrieben, welches der Zinkschicht eine gleichmäßige Schichtdicke verleihen soll.US Pat. No. 4,030,987 likewise describes a diallylammonium-sulfur dioxide copolymer as an additive for zinc and zinc alloy electroplating baths, which is intended to give the zinc layer a uniform layer thickness.
Es hat sich herausgestellt, daß die oben beschriebenen Zusätze zu nachteiligen Folgen bei der Abscheidung der Zinkschicht, insbesondere zu einer Blasenbildung der Überzüge, führen.It has been found that the additives described above lead to disadvantageous consequences in the deposition of the zinc layer, in particular to the formation of bubbles in the coatings.
Der Erfindung liegt daher die Aufgabe zugrunde, die Mängel des Stands der Technik zu überwinden und insbesondere ein wäßriges cyanidfreies alkalisches Bad zur galvanischen Abscheidung von Zink- und Zinklegierungsuberzugen bereitzustellen, mit dem Überzüge aus Zink- oder Zinklegierungen erhalten werden können, bei denen auch nach längerer Lagerung keine Tendenz zur Bildung von Abplatzern besteht. Dabei sollen die Vorteile dieser Bäder hinsichtlich einer gleichmäßigen Schichtdicke eines hohen Glanzes und der Gleichmäßigkeit der Legierungskomponenten im Überzug über einen breiten Bereich von Stromdichten aufrechterhalten werden.
Es wurde nun gefunden, daß der Zusatz einer speziellen Art von quaternären Ammoniumpolymeren zu wäßrigen alkalischen cyanidfreien Zinkbädern die Schichtdickeverteilung der erhaltenen Überzüge verbessert und die Blasenbildung der Überzüge verringert .The invention is therefore based on the object of overcoming the shortcomings of the prior art and, in particular, of providing an aqueous cyanide-free alkaline bath for the electrodeposition of zinc and zinc alloy coatings, with which coatings of zinc or zinc alloys can be obtained, in which even after prolonged use Storage there is no tendency to form flaking. The advantages of these baths with regard to a uniform layer thickness, a high gloss and the uniformity of the alloy components in the coating are to be maintained over a wide range of current densities. It has now been found that the addition of a special type of quaternary ammonium polymer to aqueous alkaline cyanide-free zinc baths improves the layer thickness distribution of the coatings obtained and reduces the blistering of the coatings.
Gegenstand der Erfindung ist daher ein wäßriges alkalisches cyandifreies Bad zur galvanischen Abscheidung von Zink- oder Zinklegierungsuberzugen auf Substratoberflächen, das dadurch gekennzeichnet ist, daß esThe invention therefore relates to an aqueous alkaline, cyano-free bath for the galvanic deposition of zinc or zinc alloy coatings on substrate surfaces, which is characterized in that it
(a) eine Zinkionenquelle und gegebenenfalls eine Quelle für weitere Metallionen,(a) a source of zinc ions and optionally a source of further metal ions,
(b) Hydroxidionen und(b) hydroxide ions and
(c) ein in dem Bad lösliches Polyτneres der allgemeinen Formel A(c) a bath-soluble polymer of the general formula A
worin m den Wert 2 oder 3 hat, n einen Wert von mindestens 2 hat, Rx, R2, R3 und R , die gleich oder verschieden sein können, jeweils für Methyl, Ethyl, Hydroxyethyl stehen, p einen Wert im Bereich von 3 bis 12 hat und X" für Cl", Br" und/oder I" stehtwherein m is 2 or 3, n is at least 2, R x , R 2 , R 3 and R, which may be the same or different, each represent methyl, ethyl, hydroxyethyl, p is in the range of 3 to 12 and X "stands for Cl " , Br " and / or I "
sowie gegebenenfallsand if necessary
(d) übliche Additive enthält.(d) contains common additives.
Das in dem erfindungsgemäßen Bad enthaltene lösliche Polymere der allgemeinen Formel A kann durch Umsetzung von N,N'-Bis[3-
(dialkylamino) alkyl] harnstoffen mit 1 , ω-Dihaiogenalkanen er halten werden. Diese Umsetzung kann durch folgendes Reaktionsschema dargestellt werden, wobei die Reste R!-R4, X sowie m und n wie oben definiert sind:The soluble polymer of the general formula A contained in the bath according to the invention can be obtained by reacting N, N'-bis [3- (Dialkylamino) alkyl] ureas with 1, ω-Dihaiogenalkanen he will keep. This reaction can be represented by the following reaction scheme, where the radicals R ! -R 4 , X and m and n are as defined above:
Die Umsetzung der Ausgangsprodukte kann beispielsweise in wäßriger Lösung und bei Temperaturen von 20 bis 100°C durchgeführt werden. Auf diese Weise können die erfindungsgemäß verwendeten Polymere der Formel A erhalten werden, bei denen die Aminoharnstoffeinheiten durch Kohlenwasserstoffbrücken verbunden sind. Der Polymerisationsgrad dieser Polymere beträgt 2-80. Die Ausgangsstoffe der allgemeinen Formeln D und E sind an sich bekannt. Die Diaminoharnstoffe der Formel D werden beispielsweise in der JP 04-198160 beschrieben.The reaction of the starting products can be carried out, for example, in aqueous solution and at temperatures of 20 to 100 ° C. In this way, the polymers of formula A used according to the invention can be obtained in which the amino urea units are connected by hydrocarbon bridges. The degree of polymerization of these polymers is 2-80. The starting materials of the general formulas D and E are known per se. The diaminoureas of the formula D are described, for example, in JP 04-198160.
Die weiteren Ausgangsprodukte für die Herstellung der erfindungsgemäß verwendeten Polymeren sind l,ω-Dihalogenalkane der allgemeinen Formel E. Einzelbeispiele für diese l,ω-Dihalo- genalkane sind 1, 3-Dichlorpropan, 1, 4-Dichlorbutan, 1,5-Di- chlorpentan, 1, 6-Dichlorhexan.
Das Polymere der Formel A ist in dem erfindungsgemaßen Bad in einer Menge von 0,1 bis 50 g/1, vorzugsweise 0,25 bis 10 g/1, enthalten. Der Polymerisationsgrad des Polymeren A spielt für die Vermeidung der Blasenbildung und die Verbesserung der Schichtdickεverteilung keine Rolle; lediglich die erforderliche Löslichkeit des Polymeren in dem galvanischen Bad setzt dem Polymerisationsgrad eine obere Grenze.The other starting products for the preparation of the polymers used according to the invention are l, ω-dihaloalkanes of the general formula E. Individual examples of these l, ω-dihaloalkanes are 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-di- chloropentane, 1, 6-dichlorohexane. The polymer of formula A is contained in the bath according to the invention in an amount of 0.1 to 50 g / 1, preferably 0.25 to 10 g / 1. The degree of polymerization of polymer A plays no role in avoiding the formation of bubbles and improving the layer thickness distribution; only the required solubility of the polymer in the galvanic bath places an upper limit on the degree of polymerization.
Gemäß einer bevorzugten Ausführungsform der Erfindung enthält das Bad als weiteres Additiv ein quaternäres Derivat einer Pyridin-3 -carbonsäure der Formel B und/oder ein quaternäres Derivat einer Pyridin-3 -carbonsäure der Formel CAccording to a preferred embodiment of the invention, the bath contains as a further additive a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and / or a quaternary derivative of a pyridine-3-carboxylic acid of the formula C.
BB
worin R6 für einen gesättigten oder ungesättigten, aliphati- schen, aromatischen oder araliphatischen Kohlenwasserstoff- rest mit 1 bis 12 Kohlenstoffatomen steht.wherein R 6 is a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.
Die Menge dieses zusätzlichen Additivs in dem erfindungsgemäßen Bad beträgt 0,005 bis 0,5 g/1, vorzugsweise 0,01 bis 0,2 g/i.The amount of this additional additive in the bath according to the invention is 0.005 to 0.5 g / l, preferably 0.01 to 0.2 g / l.
Die als weitere Additive in dem erfindungsgemäßen Bad verwendeten quaternären Derivate einer Pyridin-3 -carbonsäure der Formel 3 oder C sind an sich bekannte Verbindungen und bei¬ spielsweise in B. S. James, M Phil thesis, Aston Univ. 1979
bzw. DE 40 38 721 beschrieben. Die Herstellung dieser Derivate erfolgt im allgemeinen durch Umsetzung von Nicotinsäure mit aliphatischen, aromatischen oder araliphatischen Halogen- wasserstoffen.The quaternary derivatives of a pyridine-3-carboxylic acid of Formula 3 or C are used as further additives in the inventive bath are compounds known per se and at ¬ play, in BS James, M Phil Thesis, Aston University. 1979 or DE 40 38 721. These derivatives are generally prepared by reacting nicotinic acid with aliphatic, aromatic or araliphatic hydrogen halides.
Der Zusatz des weiteren Additivs B und/oder C ergibt eine weitere Verbesserung der Schichtdickeverteilung. Als weiterer Vorteil des Zusatzes der genannten Derivate B und C zu dem erfindungsgemäßen Bad ist die Verbesserung des Glanzes zu nennen .The addition of the further additive B and / or C results in a further improvement in the layer thickness distribution. Another advantage of adding derivatives B and C mentioned to the bath according to the invention is the improvement in gloss.
Schließlich können die erfindungsgemäßen Bäder zusätzlich zu den obengenannten Additiven A, B und/oder C auch weitere Polymere, wie beispielsweise die in den obengenannten Druckschriften genannten Polymere, enthalten.Finally, in addition to the additives A, B and / or C mentioned above, the baths according to the invention can also contain further polymers, such as, for example, the polymers mentioned in the abovementioned publications.
Abgesehen von dem erfindungsgemäß erfolgenden Zusatz des Polymeren der allgemeinen Formel A sowie gegebenenfalls des quaternären Derivats einer Pyridin-3-carbonsäure der Formel B und/oder C entsprechen die erfindungsgemäßen cyanidfreien Zinkbäder den üblichen wäßrigen alkalischen cyanidfreien Bädern, wie sie zur Abscheidung von Zink- oder Zinklegierungsuberzugen auf verschiedenen Substraten verwendet werden. Standardbäder dieses Typs werden beispielsweise in DE 25 25 264 und US 3 884 774 beschrieben.Apart from the addition of the polymer of the general formula A and, if appropriate, the quaternary derivative of a pyridine-3-carboxylic acid of the formula B and / or C, the cyanide-free zinc baths according to the invention correspond to the customary aqueous alkaline cyanide-free baths, such as those used for the deposition of zinc or Zinc alloy coatings can be used on various substrates. Standard baths of this type are described, for example, in DE 25 25 264 and US 3,884,774.
So enthalten die erfindungsgemäßen Bäder die üblichen Zinkionenquellen, wie beispielsweise Zinkmetall, Zinksalze und Zinkoxid, wobei aber Zinkoxid bevorzugt wird, das in alkalischer Lösung als Zinkat vorliegt.For example, the baths according to the invention contain the usual sources of zinc ions, such as zinc metal, zinc salts and zinc oxide, but preference is given to zinc oxide which is present as zincate in alkaline solution.
Die Konzentration des Zinks in den erfindungsgemaßen Bädern liegt in dem für derartige Bäder üblichen Bereich von 0 , 2 bis 20 g/1, vorzugsweise 5 bis 20 g/1.The concentration of the zinc in the baths according to the invention is in the range of 0.2 to 20 g / 1, preferably 5 to 20 g / 1, which is customary for such baths.
Wenn aus den erfindungsgemäßen Bädern Überzüge aus Zinkiegie- rungen abgeschieden werden sollen, dann enthalten die Bäder
eine Quelle für weitere Metallionen. Als solche kommen vorzugsweise Kobalt-, Nickel-, Mangan- und/oder Eisenionen in Betracht. Vorzugsweise werden als Quellen für diese zusätzlichen Metal-ionen Salze der entsprechenden Metalle, vorzugsweise der oben beschriebenen Metalle, gegebenenfalls auch im Gemisch, eingesetzt.If coatings of zinc alloys are to be deposited from the baths according to the invention, then the baths contain a source of additional metal ions. As such, cobalt, nickel, manganese and / or iron ions are preferred. Salts of the corresponding metals, preferably of the metals described above, optionally also in a mixture, are preferably used as sources for these additional metal ions.
Einzelbeispiele geeigneter Salze sind Nickelsulfat, Ξisensul- fat, Kobaltsulfat und Manganchlorid.Individual examples of suitable salts are nickel sulfate, iron sulfate, cobalt sulfate and manganese chloride.
Die Konzentration der Metallionen in den erfindungsgemäßen Bädern kann innerhalb eines weiten Bereichs variieren und beträgt vorzugsweise 0,01 bis 100 g/1. Da bei unterschiedlichen Legierungstypen auch ein unterschiedlicher Legierungsanteil erforderlich ist, um beispielsweise den Korrosionsschutz zu verbessern, ist diese Konzentration von Metallion zu Metallion verschieden. Vorzugsweise enthalten die Bäder Zink in einer Menge von 0,2 bis 20 g/1, Kobalt in einer Menge von 10 bis 120 mg/1, Nickel in einer Menge von 0,3 bis 3 g/1, Mangan in einer Menge von 10 bis 100 g/1 und Eisen in einer Menge von 10 bis 120 mg/1. Diese Konzentrationen beziehen sich auf die in dem Bad enthaltene Menge an Metallionen. Entsprechende Umrechnungen liefern die Mengen der jeweils einzusetzenden Salze dieser Metalle.The concentration of the metal ions in the baths according to the invention can vary within a wide range and is preferably 0.01 to 100 g / l. Since a different alloy content is required for different alloy types, for example to improve corrosion protection, this concentration differs from metal ion to metal ion. The baths preferably contain zinc in an amount of 0.2 to 20 g / 1, cobalt in an amount of 10 to 120 mg / 1, nickel in an amount of 0.3 to 3 g / 1, manganese in an amount of 10 up to 100 g / 1 and iron in an amount of 10 to 120 mg / 1. These concentrations relate to the amount of metal ions contained in the bath. Corresponding conversions provide the amounts of the salts of these metals to be used in each case.
Wenn die erfindungsgemäßen Bäder die obengenannten zusätzlichen Metallionen enthalten, dann ist es zweckmäßig, den Bädern auch auf diese zusätzlichen Metallionen abgestimmte Komplexbildner zuzusetzen, um die Abscheidungspotentiale zu steuern und um eine gemeinsame Reduktion mit den vorhandenen Zinkionen zu ermöglichen.If the baths according to the invention contain the above-mentioned additional metal ions, then it is expedient to add complexing agents which are matched to these additional metal ions in order to control the deposition potentials and to enable a joint reduction with the zinc ions present.
Ais selche Kcmplexbildner werden Chelatbildner bevorzugt. Beispiele für geeignete Chelatbildner sind Hydroxycarboxyla- te, wie Natriumgluconat, Aminoalkohole, wie Triethanolamin, Polya ine, wie Polyethylendiamin, Aminocarboxyiate, wie ΞDTA, Amincphosphonate, wie Amino-tris ( ethylenphosphonsäure) , und
mehrwertige Alkohole, wie Sorbit oder Saccharose. Der Chelatbildner kann einzeln oder im Gemisch in den erfindungsgemaßen 3ädern enthalten sein, wobei dessen Menge vorzugsweise im Bereich von 2 bis 200 g/1 liegt.Chelating agents are preferred as such complexing agents. Examples of suitable chelating agents are hydroxycarboxylates, such as sodium gluconate, amino alcohols, such as triethanolamine, polyamines, such as polyethylene diamine, aminocarboxyates, such as ΞDTA, amine phosphonates, such as amino-tris (ethylene phosphonic acid), and polyhydric alcohols, such as sorbitol or sucrose. The chelating agent can be contained individually or as a mixture in the 3-baths according to the invention, the amount of which is preferably in the range from 2 to 200 g / l.
Die erfindungsgemäßen Bäder enthalten - wie die entsprechenden Bäder des Stands der Technik - eine Hydroxidionenquellen, vorzugsweise ein Alkalihydroxid. Üblicherweise wird Natriumhydroxid in einer Konzentration von 80 bis 250 g/1 verwendet; jedoch sind auch andere Alkali- und Erdalkalimetallhydroxide sowie Mischungen davon für den Einsatz in dem erfindungsgemaßen Bad geeignet. So zeige sich durch Verwendung von z.B. Kaliumhydroxid eine Erhöhung des Glanzes der Zinkschicht .The baths according to the invention - like the corresponding baths of the prior art - contain a hydroxide ion source, preferably an alkali metal hydroxide. Sodium hydroxide is usually used in a concentration of 80 to 250 g / l; however, other alkali and alkaline earth metal hydroxides and mixtures thereof are also suitable for use in the bath according to the invention. So show by using e.g. Potassium hydroxide increases the gloss of the zinc layer.
Weiterhin können die erfindungsgemäßen Bäder bekannte Einebner, wie 3-Mercapto-l, 2, 4-triazol und/oder Thioharnstoff enthalten, wobei Thioharnstoff bevorzugt wird. Die Konzentration des Einebners ist die übliche Konzentration von Zinkbädern und beträgt beispielsweise 0,01 bis 0,50 g/1. Weitere Zusätze für die erfindungsgemäßen Bäder sind aromatische Aldehyde oder deren Bisulfitaddukte .Furthermore, the baths according to the invention can contain known levelers, such as 3-mercapto-1,2,4,4-triazole and / or thiourea, thiourea being preferred. The concentration of the leveler is the usual concentration of zinc baths and is, for example, 0.01 to 0.50 g / 1. Other additives for the baths according to the invention are aromatic aldehydes or their bisulfite adducts.
Bevorzugte aromatische Aldehyde werden aus der Gruppe 4-Hy- droxybenzaldehyd, 4-Hydroxy-3 -methoxybenzaldehyd (Vanillin) , 3 , 4-Dimethoxybenzaldehyd, 3 , 4-Methylendioxybenzaldehyd, 2- Hydroxybenzaldehyd und 4-Hydroxybenzaldehyd oder Gemischen davon ausgewählt. Diese Additive, deren Konzentration im Bereich von 0,005 bis 1,0 g/1, vorzugsweise von 0,01 bis 0,50 g/1, liegt, wirken in an sich bekannter Weise als Glanzbildner. Ein besonders bevorzugtes Beispiel für einen derartigen Glanzbildner ist Vanillin. Daneben kann das erfindungsgemäße Bad als Glanzbildner auch andere Substanzen, wie beispielsweise Substanzen, ausgewählt aus der Gruppe Schwefelverbindungen, Aldehyde, Ketone, Aminε, Polyvinyialkohol, Polyvinyi- pyrroiidon, Proteine oder Reaktionsprodukte von Halogenhydri- nen mit aliphatischen oder aromatischen A inen, Polyaminen
oder hεterocyclischen Stickstoffverbindungen und Gemische davon, enthalten.Preferred aromatic aldehydes are selected from the group 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3, 4-dimethoxybenzaldehyde, 3, 4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures thereof. These additives, the concentration of which is in the range from 0.005 to 1.0 g / 1, preferably from 0.01 to 0.50 g / 1, act in a manner known per se as brighteners. A particularly preferred example of such a brightener is vanillin. In addition, the bath according to the invention can also act as a brightener, such as substances selected from the group consisting of sulfur compounds, aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof.
Schließlich können die erfindungsgemäßen Bäder noch wasserenthärtende Mittel enthalten, da durch derartige Zusätze die Empfindlichkeit des erfindungsgemäßen Bades gegenüber Fremdmetallionen, insbesondere Calcium und Magnesium aus Leitungswasser, verringert wird. Beispiele für derartige wasserenthärtende Mittel sind EDTA, Natriumsilikate und Weinsäure.Finally, the baths according to the invention can also contain water-softening agents, since such additives reduce the sensitivity of the bath according to the invention to foreign metal ions, in particular calcium and magnesium from tap water. Examples of such water softening agents are EDTA, sodium silicates and tartaric acid.
Unter Verwendung der erfindungsgemaßen Bäder können übliche leitende Substrate aus Metall mit einem Überzug aus Zink oder einer Zinklegierung versehen werden.Using the baths according to the invention, conventional conductive substrates made of metal can be provided with a coating of zinc or a zinc alloy.
Ein weiterer Gegenstand der Erfindung ist daher ein Verfahren zur galvanischen Abscheidung von Zinküberzügen oder von Zinklegierungsuberzugen auf üblichen Substraten, das dadurch gekennzeichnet ist, daß als Bad ein Bad mit der obigen Zusammensetzung verwendet wird. Vorzugsweise erfolgt bei dem erfindungsgemaßen Verfahren die Abscheidung der Überzüge bei einer Stromdichte im Bereich von 0,01 bis 10 A/dm sowie bei einer Temperatur im Bereich von 15 bis 45°C.Another object of the invention is therefore a method for the galvanic deposition of zinc coatings or zinc alloy coatings on conventional substrates, which is characterized in that a bath with the above composition is used as the bath. In the method according to the invention, the coatings are preferably deposited at a current density in the range from 0.01 to 10 A / dm and at a temperature in the range from 15 to 45 ° C.
Das erfindungsgemäße Verfahren kann bei Anwendung für Massenteile beispielsweise als Trommelgalvanisierverfahren und zur Abscheidung auf größeren Werkstücken als Gestellgalvanisier- verfahrεn durchgeführt werden. Dabei werden Anoden verwendet, die löslich sein können, wie beispielsweise Zinkanoden, die gleichzeitig als Zinkionenquelle dienen, damit das auf der Kathode abgeschiedene Zink durch Auflösung von Zink an der Anode zurückgewonnen wird. Andererseits können auch unlösliche Anoden, wie beispielsweise Eisenanoden, eingesetzt werden, wobei die dem Elektrolyten entzogenen Zinkionen auf andere Weise wieder zugesetzt werden müssen, z.B. unter Verwendung eines Zinklösebehälters .
Wie bei der galvanischen Abscheidung üblich, kann auch das erfindtrngsgemäße Verfahren unter Lufteinblasung, mit Warenbewegung oder ohne Bewegung, betrieben werden, ohne daß sich hierdurch irgendwelche Nachteile für die erhaltenen Überzüge ergeben .When used for mass parts, the method according to the invention can be carried out, for example, as a drum electroplating process and for deposition on larger workpieces as a rack electroplating process. Anodes are used that can be soluble, such as zinc anodes, which also serve as a source of zinc ions, so that the zinc deposited on the cathode is recovered by dissolving zinc at the anode. On the other hand, insoluble anodes, such as, for example, iron anodes, can also be used, the zinc ions extracted from the electrolyte having to be added again in another way, for example using a zinc dissolving container. As is customary in the case of galvanic deposition, the process according to the invention can also be operated with air blowing in, with movement of goods or without movement, without this resulting in any disadvantages for the coatings obtained.
Die Erfindung wird in den Beispielen erläutert.The invention is illustrated in the examples.
1. In den Beispielen angewendete Testverfahren1. Test procedures used in the examples
1.1 Blasen-Schneiltest zur Beurteilung der erfindunσsσemäß verwendeten Polymeren Additive1.1 Bubble cut test to assess the polymer additives used according to the invention
Um die Erscheinung der Blasenbildung zu beobachten, wurde ein eigener Blasen-Schneiltest entwickelt, der die Phänomene aus der Produktion reproduzierbar im Labor nachstellt. Dementsprechend wurde dieser Test so gewählt, daß er alle Eigenschaften, die zu Blasenbildung führen, in sich vereint. Dies ist im besonderen die Beschichtung unter Druckspannung, unter starker Lufteinblasung, bei Raumtemperatur, unter Anwesenheit blasenfördernder Substanzen und mit hoher Schichtdicke. Es ist gelungen, die Erscheinung der Blasenbildung innerhalb von Stunden nach der Beschichtung bei solchen Elektrolyten, die Additive enthalten, die zu Blasenbildung neigen, hervorzurufen.In order to observe the appearance of the formation of bubbles, a special bubble cut test was developed, which reproducibly reproduces the phenomena from production in the laboratory. Accordingly, this test was chosen so that it combines all the properties that lead to blistering. This is especially the coating under compressive stress, with strong air injection, at room temperature, in the presence of bubble-promoting substances and with a high layer thickness. The appearance of the blistering has been successful within hours after the coating in those electrolytes which contain additives which tend to blister.
Bei dem Blasen-Schneiltest wurde eine Vorrichtung gemäß der Figur sowie folgender Grundelektrolyt verwendet :A device according to the figure and the following basic electrolyte were used in the bubble cut test:
10 g/1 Zn 130 g/1 NaOH 20 g/1 Na C03 10 g / 1 Zn 130 g / 1 NaOH 20 g / 1 Na CO 3
1.2 g/1 Diallylammonium-Schwefeldioxid-Copolymer (DE 195 09 713, US 4 030 987)1.2 g / 1 diallylammonium sulfur dioxide copolymer (DE 195 09 713, US 4 030 987)
0,19 g/1 Umsetzungsprodukt Epichlorhydrin mit Dimethylamino- propyia in (US 3 884 774)
9,2 mg/1 N-Eenzyl-pyridinium-3-carboxylat0.19 g / 1 reaction product epichlorohydrin with dimethylaminopropyia in (US 3 884 774) 9.2 mg / 1 N-eenzyl-pyridinium-3-carboxylate
1,25 g/1 Trilon D (Trinatriumsalz der Hydroxyethylethylen- diamintriessigsäure; Fa. BASF, 40%ige Lösung)1.25 g / 1 Trilon D (trisodium salt of hydroxyethylethylenediaminetriacetic acid; from BASF, 40% solution)
0,1 g/1 3-Mercaptotriazol0.1 g / 1 3-mercaptotriazole
900 ml der Lösung werden in ein breites 11-Becherglas gefüllt (Figur) . Als Anode dient eine umhüllte Zn-anode. Es wird bei starker Lufteinblasung (1 1/min) gearbeitet, welche aus einem L-förmigen Plastikrohr mit 6 kleinen Löchern (3 auf jeder Seite) unterhalb der eingesetzten Kathode ausströmt. Das Kathodenblech (18,5 cm x 5 cm) wird am unteren Ende gebogen und 35 min bei 2,8 A beschichtet. Das Bad sollte eine Temperatur von 20°C besitzen, da besonders bei niedriger Temperatur Blasen auftreten. Das Blech wird abgespült, 10 s in 0,3 Vol-% HN03 aufgehellt, wieder gespült und unter Preßluft getrocknet. Danach wird das Blech vorsichtig gerade gebogen, bis es eine gestreckte Form einnimmt, und bei Raumtemperatur gelagert. Es muß täglich nach Blasen untersucht werden.900 ml of the solution are poured into a wide 11-beaker (figure). A coated Zn anode serves as the anode. It works with strong air injection (1 1 / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode. The cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min. The bath should have a temperature of 20 ° C, as bubbles occur especially at low temperatures. The sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
1.2 Schichtdickeverteiluncrstest1.2 Layer Thickness Distribution Test
Es wird folgender Grundelektrolyt verwendet :The following basic electrolyte is used:
10 g/1 Zn 130 g/1 NaOH 20 g/1 Na2C03 10 g / 1 Zn 130 g / 1 NaOH 20 g / 1 Na 2 CO 3
250 ml der Lösung werden in eine Hullzelle gefüllt. Als Anode dient eine Zn-anode. Das Kathodenblech wird 15 min bei 1 A beschichtet. Das Bad sollte eine Temperatur von 28°C besitzen. Das Blech wird abgespült, 10 s in 0,3 Vol-% HN03 aufgehellt, wieder gespült und unter Preßluft getrocknet. Die Schichtdickemessung erfolgt an zwei Punkten 3 cm vom unteren250 ml of the solution are placed in a Hull cell. A Zn anode serves as the anode. The cathode sheet is coated at 1A for 15 minutes. The bath should have a temperature of 28 ° C. The sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. The layer thickness is measured at two points 3 cm from the bottom
Rand und 2,5 cm vom rechten und linken seitlichen Rand beiEdge and 2.5 cm from the right and left side edge at
2 2 hoher (2,8 A/dm ) und niedriger Stromdichte (0,5 A/dm ) . Gemessen wird mit XRF an vier Stellen bei der jeweiligen Position, um den Meßfehler so gering wie möglich zu halten. Die Schichtdickeverteilung entspricht dem Verhältnis der gemesse-
nen Werte für die Schichtdicke bei hoher (hcd) und niedriger Stromdichte (icd) .2 2 high (2.8 A / dm) and low current density (0.5 A / dm). XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible. The layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (icd).
Schichtdickeverteilung = hcd: IcdLayer thickness distribution = hcd: Icd
2. Herstelluncrsbeispiele für die erfindungsgemäß verwendeten Polymeren2. Manufacture examples for the polymers used according to the invention
2.1 Herstellung eines Polymeren, bei dem Rη , R2J 3J R4 =2.1 Preparation of a polymer in which Rη, R 2J 3J R 4 =
Methyl ; m = 3 ; p = 4Methyl; m = 3; p = 4
20,0 g (86,8 mmol) N,N' -Bis [3 - (dimethylamino) propyl] harnstoff werden in 200 ml Wasser gelöst. Dann werden 11,13 g (86,8 mmol) 1, 4-Dichlorbutan zugegeben. Nun wird 8 h unter Rühren auf 80°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlδsung .20.0 g (86.8 mmol) of N, N 'bis [3 - (dimethylamino) propyl] urea are dissolved in 200 ml of water. Then 11.13 g (86.8 mmol) of 1,4-dichlorobutane are added. The mixture is now heated to 80 ° C. for 8 hours with stirring. After cooling, an aqueous polymer solution is obtained.
2.2 Herstellung eines Polymeren, bei- dem R , R2-i R3_, R4 =2.2 Preparation of a polymer in which R, R 2 -i R 3 _, R 4 =
Methyl ; m = 3 ; P = 3Methyl; m = 3; P = 3
10,0 g (43,4 mmol) N,N' -Bis [3- (dimethylamino) propyl] harnsto f werden in 100 ml Wasser gelöst. Dann werden 4,95 g (43,4 mmol) 1, 3-Dichlorpropan zugegeben. Nun wird 7 h unter Rühren auf 90°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlδsung .10.0 g (43.4 mmol) of N, N 'bis [3- (dimethylamino) propyl] urea are dissolved in 100 ml of water. 4.95 g (43.4 mmol) of 1,3-dichloropropane are then added. The mixture is then heated to 90 ° C. for 7 hours with stirring. After cooling, an aqueous polymer solution is obtained.
2.3 Herstellung eines Polymeren, bei dem R-\ , R? , R3 , R4 =2.3 Production of a polymer in which R- \ , R ? , R 3 , R 4 =
Methyl ; m = 3 ; p = 6Methyl; m = 3; p = 6
20,0 g (86,8 mmol) N,N' -Bis [3- (dimethylamino) propyl] harnstoff und 13,46 g (86,6 mmol) 1, 6-Dichlorhexan werden in 50 ml Wasser 17 h auf 80°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung.
2.4 Herstellung eines Polymeren, bei dem Rl r R-? , R3J R —≡.20.0 g (86.8 mmol) of N, N 'bis [3- (dimethylamino) propyl] urea and 13.46 g (86.6 mmol) of 1,6-dichlorohexane are dissolved in 50 ml of water for 17 h to 80 ° C heated. After cooling, an aqueous polymer solution is obtained. 2.4 Preparation of a polymer in which R lr R-? , R 3J R —≡.
Methyl ; m = 3 ; p = 5Methyl; m = 3; p = 5
20,0 g (86,8 mmol) N,N' -Bis [3 - (dimethylamino) propyl] harnstoff werden in 200 ml Wasser gelöst. Dann werden 12,36 g (86,8 mmol) 1, 5-Dichlorpentan zugegeben. Nun wird 17 h unter Rühren auf 80°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung .20.0 g (86.8 mmol) of N, N 'bis [3 - (dimethylamino) propyl] urea are dissolved in 200 ml of water. Then 12.36 g (86.8 mmol) of 1,5-dichloropentane are added. The mixture is then heated to 80 ° C. for 17 hours with stirring. After cooling, an aqueous polymer solution is obtained.
2.5 Herstellung eines Polymeren, bei dem R^, R2J 3J R4 =2.5 Preparation of a polymer in which R ^, R 2J 3J R 4 =
Ethyl ; m = 3 ; p = 3Ethyl; m = 3; p = 3
5,00 g (17,3 mmol) N,N' -Bis [3 - (diethylamino) propyl] harnstoff werden in 10 ml Wasser gelöst. Dann werden 1,95 g (17,3 mmol) 1, 3-Dichlorpropan zugegeben. Nun wird 16 h unter Rühren auf 100°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung .5.00 g (17.3 mmol) of N, N 'bis [3 - (diethylamino) propyl] urea are dissolved in 10 ml of water. Then 1.95 g (17.3 mmol) of 1,3-dichloropropane are added. The mixture is now heated to 100 ° C. for 16 hours with stirring. After cooling, an aqueous polymer solution is obtained.
2.6 Herstellung eines Polymeren, bei- dem R-] , R2J 3J 4 =2.6 Preparation of a polymer in which R-], R 2J 3 J 4 =
Methyl ; m = 2 ; p = 3Methyl; m = 2; p = 3
5,00 g (24,7 mmol) N,N' -Bis [2- (dimethylamino) ethy] harnstoff werden in 10 ml Wasser gelöst. Dann werden 2,79 g (24,7 mmol) 1, 3-Dichlorpropan zugegeben. Nun wird 24 h unter Rühren auf 90°C erhitzt. Nach dem Abkühlen erhält man eine wäßrige Polymerlösung .5.00 g (24.7 mmol) of N, N 'bis [2- (dimethylamino) ethy] urea are dissolved in 10 ml of water. Then 2.79 g (24.7 mmol) of 1,3-dichloropropane are added. The mixture is now heated to 90 ° C. for 24 hours with stirring. After cooling, an aqueous polymer solution is obtained.
3. Herstellungsbeispiel des cruaternären Derivates der Pyridin-3 -carbonsäure3. Production example of the cruaternary derivative of pyridine-3-carboxylic acid
Synthese von N,N' -p-Xylylen-bis- (pyridinium-3 -carbcxylat) (Formel C, R6 = p-Xylylen) :Synthesis of N, N '-p-xylylene-bis- (pyridinium-3-carboxylate) (formula C, R 6 = p-xylylene):
5,00 g (39,80 mmol) Nicotinsäure werden in 20 ml n-3utanol bei Raumtemperatur vorgelegt, dann werden 5,41 g (19,90 mmol) α, - 'Dibrom-p-xylol bei Raumtemperatur zugegeben. Dann wird 16 h unter Rühren auf 70 °C erhitzt, das ausgefallene Produkt
abfiltriert, mit 10 ml n-Butanol gewaschen und getrocknet. Man erhält 9,85 g weiße Kristalle, die bei 220°C unter Zersetzung schmelzen.5.00 g (39.80 mmol) of nicotinic acid are placed in 20 ml of n-3utanol at room temperature, then 5.41 g (19.90 mmol) of α, - 'dibromo-p-xylene are added at room temperature. The precipitated product is then heated to 70 ° C. for 16 hours with stirring filtered off, washed with 10 ml of n-butanol and dried. 9.85 g of white crystals are obtained, which melt at 220 ° C. with decomposition.
4. Ar.wendungsbeispiele4. Application examples
Beispiele 1 - 6 :Examples 1-6:
Es wird jeweils ein Bad mit folgender Zusammensetzung verwendet:A bath with the following composition is used:
10 g/1 Zn10 g / 1 Zn
130 g/1 NaOH130 g / 1 NaOH
20 g/1 Na2C03 20 g / 1 Na 2 CO 3
1 g/1 Zusatz nach Herstellungsbeispiel 2.1 - 2.6 (berechnet als Festsubstanz)1 g / 1 additive according to production example 2.1 - 2.6 (calculated as solid substance)
250 ml der Lösung werden in eine Hullzelle gefüllt. Als Anode dient eine Zn-anode. Das Kathodenblech wird 15 min bei 1 A beschichtet. Das Bad sollte eine Temperatur von 28 °C besitzen. Das Blech wird abgespült, 10 s in 0,3 Vol-% HN03 aufgehellt , wieder gespült und unter Preßluft getrocknet . Die Schichtdickemessung erfolgt an zwei Punkten 3 cm vom unteren Rand und 2,5 cm vom rechten und linken seitlichen Rand bei hoher (2,8 A/dm2) und niedriger Stromdichte (0,5 A/dm ) . Gemessen wird mit XRF an vier Stellen bei der jeweiligen Position, um den Meßfehler so gering wie möglich zu halten. Die Schichtdickeverteilung entspricht dem Verhältnis der gemessenen Werte für die Schichtdicke bei hoher (hcd) und niedriger Stromdichte (Icd) .250 ml of the solution are placed in a Hull cell. A Zn anode serves as the anode. The cathode sheet is coated at 1A for 15 minutes. The bath should have a temperature of 28 ° C. The sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. The layer thickness measurement is carried out at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm). XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible. The layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (Icd).
Schichtdickeverteilung = hcd: IcdLayer thickness distribution = hcd: Icd
Die erhaltenen Ergebnisse sind in folgender Tabelle 1 zusammengestellt :
Tabelle 1The results obtained are summarized in the following Table 1: Table 1
Verwendetes Schichtdicke S Scchhiicchhttedicke Schichtdicke¬Layer thickness used S layer thickness
Polymeres hcd Icd verteilungPolymeric hcd icd distribution
R-t , R2, R3, R = = Methyl; m = 3; p = 4 6,11 μm 5,38 μm 1 , 14Rt, R2, R3, R = = methyl; m = 3; p = 4 6.11 μm 5.38 μm 1, 14
Ri i R21 R3, R = = Methyl; m = 3; p = 3 6,19 μm 4,15 μm 1 ,49Ri i R21 R3, R = = methyl; m = 3; p = 3 6.19 μm 4.15 μm 1.49
R1, R2, R3, R = = Methyl; m = 3; p = 6 4,71 μm 3,50 μm 1 ,35R1, R 2 , R3, R = = methyl; m = 3; p = 6 4.71 μm 3.50 μm 1.35
i i R2, R3, R z = Methyl; m = 3; p = 5 5,02 μm 4,03 μm 1 ,25ii R2, R3, R z = methyl; m = 3; p = 5 5.02 μm 4.03 μm 1.25
R1 , R2, R3, R : = Ethyl; m = 3; p = 3 0,76 μm 0,55 μm 1 ,37R1, R 2 , R3, R : = ethyl; m = 3; p = 3 0.76 μm 0.55 μm 1.37
Rι, R2, R3, R : = Methyl; m = 2; p = 3 7,70 μm 3,53 μm 2,18Rι, R 2 , R3, R : = methyl; m = 2; p = 3 7.70 µm 3.53 µm 2.18
Beispiele 7 - 12Examples 7-12
Es wird ein Bad mit folgender Zusammensetzung verwendetA bath with the following composition is used
10 g/1 Zn10 g / 1 Zn
130 g/1 NaOH130 g / 1 NaOH
20 g/1 Na2C03 20 g / 1 Na 2 CO 3
1,2 g/1 Diallylammonium-Schwefeldioxid-Copolymer (DE 195 091.2 g / 1 diallylammonium sulfur dioxide copolymer (DE 195 09
713, US 4 030 987)713, US 4,030,987)
0,19 g/1 Umsetzungsprodukt Epichlorhydrin mit Dimethylamino- propylamin (US 3 884 774)0.19 g / 1 reaction product epichlorohydrin with dimethylamino-propylamine (US 3 884 774)
9,2 mg/1 N-Benzyl-pyridinium-3-carboxylat9.2 mg / 1 N-benzyl-pyridinium-3-carboxylate
1,25 g/1 Trilon D (Trinatriumsalz der Hydroxyethylethylen- diamintriessigsäure; Fa. BASF, 40%ige Lösung)1.25 g / 1 Trilon D (trisodium salt of hydroxyethylethylenediaminetriacetic acid; from BASF, 40% solution)
0,1 g/1 3-Mercaptotriazol0.1 g / 1 3-mercaptotriazole
1 g/1 Zusatz nach Herstellungsbeispiel 2.1 - 2.6 (berechnet als Festsubstanz)
900 ml der Lösung werden in ein breites ll-Becherglas gefüllt (Figur) . Als Anode dient eine umhüllte Zn-anode. Es wird bei starker Lufteinblasung (1 i/min) gearbeitet, welche aus einem L-förmigen Plastikrohr mit 6 kleinen Löchern (3 auf jeder Seite) unterhalb der eingesetzten Kathode ausströmt. Das Kathodenblech (18,5 cm x 5 cm) wird am unteren Ende gebogen und 35 min bei 2,8 A beschichtet. Das Bad sollte eine Temperatur von 20°C besitzen, da besonders bei niedriger Temperatur Blasen auftreten. Das Blech wird abgespült, 10 s in 0,3 Vol-% HN03 aufgehellt, wieder gespült und unter Preßluft getrocknet. Danach wird das Blech vorsichtig gerade gebogen, bis es eine gestreckte Form einnimmt, und bei Raumtemperatur gelagert. Es muß täglich nach Blasen untersucht werden.1 g / 1 additive according to production example 2.1 - 2.6 (calculated as solid substance) 900 ml of the solution are poured into a wide II beaker (Figure). A coated Zn anode serves as the anode. It works with strong air injection (1 i / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode. The cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min. The bath should have a temperature of 20 ° C, as bubbles occur especially at low temperatures. The sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
Die erhaltenen Ergebnisse sind in Tabelle 2 zusammengestellt :The results obtained are summarized in Table 2:
Tabelle 2Table 2
Verwendetes Polymeres BlasenbildungPolymer used Blistering
R1, R2, R3, R4 = Methyl; m = 3; p = 4 Keine Rι, R2, R3, R = Methyl; m = 3; p = 3 KeineR1, R 2 , R3, R 4 = methyl; m = 3; p = 4 none R 1, R 2 , R 3 , R = methyl; m = 3; p = 3 none
R1 t R2, R3, R4 = Methyl; m = 3; p = 6 KeineR 1 t R 2 , R 3 , R 4 = methyl; m = 3; p = 6 none
Rι, R2, R3, R4 = Methyl; m = 3; p = 5 KeineRι, R 2 , R 3 , R4 = methyl; m = 3; p = 5 none
Rlf R2l R3l R4 = Ethyi; m = 3; p = 4 KeineR if R 2l R 3l R 4 = ethyl; m = 3; p = 4 none
R1, R2, 3, 4 = Methyl; m = 2; p = 3 KeineR1, R2, 3, 4 = methyl; m = 2; p = 3 none
Beispiel 13Example 13
Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zinkschicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:
10 g/1 ZnO 120 g/1 KOHAn aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer. The electrolyte had the following composition: 10 g / 1 ZnO 120 g / 1 KOH
1 g/1 Zusatz nach Herstεllungsbeispiel 2.1 (berechnet als Festsubstanz)1 g / 1 additive according to production example 2.1 (calculated as solid substance)
20 mg/1 N-Benzyl-pyridinium-3-carboxylat 60 mg/1 Thioharnstoff20 mg / 1 N-benzyl-pyridinium-3-carboxylate 60 mg / 1 thiourea
40 mg/1 Anisaldehyd (Aktivsubstanz als Bisulfitaddukt )40 mg / 1 anisaldehyde (active substance as bisulfite adduct)
Ein Stahlblech (5 cm x 5 cm) wurde bei 2 A/dm und 30 °C 30 Minuten lang abgeschieden.A steel sheet (5 cm x 5 cm) was deposited at 2 A / dm and 30 ° C for 30 minutes.
Das Stahlblech wurde gespült und in einer handelsüblichen Blauchromatierung (Corrotriblue, Atotech) chromatiert . Das chromatierte Blech besaß handelsüblichen Standard. Die Zinkschicht zeigte keine Tendenz zur Blasenbildung, selbst Temperung im Umluftschrank bei 220 °C für 30 Minuten und anschließendes Abschrecken in Leitungswasser mit Raumtemperatur führte nicht zu Abplatzern.The steel sheet was rinsed and chromated in a commercially available blue chromating (Corrotriblue, Atotech). The chromated sheet had a standard commercially available. The zinc layer showed no tendency to form bubbles, even tempering in a circulating air cabinet at 220 ° C for 30 minutes and subsequent quenching in tap water at room temperature did not lead to flaking.
Beispiel 1 :Example 1 :
Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zinkschicht geεignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer. The electrolyte had the following composition:
12,5 g/1 ZnO12.5 g / 1 ZnO
130 g/1 NaOH130 g / 1 NaOH
20 g/1 Na2C03 20 g / 1 Na 2 CO 3
2 g/1 Zusatz nach Herstellungsbeispiel 2.2 (berechnet als2 g / 1 additive according to production example 2.2 (calculated as
Festsubstanz)Solid substance)
25 mg/1 N-Benzyl-pyridinium-3-carboxylat25 mg / 1 N-benzyl-pyridinium-3-carboxylate
100 mg/1 3-Mercaptotriazol100 mg / 1 3-mercaptotriazole
50 mg/1 p-Hydroxybenzaldehyd (Aktivsubεtanz als Bisuifitad- dukt)
Ein Hullzellblech wurde bei 1 Ampere und Raumtemperatur 15 Minuten lang abgeschieden.50 mg / 1 p-hydroxybenzaldehyde (active substance as bisuifitad product) A Hull cell sheet was deposited at 1 ampere and room temperature for 15 minutes.
Das Hullzellblech wurde gespült und in einer handelsüblichen Gelbchromatierung (Tridur Gelb Liquid, Atotεch) chromatiεrt. Das chromatierte Blech besaß eine geringfügigε Irisiεrung und handelsüblichen Standard.The Hull cell sheet was rinsed and chromatized in a commercially available yellow chromation (Tridur Yellow Liquid, Atotεch). The chromated sheet had a slight iridescence and standard commercially available.
Die Schichtdickevertεilung wurde nach dem oben bεschriebenen Test gemessen, sie betrug 1,30.The layer thickness distribution was measured according to the test described above, it was 1.30.
Die Zinkschicht zeigte keinε Anzeichen von Blasenbildung, selbst nicht nach 30 Minuten Tεmpεrung im Umluftschrank bei 220 °C und anschliεßendem Abschrecken in Leitungswasser von Raumtemperatur.The zinc layer showed no signs of blistering, even after 30 minutes in the circulating air cabinet at 220 ° C. and subsequent quenching in tap water from room temperature.
Beispiel 15:Example 15:
Es wurde ein wäßriger Elektrolyt hergestεllt, der zum galvanischen Abscheiden einer Zinkschicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc layer. The electrolyte had the following composition:
18,5 g/1 ZnO18.5 g / 1 ZnO
115 g/1 NaOH115 g / 1 NaOH
1,5 g/1 Zusatz nach Herstellungsbeispiel 2.5 (berechnet als1.5 g / 1 additive according to production example 2.5 (calculated as
Festsubstanz)Solid substance)
25 mg/1 N,N' -p-Xylylεn-bis- (pyridinium-3-carboxylat)25 mg / 1 N, N '-p-xylylene-bis- (pyridinium-3-carboxylate)
70 mg/1 Thioharnstoff70 mg / 1 thiourea
60 mg/1 Vanillin (Aktivsubstanz als Bisulfitaddukt)60 mg / 1 vanillin (active substance as bisulfite adduct)
Schrauben aus Stahl wurdεn in εiner Trommel bei einer Strom- dichte von 0,1 - 1 A/dm und Raumtemperatur galvanisiert.Steel screws were galvanized in a drum with a current density of 0.1 - 1 A / dm and room temperature.
Anschließend wurde gespült und in εiner handelsüblichen Gelbchromatierung (Tridur Gelb Liquid, Atotech) chromatiεrt . Die chromatiertεn Schrauben besaßen handelsüblichen Standard.
Die glänzende Zinkschicht war auf den Schrauben sehr gleichmäßig verteilt und zeigtε keine Tendenz zur Blasenbildung, selbst nicht bei Temperung für 30 Minuten auf 220°C im Trok- kεnschrank und anschliεßεndεm Abschrεckεn in Wasser, weiches Raumtemperatur besitzt.It was then rinsed and chromatized in a commercially available yellow chromation (Tridur Yellow Liquid, Atotech). The chromated screws had a standard commercially available. The glossy zinc layer was very evenly distributed on the screws and showed no tendency to form bubbles, even when tempered for 30 minutes at 220 ° C. in a drying cabinet and then quenched in water, having a soft room temperature.
Beispiel 16:Example 16:
Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Nickel-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-nickel layer. The electrolyte had the following composition:
10 g/1 ZnO10 g / 1 ZnO
8 g/1 NiS04 6 H208 g / 1 NiS0 4 6 H 2 0
120 g/1 NaOH120 g / 1 NaOH
30 g/1 Triethanolamin30 g / 1 triethanolamine
1,5 g/1 Zusatz nach Herstellungsbεispiεl 2.4 (berechnet als1.5 g / 1 additive according to manufacturing example 2.4 (calculated as
Festsubstanz)Solid substance)
50 mg/1 Veretriumaldehyd (Aktivsubstanz als Bisulfitaddukt)50 mg / 1 veretrium aldehyde (active substance as bisulfite adduct)
Ein Stahlblech (5 cm x 5 cm) wurde bei 3 A/dm2 und 30 °C 30 Minuten lang abgeschieden. Es wurde eine gleichmäßigε, glänzende Zink-Nickel-Schicht abgeschiεden.A steel sheet (5 cm x 5 cm) was deposited at 3 A / dm 2 and 30 ° C for 30 minutes. A uniform, shiny zinc-nickel layer was deposited.
Die Zink-Nickel-Schicht zeigte keine Anzeichen von Blasenbildung, selbst nicht nach 30 Minuten Temperung im Umluftschrank bei 220 °C und anschließendem Abschrecken in Leitungswassεr von Raumtemperatur.The zinc-nickel layer showed no signs of blistering, even after 30 minutes of tempering in a circulating air cabinet at 220 ° C. and subsequent quenching in tap water at room temperature.
Beispiel 17 :Example 17:
Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Eisen-Schicht geεignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-iron layer. The electrolyte had the following composition:
15 g/1 ZnO 120 g/1 NaOH
25 mg/1 N-3enzyi-pyridinium-3-carboxylat15 g / 1 ZnO 120 g / 1 NaOH 25 mg / 1 N-3enzypyridinium-3-carboxylate
Ein Stahlblech (5 cm x 5 cm) wurde bei 2 A/dm" und Raumtemperatur 30 Minuten lang abgeschiedεn. Es wurde eine gleichmäßige, glänzende Zink-Eisen-Kobalt-Schicht abgeschieden.A steel sheet (5 cm x 5 cm) was deposited at 2 A / dm "and room temperature for 30 minutes. A uniform, shiny zinc-iron-cobalt layer was deposited.
Die Zink-Eisen-Kobalt-Schicht zeigte keinε Anzεichen von Blasenbildung, selbst nicht nach 30 Minuten Temperung im Umluft- schrank bei 220 °C und anschließendεm Abschrεcken in Lεitungs- wassεr von Raumtemperatur.The zinc-iron-cobalt layer showed no sign of blistering, even after 30 minutes of tempering in a circulating air cabinet at 220 ° C. and subsequent quenching in tap water at room temperature.
Beispiεl 19 :Example 19:
Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Mangan-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensetzung:An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-manganese layer. The electrolyte had the following composition:
15 g/1 ZnO15 g / 1 ZnO
120 g/1 NaOH120 g / 1 NaOH
40 g/1 MnCl2 • 4 H2040 g / 1 MnCl 2 • 4 H 2 0
40 g/1 Natriumglukonat40 g / 1 sodium gluconate
4 g/1 Ascorbinsäure4 g / 1 ascorbic acid
2 g/1 Zusatz nach Herstellungsbεispiel 2.1 (berechnet als2 g / 1 additive according to production example 2.1 (calculated as
Festsubstanz)Solid substance)
100 mg/1 3-Mercapto-l, 2, 4-triazol100 mg / 1 3-mercapto-1,2,4-triazole
20 mg/1 N-Benzyl-pyridinium-3 -carboxylat20 mg / 1 N-benzyl-pyridinium-3-carboxylate
Ein Hullzellblεch wurde bei 1 Ampere und Raumtemperatur 15 Minuten lang abgeschieden. Das Hullzellblech wurde gespült und 10 s in 0,3 Vol% HN03 aufgehellt.A Hullzellblεch was deposited at 1 ampere and room temperature for 15 minutes. The Hull cell sheet was rinsed and lightened in 0.3 vol% HN0 3 for 10 s.
Die Schichtdickeverteilung wurde nach dem oben beschriebenen Test gemessen; sie betrug 1,41.The layer thickness distribution was measured according to the test described above; it was 1.41.
Der Manganeinbau wurde an den gleichen Positionen mit XRF gemessen, an denen auch die Schichtdickemessung erfolgte. Bei
60 mg/1 Eisen (als FeSC4 • 7 H20) 25 g/1 NatriumglukonatThe manganese incorporation was measured with XRF at the same positions at which the layer thickness was also measured. at 60 mg / 1 iron (as FeSC 4 • 7 H 2 0) 25 g / 1 sodium gluconate
2 g/1 Zusatz nach Herstellungsbeispiel 2.2 (berechnet als Festsubstanz)2 g / 1 additive according to production example 2.2 (calculated as solid substance)
200 mg/1 3-Mercaptotriazol200 mg / 1 3-mercaptotriazole
40 mg/1 Hεliotropin (Aktivsubstanz als Bisulfitaddukt)40 mg / 1 hεliotropin (active substance as bisulfite adduct)
Ein Hullzellblech wurde bei 1 Amperε und Raumtεmperatur 15 Minuten lang abgeschieden.A Hull cell sheet was deposited at 1 amp and room temperature for 15 minutes.
Das Hullzellblech wurde gespült und in einεr handεlsüblichεn Schwarzehromatiεrung für Zink-Eisen-Schichten (Tridur Schwarz Liquid ZnFe, Atotεch) chromatiert. Das chromatierte Blech be- saß eine sehr gutε Schwarzfärbung.The Hull cell sheet was rinsed and chromated in a commercially available black chromation for zinc-iron layers (Tridur Schwarz Liquid ZnFe, Atotεch). The chromated sheet had a very good black color.
Diε Schichtdickeverteilung wurde nach dem oben beschriebenen Test gemessen, sie betrug 1,50.The layer thickness distribution was measured according to the test described above, it was 1.50.
Die Zink-Eisen-Schicht zeigte keine Anzeichεn von Blasεnbil- dung, sεlbst nicht nach 30 Minutεn Temperung im Umluftschrank bei 220°C und anschließendem Abschrecken in Leitungswasser von Räumtempεratur.The zinc-iron layer showed no signs of blistering, not even after 30 minutes' tempering in a circulating air cabinet at 220 ° C. and subsequent quenching in tap water at room temperature.
Beispiel 18 :Example 18:
Es wurde ein wäßriger Elektrolyt hergestellt, der zum galvanischen Abscheiden einer Zink-Eisen-Kobalt-Schicht geeignet ist. Der Elektrolyt hatte die folgende Zusammensεtzung:An aqueous electrolyte was produced which is suitable for the galvanic deposition of a zinc-iron-cobalt layer. The electrolyte had the following composition:
12,5 g/i ZnO 110 g/1 NaOH 30 mg/1 Eisen (als FeS04 • 7 H0)12.5 g / i ZnO 110 g / 1 NaOH 30 mg / 1 iron (as FeS0 4 • 7 H0)
30 mg/1 Kobalt (als CoS04 - 7 H20) 25 g/1 Natriumglukonat30 mg / 1 cobalt (as CoS0 4 - 7 H 2 0) 25 g / 1 sodium gluconate
2 g/1 Zusatz nach Herstellungsbeispiεl 2.3 (berechnet als2 g / 1 additive according to manufacturing example 2.3 (calculated as
FestSubstanz)Solid substance)
100 mg/1 3-Mercaptotriazol
2,8 A/dm2 betrug der Gehalt an Mangan 5,65%; bei 0,5 A/dm2 betrug der Mangangehalt 7,81%.100 mg / 1 3-mercaptotriazole 2.8 A / dm 2 , the manganese content was 5.65%; at 0.5 A / dm 2 the manganese content was 7.81%.
Vergleichsbeispiele 1 - 4 :Comparative Examples 1-4:
Es wird ein Bad mit folgender Zusammensetzung verwεndet :A bath with the following composition is used:
10 g/1 Zn 130 g/1 NaOH 20 g/1 Na2C03 10 g / 1 Zn 130 g / 1 NaOH 20 g / 1 Na 2 CO 3
1 g/1 Zusatz der in den genannten Druckschriften beschriebenen Additive (berechnet als Festsubstanz)1 g / 1 addition of the additives described in the publications mentioned (calculated as solid substance)
250 ml der Lösung werden in eine Hullzelle gefüllt. Als Anode dient eine Zn-anode. Das Kathodenblech wird 15 min bei 1 A beschichtet. Das Bad sollte einε Tεmperatur von 28°C besitzen. Das Blech wird abgespült, 10 s in 0,3 Vol-% HN03 aufgehellt, wieder gespült und unter Preßluft getrocknet. Die Schichtdickemessung erfolgt an zwei Punkten 3 cm vom unteren Rand und 2,5 cm vom rechten und linken seitlichen Rand bei hoher (2,8 A/dm") und niedriger Stromdichte (0,5 A/dm ) . Ge- mεssεn wird mit XRF an vier Stellen bei der jeweiligen Position, um den Meßfehler so gering wie möglich zu halten. Die Schichtdickevertεilung entspricht dem Verhältnis der gemessenen Wertε für diε Schichtdickε bεi hohεr (hcd) und niedriger Stromdichte (Icd) .250 ml of the solution are placed in a Hull cell. A Zn anode serves as the anode. The cathode sheet is coated at 1A for 15 minutes. The bath should have a temperature of 28 ° C. The sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. The layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm " ) and low current density (0.5 A / dm). Measurements are also taken XRF at four positions at the respective position in order to keep the measurement error as low as possible The layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at higher (hcd) and lower current density (icd).
Schichtdickevertεilung = hcd: IcdLayer thickness distribution = hcd: Icd
Die erhaltenen Ergebnisse sind in folgender Tabelle 3 zusammengestellt :
Tabelle 3The results obtained are summarized in Table 3 below: Table 3
Verwendetes Schichtdicke Schichtdicke Schichtdicke- Polymeres hcd Icd verteiiungLayer thickness used Layer thickness Layer thickness polymer hcd Icd distribution
Umsetzungsprodukt 11 ,0 μm 3,80 μm 2,90 Epichlorhydrin mit Imidazol DE 25 25 264Reaction product 11.0 μm 3.80 μm 2.90 epichlorohydrin with imidazole DE 25 25 264
Umsetzungsprodukt 8,65 μm 2,70 μm 3,20 Epichlorhydrin mit Dimethylaminopropylamin US 3 884 774Reaction product 8.65 μm 2.70 μm 3.20 epichlorohydrin with dimethylaminopropylamine US 3 884 774
Mirapol WT 5,89 μm 4,17 μm 1 ,41 US 5 435 898Mirapol WT 5.89 µm 4.17 µm 1.41 US 5 435 898
Diallylammonium- 7,10 μm 2,58 μm 2,75 Schwefeldioxid-Copolymer DE 195 09 713Diallylammonium - 7.10 μm 2.58 μm 2.75 sulfur dioxide copolymer DE 195 09 713
Verglεichsbεispiεlε 5 - 6 :Comparative examples 5 - 6:
Es wird εin Bad mit folgender Zusammensetzung verwendet :A bath with the following composition is used:
10 g/1 Zn 130 g/1 NaOH 20 g/1 Na2C03 10 g / 1 Zn 130 g / 1 NaOH 20 g / 1 Na 2 CO 3
1,2 g/1 Diallylammonium-Schwefeldioxid-Copolymεr (DE 195 09 713, US 4 030 987)1.2 g / 1 diallylammonium sulfur dioxide copolymer (DE 195 09 713, US 4 030 987)
0,19 g/1 Umsetzungsprodukt Epichlorhydrin mit Dimethylaminopropylamin (US 3 884 774)0.19 g / 1 reaction product epichlorohydrin with dimethylaminopropylamine (US 3 884 774)
9,2 mg/1 N-Benzyl-pyridinium-3-carboxylat 1,25 g/1 Trilon D (Fa. BASF, 40%ige Lösung) 0,1 g/1 3-Mercaptotriazol9.2 mg / 1 N-benzyl-pyridinium-3-carboxylate 1.25 g / 1 Trilon D (from BASF, 40% solution) 0.1 g / 1 3-mercaptotriazole
1 g/1 Zusatz der in den genannten Druckschriften beschriebenen Additive (berechnet als Festsubstanz)1 g / 1 addition of the additives described in the publications mentioned (calculated as solid substance)
900 ml der Lösung werdεn in εin breites ll-Becherglas gefüllt (Figur) . A.ls Anode dient eine umhüllte Zn-anode. Es wird bei
starker Lufteinblasung (1 1/min) gearbeitet, welche aus einεm L-förmigεn Plastikrohr mit 6 kiεinεn Löchεrn (3 auf j εder Seite) unterhalb der εingesetzten Kathode ausströmt. Das Kathodenblech (18,5 cm x 5 cm) wird am unteren Ende gεbogεn und 35 min bei 2,8 A beschichtet. Das Bad sollte einε Tεmpεratur von 20°C bεsitzen, da besonders bei niedriger Temperatur Blasen auftreten. Das Blech wird abgespült, 10 s in 0,3 Vol-% HN03 aufgehellt, wieder gespült und unter Preßluft getrocknet. Danach wird das Blech vorsichtig geradε gεbogen, bis es eine gestreckte Form einnimmt, und bei Raumtemperatur gelagert. Es muß täglich nach Blasen untersucht werdεn.900 ml of the solution are poured into a wide II beaker (Figure). A.l's anode is a coated Zn anode. It will be at strong air injection (1 1 / min) worked, which flows out of an L-shaped plastic tube with 6 kiεinεn holes (3 on each side) below the inserted cathode. The cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min. The bath should have a temperature of 20 ° C, since bubbles occur especially at low temperatures. The sheet is rinsed off, lightened for 10 s in 0.3% by volume of HNO 3 , rinsed again and dried under compressed air. Thereafter, the sheet is carefully straightened until it assumes an elongated shape and stored at room temperature. It must be examined daily for blisters.
Die erhaltenen Ergebnisse sind in Tabelle 4 zusammengestellt :The results obtained are summarized in Table 4:
Tabelle 4Table 4
Verwendetes Polymeres BlasenbildungPolymer used Blistering
Mirapol WT Stark innerhalb von 3 dMirapol WT Stark within 3 d
US 5 435 898US 5,435,898
Diallylammonium- Sofort sehr starkDiallylammonium- Immediately very strong
Schwefeldioxid-CopolymerSulfur dioxide copolymer
DE 195 09 713
DE 195 09 713
Claims
1. Wäßriges alkalisches cyanidfreiεs Bad zur galvanischen Abscheidung von Zink- oder Zinklegiεrungsüberzügen auf Substratoberflächen, dadurch g e k e n n z e i c h n e t , daß es1. Aqueous alkaline, cyanide-free bath for the galvanic deposition of zinc or zinc alloy coatings on substrate surfaces, due to the fact that it is
(a) einε Zinkionεnquelle und gεgebenεnfalls eine Quelle für weitere Metallionen,(a) a zinc ion source and possibly a source for further metal ions,
(b) Hydroxidionen und(b) hydroxide ions and
(c) ein in dem Bad lösliches Polymeres der allgemeinen Formel A(c) a polymer of the general formula A soluble in the bath
worin m den Wert 2 oder 3 hat, n einεn Wεrt von minde- stεns 2 hat, Rlt R2, R3 und R , diε glεich oder verschieden sein können, jeweils für Methyl, Ethyl, Hydroxyethyl stehen, p einεn Wert im Bereich von 3 bis 12 hat und X" für Cl", Br" und/oder I" stehtwhere m has the value 2 or 3, n has a value of at least 2, R lt R 2 , R 3 and R, which may be the same or different, each represent methyl, ethyl, hydroxyethyl, p a value in the range has from 3 to 12 and X "stands for Cl " , Br " and / or I "
sowie gegebenenfallsand if necessary
(d) übliche Additive enthält.(d) contains common additives.
2. Bad nach Anspruch 1 , dadurch g e k e n n z e i c h n e t , daß in der allgemeinen Formel A n einen Wert im Bereich von 2 bis 80, vorzugsweise von 3 bis 20, hat.2. Bath according to claim 1, characterized in that in the general formula A n has a value in the range from 2 to 80, preferably from 3 to 20.
3. Bad nach An pruch 1 oder 2 , dadurch g e k e n n z e i c h n e t , daß das in dem Bad lösliche Polymere der
Formel A in einer Menge von 0,1 bis 50 g/1, vorzugsweise 0,25 bis 10 g/1, vorhanden ist.3. Bath according to claim 1 or 2, characterized in that the polymer soluble in the bath Formula A is present in an amount of 0.1 to 50 g / 1, preferably 0.25 to 10 g / 1.
4. Bad nach einem der Ansprüche 1 bis 3, dadurch g e k e n n z e i c h n e t , daß es weiterhin ein quaternärεs Derivat einεr Pyridin-3 -carbonsäure der Formel B und/oder ein quaternäres Derivat einεr Pyridin-3-carbonsäure der Formel C4. Bath according to one of claims 1 to 3, characterized in that it is also a quaternary derivative of pyridine-3-carboxylic acid of formula B and / or a quaternary derivative of pyridine-3-carboxylic acid of formula C.
BB
worin R6 für einen gesättigten oder ungesättigten, aliphati- schen, aromatischen oder araliphatischen Kohlenwassεrstoff- rεst mit 1 bis 12 Kohlenstoffatomen steht, enthält.wherein R 6 represents a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.
5. Bad nach Anspruch 4 , dadurch g e k e n n z e i c h e t , daß das quaternäre Dεrivat der Pyridin-3- carbonsäure der Formel B .und/oder C in einer Menge von 0,005 bis 0,5 g/1, vorzugsweise von 0,01 bis 0,2 g/1, vorhanden ist.5. Bath according to claim 4, characterized in that the quaternary derivative of pyridine-3-carboxylic acid of the formula B. and / or C in an amount of 0.005 to 0.5 g / 1, preferably from 0.01 to 0.2 g / 1, is present.
6. Bad nach einεm dεr Ansprüche 1 bis 5, dadurch g e - k ε n n z ε i c h n ε t , daß die Zinkionenquelle Zinkoxid ist .6. Bath according to claims 1 to 5, characterized in that the source of zinc ions is zinc oxide.
7. Bad nach einem der Ansprüche 1 bis 6, dadurch g e - k e n n z e i c h n e t , daß die Konzentration der Zinkionen 0,2 bis 20 g/1 beträgt.
7. Bath according to one of claims 1 to 6, characterized in that the concentration of the zinc ions is 0.2 to 20 g / 1.
8. Bad nach einem der Ansprüche 1 bis 7, dadurch g e - k ε n n z e i c h n e t , daß diε wεitεrεn Mεtailionεn Kobalt-, Nickεl-, Mangan- und/oder Ξisenionen sind.8. Bath according to one of claims 1 to 7, characterized in that the further mestailions are cobalt, nickel, manganese and / or iron ions.
9. Bad nach Anspruch 8 , dadurch g ε k e n n z e i c h - n ε t , daß das Zink in εiner Menge von 0,2 bis 20 g/1, das Kobalt in einer Menge von 10 bis 120 mg/1, das Nickel in einer Menge von 0,3 bis 3 g/1, das Mangan in einεr Menge von 10 bis 100 g/1 und das Eisen in εiner Menge von 10 bis 120 mg/1 vorliegt .9. Bath according to claim 8, characterized in that ε indicates that the zinc in an amount of 0.2 to 20 g / 1, the cobalt in an amount of 10 to 120 mg / 1, the nickel in an amount from 0.3 to 3 g / 1, the manganese in an amount from 10 to 100 g / 1 and the iron in an amount from 10 to 120 mg / 1.
10. Bad nach einem der Ansprüche 1 bis 9, dadurch g ε - k e n n z e i c h n e t , daß das Alkali Natriumhydroxid ist.10. Bath according to one of claims 1 to 9, characterized in that the alkali is sodium hydroxide.
11. Bad nach Anspruch 10, dadurch g e k e n n z e i c h n e t , daß das Natriumhydroxid in einεr Menge von 80 bis 250 g/1 vorliegt.11. Bath according to claim 10, characterized in that the sodium hydroxide is present in an amount of 80 to 250 g / l.
12. Bad nach einem der Ansprüche 1 bis 9, dadurch g e - k ε n n z e i c h n e t , daß das Alkali Kaliumhydroxid ist.12. Bath according to one of claims 1 to 9, characterized in that the alkali is potassium hydroxide.
13. Bad nach Anspruch 12 , dadurch g e k e n n z e i c h n e t , daß das Kaliumhydroxid in einer Menge von 80 von 250 g/1 vorliegt.13. Bath according to claim 12, characterized in that the potassium hydroxide is present in an amount of 80 from 250 g / l.
14. Bad nach einem der Ansprüche 1 bis 13 , dadurch g e k e n n z e i c h n e t , daß es als Additiv einen Glanz- bildner aus der Gruppe Schwefεlverbindungen, Aldehyde, Keto- ne, Amine, Polyvinylalkohol, Polyvinylpyrrolidon, Proteine oder Reaktionsprodukte von Halogenhydrinen mit aliphatischen oder aromatischen Aminen, Polyaminen oder hetεrocyclischεn Stickstoffverbindungen und Gemische davon enthält.14. Bath according to one of claims 1 to 13, characterized in that there is an additive a brightener from the group sulfur compounds, aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, proteins or reaction products of halohydrins with aliphatic or aromatic amines, Contains polyamines or heterocyclic nitrogen compounds and mixtures thereof.
15. Bad nach Anspruch 14, dadurch g ε k ε n n z e i c h -
n e t , daß εs als Additiv einen aromatischen Aldehyd oder ein Bisulfitaddukt davon enthält .15. Bath according to claim 14, characterized g ε k ε nnzeich - net that εs contains an aromatic aldehyde or a bisulfite adduct thereof as an additive.
16. Bad nach Anspruch 15, dadurch g e k ε n n z ε i c h - n e t , daß der aromatische Aldehyd aus der Gruppe 4- Hydroxybenzaldehyd, 4-Hydroxy-3 -methoxybenzaldehyd, 3,4- Dimethoxybenzaldehyd, 3,4-Methylendioxybenzaldεhyd, 2 - Hydroxybenzaldεhyd und 4-Hydroxybenzaldehyd oder Gemischen davon ausgewählt ist .16. Bath according to claim 15, characterized in that the aromatic aldehyde from the group 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures thereof.
17. Bad nach Anspruch 15 oder 16, dadurch g e k ε n n - z e i c h n e t , daß der aromatische Aldehyd in einεr Menge von 0,005 bis 1,0 g/1, vorzugsweise von 0,01 bis 0,50 g/1, vorhanden ist .17. Bath according to claim 15 or 16, characterized in that the aromatic aldehyde is present in an amount of 0.005 to 1.0 g / 1, preferably 0.01 to 0.50 g / 1.
18. Bad nach einem der Ansprüche 1 bis 17, dadurch g e - k e n n z ε i c h n e t , daß es weiterhin einen Komplexbildner oder ein Wasserenthärtungsmittεl εnthält .18. Bath according to one of claims 1 to 17, characterized in that it also contains a complexing agent or a water softening agent.
19. Bad nach Anspruch 18, dadurch g ε k ε n n z e i c h - n e t , daß εs als Komplexbildner einen Chelatbildnεr enthält.19. Bath according to claim 18, characterized in that ε k ε n n z e i c h - n e t that εs contains a chelating agent as a complexing agent.
20. Bad nach Anspruch 19, dadurch g e k e n n z e i c h n e t , daß der Chelatbildnεr aus dεr Gruppε Hydroxycar- boxylatε, Aminoalkohole, Polyamine, Aminocarboxylate, Amino- phosphonatε und mehrwertige Alkohole sowie Gemischen davon ausgewählt ist .20. Bath according to claim 19, characterized in that the chelating agent is selected from the group consisting of hydroxycarboxylates, amino alcohols, polyamines, amino carboxylates, amino phosphonates and polyhydric alcohols and mixtures thereof.
21. Bad nach Anspruch 18 oder 19, dadurch g e k e n n z e i c h n e t , daß der Chelatbildner in einεr Menge von 2 bis 200 g/1 vorliegt.21. Bath according to claim 18 or 19, characterized in that the chelating agent is present in an amount of 2 to 200 g / l.
22. Bad nach einem der Ansprüche 1 bis 21, dadurch g e k e n z e i c h n e t , daß es weiterhin als Einεbner eine Schwefeiverbindung enthält .
22. Bath according to one of claims 1 to 21, characterized in that it also contains a sulfur compound as a leveler.
23. Bad nach Anspruch 22, dadurch g e k e n n z e i c h n e t , daß es als Einebner 3 -Mercapto-i, 2 , 4-triazoi und/oder Thioharnstoff enthäl .23. Bath according to claim 22, characterized in that it contains 3-mercapto-i, 2, 4-triazoi and / or thiourea as leveling agent.
24. Bad nacn Anspruch 22 oder 23, dadurch g e k e n n z e i c h n e t , daß es die Schwefelverbindung in einer Menge von 0,01 bis 0,50 g/1 enthält.24. Bath according to claim 22 or 23, characterized in that it contains the sulfur compound in an amount of 0.01 to 0.50 g / 1.
25. Verfahren zur galvanischen Abscheidung von Zinküberzügen oder von Zinklegierungsüberzügεn, dadurch g ε k ε n n - z ε i c h n ε t , daß als Bad εin Bad nach den Ansprüchen 1 bis 24 verwendet wird.25. A method for the galvanic deposition of zinc coatings or of zinc alloy coatings, characterized in that ε k ε n n - z ε i c h n ε t that a bath according to claims 1 to 24 is used as the bath.
26. Verfahren nach Anspruch 25, dadurch g e k e n n z e i c h n e t , daß das Bad bei einer Stromdichte von 0,01 bis 10 A/dm betrieben wird.26. The method according to claim 25, characterized in that the bath is operated at a current density of 0.01 to 10 A / dm.
27. Verfahren nach Anspruch 25 oder 26, dadurch g e - k ε n n z e i c h n e t , daß das Bad bei Temperaturεn von 15 bis 45°C betrieben wird.27. The method according to claim 25 or 26, characterized in that the bath is operated at temperatures of 15 to 45 ° C.
28. Verfahren nach einem der Ansprüche 25 bis 27, dadurch g e k ε n n z e i c h n e t , daß Überzüge auf einem leitenden Substrat unter Anwendung eines Trommelgalvanisierungs- vεrfahrεns abgeschieden werden.28. The method according to any one of claims 25 to 27, characterized in that coatings are deposited on a conductive substrate using a drum electroplating method.
29. Verfahren nach einem der Ansprüchε 25 bis 27, dadurch g ε k ε n n z ε i c h n e t , daß die Überzüge auf einem leitenden Substrat unter Anwendung eines Gestellgalvanisie- rungsverfahrens abgeschieden werden.29. Method according to one of claims 25 to 27, characterized in that the coatings are deposited on a conductive substrate using a rack electroplating method.
30. Verfahren nach einem der Ansprüche 25 bis 29, dadurch g e k ε n n z ε i c h n ε t , daß ein Zinküberzug abgeschieden wird.
30. The method according to any one of claims 25 to 29, characterized in that a zinc coating is deposited.
31. Verfahren nach einεm dεr Ansprüchε 25 bis 29, dadurch g ε k e n n z e i c h n e t , daß ein Zinklegiεrungsübεrzug abgeschiedεn wird.31. The method according to one of claims 25 to 29, characterized in that a zinc alloy coating is deposited.
32. Verfahren nach Anspruch 31,- dadurch g e k ε n n - z e i c h n e t , daß ein Überzug aus einer Zinklegierung mit ein oder mehrεrεn Mεtallεn aus dεr Gruppe Kobalt, Nickel, Mangan oder Eisen abgeschieden wird.
32. The method according to claim 31, characterized in that a coating of a zinc alloy is deposited with one or more metals from the group consisting of cobalt, nickel, manganese or iron.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19840019A DE19840019C1 (en) | 1998-09-02 | 1998-09-02 | Aqueous alkaline cyanide-free bath for the electrodeposition of zinc or zinc alloy coatings and method |
| DE19840019 | 1998-09-02 | ||
| PCT/EP1999/005318 WO2000014305A1 (en) | 1998-09-02 | 1999-07-26 | Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1114206A1 true EP1114206A1 (en) | 2001-07-11 |
| EP1114206B1 EP1114206B1 (en) | 2003-02-26 |
Family
ID=7879582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99936607A Expired - Lifetime EP1114206B1 (en) | 1998-09-02 | 1999-07-26 | Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6652728B1 (en) |
| EP (1) | EP1114206B1 (en) |
| JP (1) | JP4263363B2 (en) |
| AT (1) | ATE233329T1 (en) |
| CA (1) | CA2342219C (en) |
| DE (2) | DE19840019C1 (en) |
| ES (1) | ES2193728T3 (en) |
| PT (1) | PT1114206E (en) |
| WO (1) | WO2000014305A1 (en) |
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| EP2801640A1 (en) | 2013-05-08 | 2014-11-12 | ATOTECH Deutschland GmbH | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy |
| CN103320821B (en) * | 2013-07-12 | 2016-08-10 | 贵阳华科电镀有限公司 | A kind of Alkaline Zinc Cobalt Alloy Plating liquid |
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| CN103952733B (en) * | 2013-12-23 | 2017-06-20 | 韶关美妥维志化工有限公司 | For carrier brightener precursor and carrier brightener and electroplate liquid in alkaline zinc plating or Zinc alloy electroplating liquid |
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| CN107513733A (en) * | 2017-09-08 | 2017-12-26 | 湖北吉和昌化工科技有限公司 | A kind of zinc-plated complexant of new non-cyanide alkali |
| US11661666B2 (en) * | 2019-10-10 | 2023-05-30 | The Boeing Company | Electrodeposited zinc and iron coatings for corrosion resistance |
| KR102173164B1 (en) * | 2020-05-20 | 2020-11-02 | 주식회사 지에스켐텍 | Mixed brighteners for zincate plating solution and Zincate plating solution containing the same |
| CN111733433A (en) * | 2020-06-15 | 2020-10-02 | 武汉钢铁有限公司 | Alkaline electro-galvanized iron alloy plating solution additive for low-iron-content plating layer and application thereof |
| CN121204749A (en) * | 2025-11-28 | 2025-12-26 | 山东力净环保科技有限公司 | A method for preparing zinc electrodes in an alkaline system with multi-stage current-interface synergistic regulation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LT5481B (en) | 2006-07-11 | 2008-03-26 | Chemijos Institutas | Sarminis cinko-kobalto lydinio dangu nusodinimo elektrolitas |
| EP2096193A1 (en) | 2008-02-21 | 2009-09-02 | Atotech Deutschland Gmbh | Process for the preparation of corrosion resistant zinc and zinc-nickel plated linear or complex shaped parts |
| CN102171386A (en) * | 2008-10-17 | 2011-08-31 | 麦克德米德股份有限公司 | Zinc alloy electroplating baths and processes |
| CN102171386B (en) * | 2008-10-17 | 2013-11-06 | 麦克德米德股份有限公司 | Zinc alloy electroplating baths and processes |
| US9322107B2 (en) | 2009-09-08 | 2016-04-26 | Atotech Deutschland Gmbh | Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19840019C1 (en) | 2000-03-16 |
| JP2002524662A (en) | 2002-08-06 |
| DE59904390D1 (en) | 2003-04-03 |
| WO2000014305A9 (en) | 2000-08-24 |
| CA2342219A1 (en) | 2000-03-16 |
| PT1114206E (en) | 2003-07-31 |
| ES2193728T3 (en) | 2003-11-01 |
| JP4263363B2 (en) | 2009-05-13 |
| ATE233329T1 (en) | 2003-03-15 |
| WO2000014305A1 (en) | 2000-03-16 |
| CA2342219C (en) | 2008-09-23 |
| EP1114206B1 (en) | 2003-02-26 |
| US6652728B1 (en) | 2003-11-25 |
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