WO2023241905A1 - Stable alkaline electroplating bath with a diacid - Google Patents
Stable alkaline electroplating bath with a diacid Download PDFInfo
- Publication number
- WO2023241905A1 WO2023241905A1 PCT/EP2023/064422 EP2023064422W WO2023241905A1 WO 2023241905 A1 WO2023241905 A1 WO 2023241905A1 EP 2023064422 W EP2023064422 W EP 2023064422W WO 2023241905 A1 WO2023241905 A1 WO 2023241905A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- diacid
- electroplating bath
- salts
- electroplating
- Prior art date
Links
- 238000009713 electroplating Methods 0.000 title claims abstract description 78
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000004902 Softening Agent Substances 0.000 claims abstract description 7
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- -1 alkyl naphthalenes Chemical class 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical group 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WWNNZCOKKKDOPX-UHFFFAOYSA-N N-methylnicotinate Chemical compound C[N+]1=CC=CC(C([O-])=O)=C1 WWNNZCOKKKDOPX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 229950004580 benzyl nicotinate Drugs 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229940071118 cumenesulfonate Drugs 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229940012017 ethylenediamine Drugs 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 238000005375 photometry Methods 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 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 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- VSRWCQJUAYPITR-UHFFFAOYSA-N 1-benzylpyridin-1-ium-3-carboxylic acid;chloride Chemical compound [Cl-].OC(=O)C1=CC=C[N+](CC=2C=CC=CC=2)=C1 VSRWCQJUAYPITR-UHFFFAOYSA-N 0.000 description 1
- QQLIGMASAVJVON-UHFFFAOYSA-N 1-naphthalen-1-ylethanone Chemical compound C1=CC=C2C(C(=O)C)=CC=CC2=C1 QQLIGMASAVJVON-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
- 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 1
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical compound NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 1
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
- AYOUUPNRQOLHKM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]propyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C(C)CN(CCO)CCO AYOUUPNRQOLHKM-UHFFFAOYSA-N 0.000 description 1
- LBKQJGBYHPBRDC-UHFFFAOYSA-N 2-[ethyl-[2-[ethyl(2-hydroxyethyl)amino]ethyl]amino]ethanol Chemical compound OCCN(CC)CCN(CC)CCO LBKQJGBYHPBRDC-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- SHHKMWMIKILKQW-UHFFFAOYSA-N 2-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=O SHHKMWMIKILKQW-UHFFFAOYSA-N 0.000 description 1
- 229940080296 2-naphthalenesulfonate Drugs 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical class C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- FPMXPTIRDWHULR-UHFFFAOYSA-N 2-pyridin-1-ium-1-ylacetate;hydrochloride Chemical compound [Cl-].OC(=O)C[N+]1=CC=CC=C1 FPMXPTIRDWHULR-UHFFFAOYSA-N 0.000 description 1
- QPVYSIXKPUDBJG-UHFFFAOYSA-N 3,3-dihydroxypropane-1-sulfonic acid Chemical compound OC(O)CCS(O)(=O)=O QPVYSIXKPUDBJG-UHFFFAOYSA-N 0.000 description 1
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- WRBSVISDQAINGQ-UHFFFAOYSA-N 3-(dimethylcarbamothioylsulfanyl)propane-1-sulfonic acid Chemical compound CN(C)C(=S)SCCCS(O)(=O)=O WRBSVISDQAINGQ-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- VSVSRNTZDSTNLP-UHFFFAOYSA-N 3-prop-2-ynoxypropan-1-ol Chemical compound OCCCOCC#C VSVSRNTZDSTNLP-UHFFFAOYSA-N 0.000 description 1
- IQSKZUZFUMDBAG-UHFFFAOYSA-N 3-thioureidopropionic acid Chemical compound NC(=S)NCCC(O)=O IQSKZUZFUMDBAG-UHFFFAOYSA-N 0.000 description 1
- JJKVMNNUINFIRK-UHFFFAOYSA-N 4-amino-n-(4-methoxyphenyl)benzamide Chemical compound C1=CC(OC)=CC=C1NC(=O)C1=CC=C(N)C=C1 JJKVMNNUINFIRK-UHFFFAOYSA-N 0.000 description 1
- JSFATNQSLKRBCI-NLORQXDXSA-N 73945-47-8 Chemical compound CCCCCC(O)\C=C\C=C\C\C=C\C\C=C\CCCC(O)=O JSFATNQSLKRBCI-NLORQXDXSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BFBNYRRHXRBIIO-UHFFFAOYSA-N SSOSS Chemical compound SSOSS BFBNYRRHXRBIIO-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- MHWVMMHIJHHXQP-UHFFFAOYSA-N benzene-1,2,3-trisulfonic acid Chemical class OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1S(O)(=O)=O MHWVMMHIJHHXQP-UHFFFAOYSA-N 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- 150000008331 benzenesulfonamides Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KVYGGMBOZFWZBQ-UHFFFAOYSA-N benzyl nicotinate Chemical compound C=1C=CN=CC=1C(=O)OCC1=CC=CC=C1 KVYGGMBOZFWZBQ-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LXSLZSJZGMWGOL-UHFFFAOYSA-N butane-1-sulfonate;pyridin-1-ium Chemical compound C1=CC=[NH+]C=C1.CCCCS([O-])(=O)=O LXSLZSJZGMWGOL-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 1
- 229960002327 chloral hydrate Drugs 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- JOXWSDNHLSQKCC-UHFFFAOYSA-N ethenesulfonamide Chemical class NS(=O)(=O)C=C JOXWSDNHLSQKCC-UHFFFAOYSA-N 0.000 description 1
- IIWMSIPKUVXHOO-UHFFFAOYSA-N ethyl hexyl sulfate Chemical compound CCCCCCOS(=O)(=O)OCC IIWMSIPKUVXHOO-UHFFFAOYSA-N 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- WBIWIXJUBVWKLS-UHFFFAOYSA-N n'-(2-piperazin-1-ylethyl)ethane-1,2-diamine Chemical compound NCCNCCN1CCNCC1 WBIWIXJUBVWKLS-UHFFFAOYSA-N 0.000 description 1
- OVQABVAKPIYHIG-UHFFFAOYSA-N n-(benzenesulfonyl)benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NS(=O)(=O)C1=CC=CC=C1 OVQABVAKPIYHIG-UHFFFAOYSA-N 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- ZFIFHAKCBWOSRN-UHFFFAOYSA-N naphthalene-1-sulfonamide Chemical class C1=CC=C2C(S(=O)(=O)N)=CC=CC2=C1 ZFIFHAKCBWOSRN-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-M naphthalene-2-sulfonate Chemical compound C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-M 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZMLDXWLZKKZVSS-UHFFFAOYSA-N palladium tin Chemical compound [Pd].[Sn] ZMLDXWLZKKZVSS-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- XSUMSESCSPMNPN-UHFFFAOYSA-N propane-1-sulfonate;pyridin-1-ium Chemical compound C1=CC=NC=C1.CCCS(O)(=O)=O XSUMSESCSPMNPN-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- KMZJQQHWMFWLEK-UHFFFAOYSA-N pyrazol-3-one;pyridine Chemical compound C1=CC=NC=C1.O=C1C=CN=N1 KMZJQQHWMFWLEK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 239000001601 sodium adipate Substances 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 description 1
- ILJOYZVVZZFIKA-UHFFFAOYSA-M sodium;1,1-dioxo-1,2-benzothiazol-3-olate;hydrate Chemical compound O.[Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 ILJOYZVVZZFIKA-UHFFFAOYSA-M 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- LDHXNOAOCJXPAH-UHFFFAOYSA-M sodium;prop-2-yne-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC#C LDHXNOAOCJXPAH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Definitions
- the present invention relates to a method for electroplating a substrate comprising a step of applying a current through an aqueous electroplating bath which comprises the substrate and a diacid of the formula (I) or salts thereof, where n is 2, 3 or 4.
- the invention also relates to an aqueous alkaline electroplating bath which comprises the diacid of the formula (I) or salts thereof, a metal ion source, and optionally further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
- the invention also relates to the diacid of the formula (I) or salts thereof, and to a method for preparing the diacid of the formula (I) or salts thereof, comprising a hydrolysis of a dinitrile of the formula (II); and to a method for preparing the dinitrile of the formula (II) where n is 2, 3 or 4, comprising an addition of acrylonitrile to a diamine of the formula (III); and to a use of the diacid of the formula (I) or salts thereof for reducing the cyanide formation during electroplating. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.
- Electroplating is widely used in industry to improve the surface qualities of objects. For example the resistance to abrasion and corrosion, lubricity, reflectivity, electrical conductivity, or appearance of objects can be improved.
- a metal coating is made on a substrate through the reduction of cations of that metal by means of a direct electric current.
- the part to be coated acts is usually the cathode of an electrolytic cell filled with an electroplating bath.
- the electroplating bath is a typically solution of a salt of the metal to be coated.
- the anode is usually either a block of that metal, or of some inert conductive material.
- the electroplating bath usually contains complexing agents which keep the metal salts in solution.
- complexing agents which keep the metal salts in solution.
- amine-containing complexing agents such as diethylenetriaamine (DETA)
- DETA diethylenetriaamine
- amine-containing complexing agents form cyanides and byproducts during undesired anoxic oxidation. Cyanides are not only toxic, but also too strong complexing agents which reduce the concentration of metal salts can be electrodeposited.
- Beside reducing the cyanide formation in the electroplating bath during electroplating further objects of the inventions were to achieve a high quality optical appearance, homogenous composition of the metals in the layer, linear gradient of the layer thickness of the deposited metals according to the gradient of the current density.
- the objects were achieved by a method for electroplating a substrate comprising a step of applying a current through an aqueous electroplating bath which comprises the substrate and a diacid of the formula (I) or salts thereof, where n is 2, 3 or 4.
- n is 3. In another form n is 2. In another form n is 4. In another preferred form n is 3 or 4.
- the electroplating bath may comprise from 0.1 to 200 g/l, 1 to 100 g/l, 2 to 50 g/l or 3 to 30 g/l of the diacid.
- Suitable salts of the diacid are alkali, earth alkali, ammonium, organic salts, or mixtures thereof.
- Preferred salts of the diacid are alkali salts, such as sodium or potassium salts.
- the diacid may be present in acid form, salt form and mixtures thereof, e.g. in aqueous solution depending on the pH value.
- the electroplating bath usually contains an alkaline component, such as a hydroxide of an alkali metal. Suitable alkaline components are sodium hydroxide, potassium hydroxide or lithium hydroxide. The concentration of the alkaline component can be from 50 to 250 g/l, or 100 to 200 g/l.
- the electroplating bath may have a pH >10, or preferably pH > 11.
- the current usually flows between an anode and a cathode through the electroplating bath.
- the anode is can be made of zinc, manganese, iron, stainless steel, nickel, carbon, or a corrosion resistant metal such as platinum-plated titanium or palladium-tin alloy.
- the cathode can be the substrate to be electroplated.
- the substrate can made of a metal or an alloy, such as iron, nickel, and copper, an alloy thereof, or zincated aluminum.
- the substrate can have any shape, such as a plate, a cuboid, a solid cylinder, a hollow cylinder, a sphere.
- the cathode current density can be 0.1 to 20 A/dm 2 , or 0.2 to 10 A/dm 2 , or 0.5 to 6 A/dm 2 .
- the cathode current can be applied for 1 min to 5 hours, or 5 min to 2 hours, or 10 min to 1 hour.
- the electroplating can be carried out as barrel electroplating or rack electroplating.
- the electroplating can be carried out with or without injection of air, and with or without agitation of the substrate.
- the anode or cathode regions may be separated or membrane anodes may be used.
- the electroplating is performed without separating the anode and cathode from another by a membrane or by separators.
- the electroplating can be performed at a temperature from 5 to 50 °C, or 10 to 40 °C.
- the electroplating bath is a aqueous electroplating bath, where the water content may be at least 500, 600, 700, or 800 g/l.
- the electroplating bath usually comprises a metal ion source.
- Suitable metal ion sources are any materials capable of providing free metal cations when in an aqueous solution.
- the metal ion source may include salts of the metals, or elemental metal.
- Suitable metal ion sources are ion sources of zinc, nickel, cobalt, manganese or iron, wherein zinc and nickel are preferred.
- the metal ion source may comprise a single or a mixture of different metal ion sources.
- the electroplating bath comprises a zinc ion source, and optionally a further metal ion source, such as a nickel ion source.
- the zinc ion source or the nickel ion source may include salts of the metals, or the sources can be any material providing at least some free zinc ions and nickel ions, such as elemental zinc and elemental nickel.
- the zinc and nickel sources can further include other metal alloys, zinc- or nickel-containing compounds.
- Suitable salts of the metal are inorganic metal salts, such as halides, carbonates, hydroxides, ammonium sulfates, sulfamates, acetates, formates, nitrates, and sulfates, as well as hydrates thereof.
- Preferred zinc ion sources are zinc chloride, zinc sulfate, zinc oxide, zinc hydroxide, zinc acetate, zinc carbonate, zinc tartrate, and zinc sulfamate, wherein zinc chloride and zinc sulfate are in particular preferred.
- Preferred nickel ion sources are nickel chloride, nickel sulfate, nickel hydroxide, nickel acetate, ammonium nickel sulfate, nickel carbonate, nickel formate, and nickel sulfamate, wherein nickel chloride and nickel sulfate are in particular preferred.
- the concentration of the metal ion source e.g. of the zinc ion source or of the nickel ion source, can be in the range from 0.1 to 100 g/l, or 0.5 to 50 g/l, or 1 to 30 g/l.
- the concentration of the metal ions can be in the range from 0.01 to 100 g/l, or 0.1 to 50 g/l, or 0.2 to 20 g/l.
- the electroplating bath may comprise further electroplating additives in addition to the diacid, such as brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
- Suitable brighteners are alkyl naphthalenes, benzene sulfonic acids, benzene disulfonic acids, benzene trisulfonic acids, naphthalene disulfonic acids, naphthalene trisulfonic acids, benzene sulfonamides, naphthalene sulfonamides, benzene sulfonimides, naphthalene sulfonimides, vinyl sulfonamides, allyl sulfonamides, salts thereof, and combinations thereof.
- brighteners are the condensation product of piperazine, guanidine, formalin, and epichlorohydrin; pyridinium propyl sulfonate; N-benzyl-3-carboxy pyridinium chloride; trigonelline; sodium propargyl sulphonate; propargyl alcohol; ethyleneglycolpropargylalcohol ether; ethoxylated butyne diol; sodium diamylsulfosuccinate; N,N'-bis[3-(dimethylamino)propyl]urea, polymer with 1,3-dichloropropane; carboxyethylisothiuronium betaine; ethyl hexyl sulfate; benzothiazole; N-benzyl nicotinate; benzyl-2-methylimidiazole; formaldehyde condensate of 2-naphthalene sulfonate; methyl naphthy
- Suitable leveling agents are a sulfur compounds, for example 3-mercapto-1 ,2,4-triazole or thiourea.
- concentration of leveling agent in the electroplating bath can range from 0.01 g/l to 1 g/l.
- Suitable complexing agents are alkyleneamine compounds such as ethylenediamine, triethylenetetramine, and tetraethylenepentamine; ethylene oxide or propylene oxide adducts of the above-described alkyleneamines; amino alcohols such as N-(2-aminoethyl)- ethanolamine and 2-hydroxyethylaminopropylamine; poly(hydroxyalkyl)alkylenediamines such as N-2(-hydroxyethyl)-N,N',N'-triethylethylenediamine, N,N'-di(2-hydroxyethyl)-N,N'- diethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxyethyl)propylenediamine, and N,N,N',N'- tetrakis(2-hydroxypropyl)ethylenediamine; poly(alkyleneimines) obtained from ethyleneimine, 1 ,2-propyleneimine
- the invention also relates to the aqueous alkaline electroplating bath which comprises the diacid of the formula (I) or salts thereof, where n is 2, 3 or 4, the metal ion source, and optionally the further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
- the invention also relates to the aqueous alkaline electroplating bath which comprises the diacid of the formula (I) or salts thereof, where n is 2, 3 or 4,
- the metal ion source which is a zinc ion source, and optionally a further metal ion source, and optionally the further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
- the aqueous alkaline electroplating bath comprises preferably the diacid of the formula (I) where n is 3 or 4.
- the invention also relates to the diacid of the formula (I) where n is 2, 3 or 4, or salts thereof.
- n is 3.
- n is 3 or 4.
- Suitable salts of the diacid are alkali, earth alkali, ammonium, organic salts, or mixtures thereof.
- Preferred salts of the diacid are alkali salts, such as sodium or potassium salts.
- the diacid may be present in acid form, salt form and mixtures thereof, e.g. in aqueous solution depending on the pH value.
- the invention also relates to a method for preparing a diacid of the formula (I) or salts thereof, where n is 2, 3 or 4, comprising a hydrolysis of a dinitrile of the formula (II)
- the dinitrile is usually hydrolyzed in the presence of a base, e.g. in aqueous solution.
- the base is preferably a hydroxide of an alkali metal, such as sodium hydroxide, potassium hydroxide or lithium hydroxide.
- the molar ratio of the dinitrile to the hydroxide of the alkali metal can be from 1:1 to 1 :4, or 1 :1.5 to 1:3, or 1:1.7 to 1 :2.3.
- the dinitrile is usually hydrolyzed at temperatures between 5 to 100 °C, or 50 to 100 °C, or 70 to 100 °C. An excess of water can be removed from the resulting diacid by heat or vacuum.
- the invention also relates to a method for preparing a derivativeile of the formula (II) where n is 2, 3 or 4, comprising an addition of acrylonitrile to a diamine of the formula (III)
- the acrylonitrile and the diamine are usually present in a molar ratio from 1.9:1 to 2.5:1 , or 2.0:1 to 2.4:1, or 2.0:1 to 2.3:1.
- the addition usually takes place at a temperature from 5 to 100 °C, or 10 to 80 °C, or 15 to 60 °C. During the addition the reactants can be cooled to maintain the temperature.
- the addition of the acrylonitrile to the diamine is also known as Michael addition.
- the addition can take place in an aqueous solution, e.g. where the diamine is present in water and the acrylonitrile is added to the aqueous solution.
- the diamine of the formula (III) can be used as high purity grade (e.g. at least 90, 95, or 98 wt% purity) or as technical grade (e.g. with a purity of 50 to 90 wt%, or of 60 to 80 wt%).
- the diamine of the formula (III) in technical grade may comprise amine-containing byproducts, such as a branched amine or a cyclic amine comprising a piperazine unit.
- TETA Technical grade triethylenetetraamine
- branched TETA tris-aminoethylamine
- N,N’-bisaminoethylpiperazine also known as “Bis AEP”
- PEEDA N-[(2-aminoethyl) 2- aminoethyl]piperazine
- the amine-containing byproducts may react with the acrylonitrile to prepare corresponding dinitriles and optionally corresponding higher nitriles.
- the method for preparing the diacid of the formula (I) comprises the hydrolysis of the dinitrile of the formula (II), which may contain the dinitriles and optionally higher nitriles resulting from the addition of the acrylonitrile to the amine-containing byproducts.
- the diacid of the formula (I) may contain corresponding diacids and optionally higher acids resulting from the hydrolysis of the dinitriles and optionally higher nitriles, which result from the addition of the acrylonitrile to the amine-containing byproducts.
- the invention also relates to a use of the diacid of the formula (I) or salts thereof, where n is 2, 3 or 4 (preferably where n is 3 or 4), for reducing the cyanide formation during electroplating.
- the cyanide formation can be reduced to a achieve a concentration of cyanide (CN _ ) concentration in the electroplating bath of below 100 mg/l, or below 80 mg/l, or below 50 mg/l.
- the cyanide concentration can be determined by photometry, e.g. after an electric charge of 25 Ah.
- Example 2 Hydrolysis of Dinitril 491 ,73g (1 ,947mol) of the dinitrile made in Example 1 were heated and 417,62g water was added. At 85°C NaOH dosage was started and a total amount of 623,16g NaOH 25% (155,79g NaOH 100%, 3,895mol)were added. Shortly after the dosage was initiated gas development was visible. After the NaOH dosage was completed a post reaction was maintained at 90°C until no further gas development was visible.
- the content was cooled to a temperature of about 70°C and the vessel was slowly evacuated and a slow nitrogen flow while heating was applied. Reflux was maintained until stable conditions were reached. Following distillation was started. After a duration of 30 minutes the vessel was aerated with nitrogen and cooled before the distilled amount of water was compensated and the vessel emptied.
- the yield was 95 wt% at the purity 90 %.
- the amine number and the H-NMR confirmed the structure of the diacid of the following formula:
- the yield was 80 wt% at the purity 80 %.
- the amine number and the H-NMR confirmed the structure as in Example 2.
- the electroplating application tests were performed in a standard Hull cell with a rectifier and each repeated two or three times.
- the Hull cell was a trapezoidal container filled with 250 ml of the electroplating bath. This shape allowed to place the test steel panel on an angle to the stainless-steel anode. An electric current of 1 A was applied for 25 min at 38 °C. At the end the panel was rinsed with water and dried with pressured air.
- the aqueous alkaline electroplating bath contained the following components as shown in Table 1 :
- Lutron® Q 75 is an aqueous solution of N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylene- diamine, pH 10-12, about 25 % water content, commercially available from BASF SE.
- Lugalvan® IZE is an aqueous solution of an addition product of imidazole and epichlorohydrin, pH 8-10, about 55 % water content, commercially available from BASF SE.
- Lugalvan® BPC 48 is an aqueous solution of benzylpyridine-3-carboxylate, pH about 6, about 52 % water content, commercially available from BASF SE.
- - DETA is diethylenetriamine, commercially available from BASF SE.
- the comparative electroplating bath A included DETA instead of the Diacid of Example 1 or 2.
- DETA is the standard complexing agent used in electroplating industry.
- the comparative electroplating bath B included TETA instead of the Diacid of Example 1 or 2. TETA used was the starting material in Example 1.
- Example 5 A, B, C and D were further analyzed in Examples 6-8.
- TETA contains only one ethylene amine unit more than DETA and is the base unit for the preparation of the Diacids in Example 1 and 2. However, TETA was clearly not suitable for achieving the required optical appearance.
- Example 7 Layer thickness
- the Hull cell was a trapezoidal container. This shape allowed to place the test steel panel on an angle to the stainless-steel anode, so one side of the panel is closer to the anode (which results in a higher current density) and the other side of the panel is more far away (which results in a lower current density).
- the layer thickness [pm] on the electroplated panels from Examples 5 A, C and D was analyzed by Fischerscope® X-Ray XDal from Helmut Fischer GmbH (Germany) on nine spots with 1 cm distance and starting 1 cm from the left edge. The results are summarized in Table 2 and in Figure 1.
- Figure 1 shows the deposited layer thickness in pm as determined in Example 7 on the panels at nine spots with 1 cm distance and starting 1 cm from the left edge after electroplating according to Example 5.
- the good linear gradient of the layer thickness can be best seen in Figure 1b) (Example 5D) and Figure 1c) (Example 50).
- the comparative electrobath Example 5A in Figure 1a) is not linear, but rather curved.
- cyanide CN _
- the state-of-the-art electroplating additives like DETA are slowly oxidized at the anode to form cyanide (CN _ ) byproduct. This is very problematic, because cyanide is not only toxic, but also a strong complexing agent. Thus the electroplating bath has to be exchanged often and laboriously.
- Long term stability tests of the electroplating baths were performed in a 1 liter right-angled cell (15x10x6 cm) including 750 ml electroplating bath, which had the same composition as in Example 5. Steel plating panels with an area of 1 dm 2 were used, and two opposite electrodes with 1 dm 2 . The applied current density at 35 °C was 5 A/dm 2 for 30 min.
- additives are usually consumed during electroplating and thus some additives were added as following:
- the sample was weighed into the reaction apparatus and mixed with 100 ml water. After adding 10 ml of copper (II) sulfate solution and 300 mg of tin (II) chloride, the apparatus was be closed with the reflux condenser and the absorption vessel, which was filled with 10 ml of sodium hydroxide solution. 10 ml of hydrochloric acid was added and heated up to the boiling point. A nitrogen flow transferred the developing hydrogen cyanide in the absorption vessel. The transfer was completed after 1 hour of reaction time. The content of the absorption vessel was transferred with pure water into a 50 ml volumetric flask and the volumetric flask was filled up. b) Measurement
- the butanol phase was filtered through a dry pleated filter into a dry 25 ml volumetric flask. At 632 nm in a 10 mm cuvette the solution was measured against butanol (as zero value), on the photometer. The calibration points were applied from a KCN reference material and measured with the corresponding aliquots.
Abstract
The present invention relates to a method for electroplating a substrate comprising a step of applying a current through an aqueous electroplating bath which comprises the substrate and a diacid of the formula (I) or salts thereof, where n is 2, 3 or 4. The invention also relates to an aqueous alkaline electroplating bath which comprises the diacid of the formula (I) or salts thereof, a metal ion source, and optionally further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents. The invention also relates to the diacid of the formula (I) or salts thereof, and to a method for preparing the diacid of the formula (I) or salts thereof, comprising a hydrolysis of a dinitrile of the formula (II); and to a method for preparing the dinitrile of the formula (II) where n is 2, 3 or 4, comprising an addition of acrylonitrile to a diamine of the formula (III); and to a use of the diacid of the formula (I) or salts thereof for reducing the cyanide formation during electroplating.
Description
Stable alkaline electroplating bath with a diacid
The present invention relates to a method for electroplating a substrate comprising a step of applying a current through an aqueous electroplating bath which comprises the substrate and a diacid of the formula (I) or salts thereof, where n is 2, 3 or 4. The invention also relates to an aqueous alkaline electroplating bath which comprises the diacid of the formula (I) or salts thereof, a metal ion source, and optionally further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents. The invention also relates to the diacid of the formula (I) or salts thereof, and to a method for preparing the diacid of the formula (I) or salts thereof, comprising a hydrolysis of a dinitrile of the formula (II); and to a method for preparing the dinitrile of the formula (II) where n is 2, 3 or 4, comprising an addition of acrylonitrile to a diamine of the formula (III); and to a use of the diacid of the formula (I) or salts thereof for reducing the cyanide formation during electroplating. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.
Electroplating is widely used in industry to improve the surface qualities of objects. For example the resistance to abrasion and corrosion, lubricity, reflectivity, electrical conductivity, or appearance of objects can be improved.
Typically, during electroplating a metal coating is made on a substrate through the reduction of cations of that metal by means of a direct electric current. The part to be coated acts is usually the cathode of an electrolytic cell filled with an electroplating bath. The electroplating bath is a typically solution of a salt of the metal to be coated. The anode is usually either a block of that metal, or of some inert conductive material.
The electroplating bath usually contains complexing agents which keep the metal salts in solution. Especially amine-containing complexing agents, such as diethylenetriaamine (DETA), are important additives widely used in electroplating industry. However, such amine- containing complexing agents form cyanides and byproducts during undesired anoxic oxidation. Cyanides are not only toxic, but also too strong complexing agents which reduce the concentration of metal salts can be electrodeposited.
Beside reducing the cyanide formation in the electroplating bath during electroplating further objects of the inventions were to achieve a high quality optical appearance, homogenous composition of the metals in the layer, linear gradient of the layer thickness of the deposited metals according to the gradient of the current density.
The objects were achieved by a method for electroplating a substrate comprising a step of applying a current through an aqueous electroplating bath which comprises the substrate and a diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4.
Preferably, n is 3. In another form n is 2. In another form n is 4. In another preferred form n is 3 or 4.
The electroplating bath may comprise from 0.1 to 200 g/l, 1 to 100 g/l, 2 to 50 g/l or 3 to 30 g/l of the diacid.
Suitable salts of the diacid are alkali, earth alkali, ammonium, organic salts, or mixtures thereof. Preferred salts of the diacid are alkali salts, such as sodium or potassium salts. The diacid may be present in acid form, salt form and mixtures thereof, e.g. in aqueous solution depending on the pH value.
The electroplating bath usually contains an alkaline component, such as a hydroxide of an alkali metal. Suitable alkaline components are sodium hydroxide, potassium hydroxide or lithium hydroxide. The concentration of the alkaline component can be from 50 to 250 g/l, or 100 to 200 g/l. The electroplating bath may have a pH >10, or preferably pH > 11.
The current usually flows between an anode and a cathode through the electroplating bath. The anode is can be made of zinc, manganese, iron, stainless steel, nickel, carbon, or a corrosion resistant metal such as platinum-plated titanium or palladium-tin alloy.
The cathode can be the substrate to be electroplated. The substrate can made of a metal or an alloy, such as iron, nickel, and copper, an alloy thereof, or zincated aluminum. The substrate can have any shape, such as a plate, a cuboid, a solid cylinder, a hollow cylinder, a sphere.
The cathode current density can be 0.1 to 20 A/dm2, or 0.2 to 10 A/dm2, or 0.5 to 6 A/dm2. The cathode current can be applied for 1 min to 5 hours, or 5 min to 2 hours, or 10 min to 1 hour.
The electroplating can be carried out as barrel electroplating or rack electroplating. The electroplating can be carried out with or without injection of air, and with or without agitation of the substrate.
The anode or cathode regions may be separated or membrane anodes may be used. Preferably, the electroplating is performed without separating the anode and cathode from another by a membrane or by separators.
The electroplating can be performed at a temperature from 5 to 50 °C, or 10 to 40 °C.
The electroplating bath is a aqueous electroplating bath, where the water content may be at least 500, 600, 700, or 800 g/l.
The electroplating bath usually comprises a metal ion source. Suitable metal ion sources are any materials capable of providing free metal cations when in an aqueous solution. The metal ion source may include salts of the metals, or elemental metal. Suitable metal ion sources are ion sources of zinc, nickel, cobalt, manganese or iron, wherein zinc and nickel are preferred. The metal ion source may comprise a single or a mixture of different metal ion sources.
Preferably, the electroplating bath comprises a zinc ion source, and optionally a further metal ion source, such as a nickel ion source. The zinc ion source or the nickel ion source may include salts of the metals, or the sources can be any material providing at least some free zinc ions and nickel ions, such as elemental zinc and elemental nickel. The zinc and nickel sources can further include other metal alloys, zinc- or nickel-containing compounds.
Suitable salts of the metal, such as zinc or nickel, are inorganic metal salts, such as halides, carbonates, hydroxides, ammonium sulfates, sulfamates, acetates, formates, nitrates, and sulfates, as well as hydrates thereof.
Preferred zinc ion sources are zinc chloride, zinc sulfate, zinc oxide, zinc hydroxide, zinc acetate, zinc carbonate, zinc tartrate, and zinc sulfamate, wherein zinc chloride and zinc sulfate are in particular preferred.
Preferred nickel ion sources are nickel chloride, nickel sulfate, nickel hydroxide, nickel acetate, ammonium nickel sulfate, nickel carbonate, nickel formate, and nickel sulfamate, wherein nickel chloride and nickel sulfate are in particular preferred.
The concentration of the metal ion source, e.g. of the zinc ion source or of the nickel ion source, can be in the range from 0.1 to 100 g/l, or 0.5 to 50 g/l, or 1 to 30 g/l.
The concentration of the metal ions, e.g. of the zinc ions or of the nickel ions, can be in the range from 0.01 to 100 g/l, or 0.1 to 50 g/l, or 0.2 to 20 g/l.
The electroplating bath may comprise further electroplating additives in addition to the diacid, such as brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
Suitable brighteners are alkyl naphthalenes, benzene sulfonic acids, benzene disulfonic acids, benzene trisulfonic acids, naphthalene disulfonic acids, naphthalene trisulfonic acids, benzene sulfonamides, naphthalene sulfonamides, benzene sulfonimides, naphthalene sulfonimides, vinyl sulfonamides, allyl sulfonamides, salts thereof, and combinations thereof.
Further examples of brighteners are the condensation product of piperazine, guanidine, formalin, and epichlorohydrin; pyridinium propyl sulfonate; N-benzyl-3-carboxy pyridinium chloride; trigonelline; sodium propargyl sulphonate; propargyl alcohol; ethyleneglycolpropargylalcohol ether; ethoxylated butyne diol; sodium diamylsulfosuccinate; N,N'-bis[3-(dimethylamino)propyl]urea, polymer with 1,3-dichloropropane; carboxyethylisothiuronium betaine; ethyl hexyl sulfate; benzothiazole; N-benzyl nicotinate; benzyl-2-methylimidiazole; formaldehyde condensate of 2-naphthalene sulfonate; methyl naphthyl ketone; benzalacetone; cumene sulfonate; sodium vinyl sulfonate; benzothiazolium- 2-[4-(dimethylamino)phenyl]-3,6-dimethyl chloride; N,N-dimethyl-dithiocarbamyl propyl sulfonic acid sodium salt; 3-mercapto-1-proanesulfonic acid, sodium salt; O- ethyldithiocarbonato-S-(3-sulfopropyl)-ester, potassium salt; bis-(3-sulfopropyl)-disulfide, disodium salt; 3-S-iosthiouronium propyl sulfonate; 3-(benzothiazolyl-2-mercapto)-propyl- sulfonic acid, sodium salt; N-(polyacrylamide); safranin; crystal violet and derivatives thereof; phenazonium dyes and derivatives thereof; thiodiglycol ethoxylate; sodium lauryl sulfate; 1- hydroxyethylen-1,1-diphosphonic acid; ethoxylated beta naphthol; sodium salt of a sulphonated alkylphenol ethoxylate; sulfurized benzene sulfonic acid; butynediol dihydroxypropyl sulfonate; sodium saccharin; 3-mercapto-1 -propanesulfonic acid, sodium salt; the formaldehyde condensate of 1 -naphthalene sulfonic acid; benzotriazole; sodium
benzoate; the aqueous reaction product of 2-aminopyridine with epichlorohydrin; ureylene quaternary ammonium polymer; the aqueous reaction product of imidazole and epichlorohydrin; vanillin; anisaldehyde; piperonal; thiourea; polyvinyl alcohol; reduced polyvinyl alcohol; o-chlorobenzaldehyde; a-napthaldehyde; condensed naphthalene sulfonate; niacin; pyridine; 3-hydroxypropane sulfonate; allyl pyridinium chloride; dibenzenesulfonamide; pyridinium butane sulfonate; sodium allyl sulfonate; sodium vinyl sulfonate; naphthalene trisulfonic acid; cumene sulfonate; carboxymethylpyridinium chloride; propargyl hydroxypropyl ether sulfonate; o-sulfobenzaldehyde; aqueous reaction product of imidazole and epichlorohydrin; mercaptothio ether; polyvinylpyrrolidone; sodium adipate; chloral hydrate; sodium gluconate; sodium salicylate; manganese sulfate; cadmium sulfate; sodium tellurite; and glycine. The concentration of brightener in the electroplating bath can range from 0.01 g/l to 10 g/l.
Suitable leveling agents are a sulfur compounds, for example 3-mercapto-1 ,2,4-triazole or thiourea. The concentration of leveling agent in the electroplating bath can range from 0.01 g/l to 1 g/l.
Suitable complexing agents are alkyleneamine compounds such as ethylenediamine, triethylenetetramine, and tetraethylenepentamine; ethylene oxide or propylene oxide adducts of the above-described alkyleneamines; amino alcohols such as N-(2-aminoethyl)- ethanolamine and 2-hydroxyethylaminopropylamine; poly(hydroxyalkyl)alkylenediamines such as N-2(-hydroxyethyl)-N,N',N'-triethylethylenediamine, N,N'-di(2-hydroxyethyl)-N,N'- diethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxyethyl)propylenediamine, and N,N,N',N'- tetrakis(2-hydroxypropyl)ethylenediamine; poly(alkyleneimines) obtained from ethyleneimine, 1 ,2-propyleneimine, and the like; poly(alkyleneamines) and poly(amino alcohols) obtained from ethylenediamine, triethylenetetramine, ethanolamine, diethanolamine; or mixtures thereof. The concentration of the complexing agent may be 5 to 200 g/L, or 30 to 100 g/L.
The invention also relates to the aqueous alkaline electroplating bath which comprises the diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4, the metal ion source, and
optionally the further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
The invention also relates to the aqueous alkaline electroplating bath which comprises the diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4,
- the metal ion source, which is a zinc ion source, and optionally a further metal ion source, and optionally the further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
The aqueous alkaline electroplating bath comprises preferably the diacid of the formula (I) where n is 3 or 4.
The invention also relates to the diacid of the formula (I)
where n is 2, 3 or 4, or salts thereof. Preferably, n is 3. In another preferred form of the diacid of the formula (I) n is 3 or 4. Suitable salts of the diacid are alkali, earth alkali, ammonium, organic salts, or mixtures thereof. Preferred salts of the diacid are alkali salts, such as sodium or potassium salts. The diacid may be present in acid form, salt form and mixtures thereof, e.g. in aqueous solution depending on the pH value.
The invention also relates to a method for preparing a diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4, comprising a hydrolysis of a dinitrile of the formula (II)
The dinitrile is usually hydrolyzed in the presence of a base, e.g. in aqueous solution. The base is preferably a hydroxide of an alkali metal, such as sodium hydroxide, potassium hydroxide or lithium hydroxide. The molar ratio of the dinitrile to the hydroxide of the alkali metal can be from 1:1 to 1 :4, or 1 :1.5 to 1:3, or 1:1.7 to 1 :2.3. The dinitrile is usually hydrolyzed at temperatures between 5 to 100 °C, or 50 to 100 °C, or 70 to 100 °C. An excess of water can be removed from the resulting diacid by heat or vacuum.
The invention also relates to a method for preparing a dintrile of the formula (II)
where n is 2, 3 or 4, comprising an addition of acrylonitrile to a diamine of the formula (III)
The acrylonitrile and the diamine are usually present in a molar ratio from 1.9:1 to 2.5:1 , or 2.0:1 to 2.4:1, or 2.0:1 to 2.3:1. The addition usually takes place at a temperature from 5 to 100 °C, or 10 to 80 °C, or 15 to 60 °C. During the addition the reactants can be cooled to maintain the temperature. The addition of the acrylonitrile to the diamine is also known as Michael addition. The addition can take place in an aqueous solution, e.g. where the diamine is present in water and the acrylonitrile is added to the aqueous solution.
The diamine of the formula (III) can be used as high purity grade (e.g. at least 90, 95, or 98 wt% purity) or as technical grade (e.g. with a purity of 50 to 90 wt%, or of 60 to 80 wt%). The diamine of the formula (III) in technical grade may comprise amine-containing byproducts, such as a branched amine or a cyclic amine comprising a piperazine unit. Technical grade triethylenetetraamine (TETA) may contain tris-aminoethylamine (also known as “branched TETA”), N,N’-bisaminoethylpiperazine (also known as “Bis AEP”) and/or N-[(2-aminoethyl) 2- aminoethyl]piperazine (also known as “PEEDA”).
When adding acrylonitrile to the diamine of the formula (III) the amine-containing byproducts may react with the acrylonitrile to prepare corresponding dinitriles and optionally corresponding higher nitriles.
The method for preparing the diacid of the formula (I) comprises the hydrolysis of the dinitrile of the formula (II), which may contain the dinitriles and optionally higher nitriles resulting from the addition of the acrylonitrile to the amine-containing byproducts. The diacid of the formula (I) may contain corresponding diacids and optionally higher acids resulting from the hydrolysis of the dinitriles and optionally higher nitriles, which result from the addition of the acrylonitrile to the amine-containing byproducts.
The invention also relates to a use of the diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4 (preferably where n is 3 or 4), for reducing the cyanide formation during electroplating. The cyanide formation can be reduced to a achieve a concentration of cyanide (CN_) concentration in the electroplating bath of below 100 mg/l, or below 80 mg/l, or below 50 mg/l. The cyanide concentration can be determined by photometry, e.g. after an electric charge of 25 Ah.
Examples
Example 1 - Michael Addition of Acrylonitrile to linear TETA
694,68g (4,751 mol) of linear triethylenetetramine (TETA, purity 99%) was cooled and 140,39g water were added. 529,34g (9,976mol) of acrylonitrile (ACN) were added at 40 °C After the ACN dosage a post reaction time of about one hour was maintained before the vessel was emptied. The yields was 95 wt% according to NMR.
Example 2 - Hydrolysis of Dinitril
491 ,73g (1 ,947mol) of the dinitrile made in Example 1 were heated and 417,62g water was added. At 85°C NaOH dosage was started and a total amount of 623,16g NaOH 25% (155,79g NaOH 100%, 3,895mol)were added. Shortly after the dosage was initiated gas development was visible. After the NaOH dosage was completed a post reaction was maintained at 90°C until no further gas development was visible.
The content was cooled to a temperature of about 70°C and the vessel was slowly evacuated and a slow nitrogen flow while heating was applied. Reflux was maintained until stable conditions were reached. Following distillation was started. After a duration of 30 minutes the vessel was aerated with nitrogen and cooled before the distilled amount of water was compensated and the vessel emptied.
The yield was 95 wt% at the purity 90 %. The amine number and the H-NMR confirmed the structure of the diacid of the following formula:
Example 3 - Michael Addition of Acrylonitrile to technical TETA
528,42g (3,61 mol) of technical grade triethylenetetraamine (TETA, purity 70 %, contains about 20% N,N’-bisaminoethylpiperazine and about 10% Tris-aminoethylamin) was cooled and 106,68g water were added. 421,36g (7,941 mol) of acrylonitrile were added at 40 °C. After the ACN dosage a post reaction time of about one hour was maintained before the vessel was emptied. The yield was 95 wt% based on all primary amino groups in the technical TETA.
Example 4 - Hydrolysis of Dinitril
517,12g (2,048mol) of the dinitrile made in Example 3 were heated and 417,62g water were added. At 85°C NaOH dosage was started to achieve a total amount of 655,33g NaOH 25% (175,36g NaOH 100%, 4,096mol)Shortly after the dosage was initiated gas development was visible. After the NaOH dosage was completed a post reaction was maintained at 90°C until no further gas development was visible.
The content was cooled to a temperature of about 70°C and the vessel was slowly evacuated and slow nitrogen flow while heating was applied. Reflux was maintained until stable conditions were reached. Following distillation was started. After a duration of 30 minutes the vessel was aerated with nitrogen and cooled before the distilled amount of water was compensated and the vessel emptied.
The yield was 80 wt% at the purity 80 %. The amine number and the H-NMR confirmed the structure as in Example 2.
Example 5 - Electroplating in standard Hull cell
The electroplating application tests were performed in a standard Hull cell with a rectifier and each repeated two or three times. The Hull cell was a trapezoidal container filled with 250 ml of the electroplating bath. This shape allowed to place the test steel panel on an angle to the stainless-steel anode. An electric current of 1 A was applied for 25 min at 38 °C. At the end the panel was rinsed with water and dried with pressured air.
The aqueous alkaline electroplating bath contained the following components as shown in Table 1 :
- Lutron® Q 75 is an aqueous solution of N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylene- diamine, pH 10-12, about 25 % water content, commercially available from BASF SE.
- Lugalvan® IZE is an aqueous solution of an addition product of imidazole and epichlorohydrin, pH 8-10, about 55 % water content, commercially available from BASF SE.
- Lugalvan® BPC 48 is an aqueous solution of benzylpyridine-3-carboxylate, pH about 6, about 52 % water content, commercially available from BASF SE.
- DETA is diethylenetriamine, commercially available from BASF SE.
The comparative electroplating bath A included DETA instead of the Diacid of Example 1 or 2. DETA is the standard complexing agent used in electroplating industry.
The comparative electroplating bath B included TETA instead of the Diacid of Example 1 or 2. TETA used was the starting material in Example 1.
The test panels prepared in Example 5 A, B, C and D were further analyzed in Examples 6-8.
Example 6 - Optical appearance
The optical appearance of the Zn/Ni deposition layer on the test panels was similar when using electroplating baths A, C and D. A homogenously grey and dull surface was observed. This results demonstrated that the Diacids of Example 1 and 2 give a at least similar optical appearance like the industry standard DETA.
The electroplating bath B resulted in unsuitable depositions: a very low layer thickness, and a bad and inhomogeneous alloy composition. TETA contains only one ethylene amine unit more than DETA and is the base unit for the preparation of the Diacids in Example 1 and 2. However, TETA was clearly not suitable for achieving the required optical appearance.
Example 7 - Layer thickness
The Hull cell was a trapezoidal container. This shape allowed to place the test steel panel on an angle to the stainless-steel anode, so one side of the panel is closer to the anode (which
results in a higher current density) and the other side of the panel is more far away (which results in a lower current density).
Since there is a uniformly linear gradient of the current density also a linear gradient of the layer thickness of the deposited metals are expected.
The layer thickness [pm] on the electroplated panels from Examples 5 A, C and D was analyzed by Fischerscope® X-Ray XDal from Helmut Fischer GmbH (Germany) on nine spots with 1 cm distance and starting 1 cm from the left edge. The results are summarized in Table 2 and in Figure 1.
Figure 1 shows the deposited layer thickness in pm as determined in Example 7 on the panels at nine spots with 1 cm distance and starting 1 cm from the left edge after electroplating according to Example 5. The good linear gradient of the layer thickness can be best seen in Figure 1b) (Example 5D) and Figure 1c) (Example 50). For comparison, the comparative electrobath Example 5A in Figure 1a) is not linear, but rather curved.
Example 8 - Alloy composition
As explained above, one side of the panel is closer to the anode (which results in a higher current density) and the other side of the panel is more far away (which results in a lower current density). During the electroplating Zn and Ni are deposited simultaneously. Goal was
to have the same Zinc-Nickel alloy composition independent of the distance from the substrate to the anode.
The alloy composition on the electroplated panels from Examples 5 A, C and D was analyzed with a Fischerscope® X-Ray XDal from Helmut Fischer GmbH (Germany) on nine spots with 1 cm distance and starting 1 cm from the left edge. The results are summarized in Table 3.
The data in Table 3 showed that the new diacid additives allow the similar good uniformity of alloy composition independent of the distance from the substrate to the anode (and thus independent of the current density).
Example 9 - Cyanide Formation
The state-of-the-art electroplating additives like DETA are slowly oxidized at the anode to form cyanide (CN_) byproduct. This is very problematic, because cyanide is not only toxic, but also a strong complexing agent. Thus the electroplating bath has to be exchanged often and laboriously.
Long term stability tests of the electroplating baths were performed in a 1 liter right-angled cell (15x10x6 cm) including 750 ml electroplating bath, which had the same composition as in Example 5. Steel plating panels with an area of 1 dm2 were used, and two opposite electrodes with 1 dm2. The applied current density at 35 °C was 5 A/dm2 for 30 min.
Additives are usually consumed during electroplating and thus some additives were added as following:
- After every plated panel 100 mg/L Lugalvan® BPC 48.
- After every two plated panels: 3,25 g/L Zn (as ZnO); 24,25 g/L NaOH; 33,3 mg/L Ni (as NiSCL) complexed with 3,33 g/L diacid or the comparative compound as shown in Table 4; and 1,5 g/L Lugalvan® IZE.
- After every four plated 10 g/L Lutron® Q 75; and 2 g/L triethanolamine
After an electric charge of each 5 Ah (ampere hours) a sample of the electroplating bath was taken and analyzed on cyanide via photometry as follows: a) Sample preparation
The sample was weighed into the reaction apparatus and mixed with 100 ml water. After adding 10 ml of copper (II) sulfate solution and 300 mg of tin (II) chloride, the apparatus was be closed with the reflux condenser and the absorption vessel, which was filled with 10 ml of sodium hydroxide solution. 10 ml of hydrochloric acid was added and heated up to the boiling point. A nitrogen flow transferred the developing hydrogen cyanide in the absorption vessel. The transfer was completed after 1 hour of reaction time. The content of the absorption vessel was transferred with pure water into a 50 ml volumetric flask and the volumetric flask was filled up. b) Measurement
An aliquot of the prepared sample was placed in a 100 ml separating funnel and, if necessary, supplemented with ultrapure water to a volume of 25 ml. 10 ml of phosphate buffer solution was added, the solution is checked whether the pH value was around 7. After adding 0.5 ml of chloramine T the solution was shaken. 15 ml of pyridine - pyrazolone reagent (3-methyl-1-phenyl-2-pyrazolin-5-one and 4,4'-bis(3- methyl-1-phenyle-5-pyrazolone) was added and allowed to stand for 30 min. Then exactly 20 ml of n-butanol was added and, and the aqueous phase discarded. The butanol phase was filtered through a dry pleated filter into a dry 25 ml volumetric flask. At 632 nm in a 10 mm cuvette the solution was measured against butanol (as zero
value), on the photometer. The calibration points were applied from a KCN reference material and measured with the corresponding aliquots.
The results are summarized in Table 4. It was demonstrated that the diacids used in the electroplating baths of Example 5 C and 5 D resulted in a significant lower cyanide formation. Additionally, in the comparative electroplating bath of Example 5 A a sediment was observed after 20 Ah, which was not seen when the electroplating baths of Example 5 C and 5 D were used.
Claims
2. The method according to claim 1 where the electroplating bath comprises 0.1 to 200 g/l of the diacid.
3. The method according to claim 1 or 2, where the electroplating bath comprises a metal ion source, which is preferably a zinc ion source, and optionally a further metal ion source.
4. The method according to any of claims 1 to 3 where the electroplating bath comprises a zinc ion source and a nickel ion source.
5. The method according to any of claims 1 to 4 where the electroplating bath has a pH >10.
6. The method according to any of claims 1 to 5 where the electroplating bath comprises further electroplating additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents.
7. The method according to any of claims 1 to 6 where n is 3.
8. An aqueous alkaline electroplating bath which comprises a diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4,
a metal ion source, which is a zinc ion source, and optionally a further metal ion source, and optionally further additives selected from brighteners, leveling agents, complexing agents, water softening agent, or anti-foaming agents. The aqueous alkaline electroplating bath according to claim 8 where the electroplating bath comprises 0.1 to 200 g/l of the diacid. The aqueous alkaline electroplating bath according to claim 8 or 9 where n is 3 or 4. A diacid of the formula (I)
or salts thereof, where n is 3 or 4. A method for preparing a diacid of the formula (I)
or salts thereof, where n is 3 or 4, comprising a hydrolysis of a dinitrile of the formula (II)
The method according to claim 12 where the dinitrile is hydrolyzed in the presence of base, preferably in the presence of a hydroxide of an alkali metal. A method for preparing a dinitrile of the formula (II)
where n is 3 or 4, comprising an addition of acrylonitrile to a diamine of the formula (III)
The method according to claim 14 where the molar ratio of the acrylonitrile to the diamine is from 1.9: 1 to 2.5: 1. A use of a diacid of the formula (I)
or salts thereof, where n is 2, 3 or 4, for reducing the cyanide formation during electroplating.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP22178602.3 | 2022-06-13 | ||
EP22178602 | 2022-06-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023241905A1 true WO2023241905A1 (en) | 2023-12-21 |
Family
ID=82020883
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2023/064422 WO2023241905A1 (en) | 2022-06-13 | 2023-05-30 | Stable alkaline electroplating bath with a diacid |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2023241905A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB461001A (en) * | 1935-07-02 | 1937-02-02 | Ig Farbenindustrie Ag | Improvements in the removal of organically combined sulphur from gases |
GB487673A (en) * | 1936-11-23 | 1938-06-23 | Ig Farbenindustrie Ag | Improvements in and apparatus for the removal of hydrogen sulphide from hydrocarbon liquids |
US20170211198A1 (en) * | 2005-05-11 | 2017-07-27 | The Boeing Company | Low hydrogen embrittlement zinc/nickel plating for high strength steels |
EP3415665A1 (en) * | 2017-06-14 | 2018-12-19 | Dr.Ing. Max Schlötter GmbH & Co. KG | Method for the galvanic deposition of zinc-nickel alloy layers from an alkaline zinc-nickel alloy bath with reduced degradation of additives |
CN109553744A (en) * | 2017-09-25 | 2019-04-02 | 赢创德固赛有限公司 | The generation of polyurethane system |
-
2023
- 2023-05-30 WO PCT/EP2023/064422 patent/WO2023241905A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB461001A (en) * | 1935-07-02 | 1937-02-02 | Ig Farbenindustrie Ag | Improvements in the removal of organically combined sulphur from gases |
GB487673A (en) * | 1936-11-23 | 1938-06-23 | Ig Farbenindustrie Ag | Improvements in and apparatus for the removal of hydrogen sulphide from hydrocarbon liquids |
US20170211198A1 (en) * | 2005-05-11 | 2017-07-27 | The Boeing Company | Low hydrogen embrittlement zinc/nickel plating for high strength steels |
EP3415665A1 (en) * | 2017-06-14 | 2018-12-19 | Dr.Ing. Max Schlötter GmbH & Co. KG | Method for the galvanic deposition of zinc-nickel alloy layers from an alkaline zinc-nickel alloy bath with reduced degradation of additives |
CN109553744A (en) * | 2017-09-25 | 2019-04-02 | 赢创德固赛有限公司 | The generation of polyurethane system |
Non-Patent Citations (2)
Title |
---|
GAMPP H ET AL: "COPPER(II) COMPLEXES WITH LINEAR PENTADENTATE CHELATORS", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, EASTON , US, vol. 23, no. 23, 1 January 1984 (1984-01-01), pages 3724 - 3730, XP009046999, ISSN: 0020-1669, DOI: 10.1021/IC00191A012 * |
MUKHERJEE G S ET AL: "Curing exotherm and processing temperature of a family of epoxy resins in the light of fabrication of composites", JOURNAL OF THE INDIAN CHEMICAL SOCIETY, INDIAN CHEMICAL SOCIETY, IN, vol. 77, no. 7, 1 July 2000 (2000-07-01), pages 332 - 335, XP009548570, ISSN: 0019-4522, DOI: 10.5281/ZENODO.5867296 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20100155257A1 (en) | Aqueous, alkaline, cyanide-free bath for the galvanic deposition of zinc alloy coatings | |
TWI486490B (en) | Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths | |
EP0649918B1 (en) | Alkaline zinc-nickel alloy plating baths | |
CA2342219C (en) | Aqueous alkaline cyanide-free bath for the galvanic deposition of zinc or zinc alloy coatings | |
US5405523A (en) | Zinc alloy plating with quaternary ammonium polymer | |
EP2111484B1 (en) | Polyamine brightening agent | |
JP2007525598A (en) | Bathes, systems, and methods for electroplating zinc-nickel ternary alloys and higher ternary alloys and articles electroplated so | |
US4717458A (en) | Zinc and zinc alloy electrolyte and process | |
TW201006967A (en) | Pd and Pd-Ni electrolyte baths | |
CN109642337B (en) | Ternary zinc-nickel-iron alloy and alkaline electrolyte for electroplating such an alloy | |
JPH0246676B2 (en) | ||
WO2023241905A1 (en) | Stable alkaline electroplating bath with a diacid | |
CA1075695A (en) | Alkaline zinc electroplating baths and additive compositions therefor | |
JP5005849B2 (en) | Alkaline zinc and zinc alloy plating bath | |
TW202409351A (en) | Stable alkaline electroplating bath with a diacid | |
US4792383A (en) | Polymer compositions and alkaline zinc electroplating baths and processes | |
US4100040A (en) | Electrodeposition of bright zinc utilizing aliphatic ketones | |
JP5551094B2 (en) | Alkaline zinc and zinc alloy plating bath | |
US4397718A (en) | Zinc plating baths with condensating polymer brighteners | |
WO1999050479A1 (en) | Electroplating solution | |
JP5747359B2 (en) | Zincate-type zinc-based plating bath, additive for zincate-type zinc-based plating bath, and method for producing zinc-based plated member | |
GB2109789A (en) | Benzaldehyde ether derivatives and their use in zn-electroplating | |
JP4855631B2 (en) | Zinc and zinc alloy electroplating additive and electroplating method | |
JP6645609B2 (en) | Tin alloy plating solution | |
GB1564332A (en) | Non-cyanide silver bath |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23728793 Country of ref document: EP Kind code of ref document: A1 |