EP4269663A1 - Procédé et système de placage électrolytique d'un article avec un métal - Google Patents
Procédé et système de placage électrolytique d'un article avec un métal Download PDFInfo
- Publication number
- EP4269663A1 EP4269663A1 EP21915031.5A EP21915031A EP4269663A1 EP 4269663 A1 EP4269663 A1 EP 4269663A1 EP 21915031 A EP21915031 A EP 21915031A EP 4269663 A1 EP4269663 A1 EP 4269663A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- iron
- oxide
- conductive substrate
- layer
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000009713 electroplating Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 310
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 247
- 238000007747 plating Methods 0.000 claims abstract description 165
- 229910052742 iron Inorganic materials 0.000 claims abstract description 152
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 120
- 239000000758 substrate Substances 0.000 claims abstract description 61
- 239000000654 additive Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- 150000004767 nitrides Chemical class 0.000 claims abstract description 30
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000002738 chelating agent Substances 0.000 claims description 26
- 238000005282 brightening Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 15
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 12
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229940081974 saccharin Drugs 0.000 claims description 10
- 235000019204 saccharin Nutrition 0.000 claims description 10
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000009499 grossing Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 36
- 229910003271 Ni-Fe Inorganic materials 0.000 description 27
- -1 iron ions Chemical class 0.000 description 23
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 235000006408 oxalic acid Nutrition 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 229960003512 nicotinic acid Drugs 0.000 description 10
- 235000001968 nicotinic acid Nutrition 0.000 description 10
- 239000011664 nicotinic acid Substances 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000013507 mapping Methods 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- ASWARDGCARWTOM-UHFFFAOYSA-N oxalic acid;pyridine-3-carboxylic acid Chemical compound OC(=O)C(O)=O.OC(=O)C1=CC=CN=C1 ASWARDGCARWTOM-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QDZDZWXGCODFPU-UHFFFAOYSA-N 2-methyl-6-phenyl-1-propylpyridin-1-ium-3-carboxylic acid chloride Chemical compound [Cl-].CCC[N+]1=C(C)C(=CC=C1C1=CC=CC=C1)C(O)=O QDZDZWXGCODFPU-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052603 melanterite Inorganic materials 0.000 description 2
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CJNLYMOAHJMZRX-UHFFFAOYSA-M (1-butyl-3-methylimidazol-3-ium-2-yl)methanol chloride Chemical compound [Cl-].CCCC[N+]1=C(CO)N(C)C=C1 CJNLYMOAHJMZRX-UHFFFAOYSA-M 0.000 description 1
- 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
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- CGCMUAXRYMWMPX-UHFFFAOYSA-N 1-(2-hydroxyethyl)-6-methoxypyridin-1-ium-3-carboxylic acid chloride Chemical compound [Cl-].COC1=CC=C(C=[N+]1CCO)C(O)=O CGCMUAXRYMWMPX-UHFFFAOYSA-N 0.000 description 1
- ZNLHVKQDEYCOFT-UHFFFAOYSA-N 1-(2-phenylethyl)pyridin-1-ium-4-carboxylic acid chloride Chemical compound [Cl-].OC(=O)C1=CC=[N+](CCC2=CC=CC=C2)C=C1 ZNLHVKQDEYCOFT-UHFFFAOYSA-N 0.000 description 1
- PXAMYXCUNUKMLI-UHFFFAOYSA-N 1-(chloromethyl)pyridin-1-ium-3-carboxylic acid bromide Chemical compound [Br-].ClC[N+]1=CC(=CC=C1)C(=O)O PXAMYXCUNUKMLI-UHFFFAOYSA-N 0.000 description 1
- VSRWCQJUAYPITR-UHFFFAOYSA-N 1-benzylpyridin-1-ium-3-carboxylic acid;chloride Chemical group [Cl-].OC(=O)C1=CC=C[N+](CC=2C=CC=CC=2)=C1 VSRWCQJUAYPITR-UHFFFAOYSA-N 0.000 description 1
- KOBSYWNBDOPAPH-UHFFFAOYSA-N 1-butyl-1,3-dimethylpyrrolidin-1-ium-2-carboxylic acid chloride Chemical compound [Cl-].C(CCC)[N+]1(C(C(CC1)C)C(=O)O)C KOBSYWNBDOPAPH-UHFFFAOYSA-N 0.000 description 1
- PBTCBBZWZPKYBX-UHFFFAOYSA-N 1-butyl-1,4-dimethylpiperidin-1-ium-2-carboxylic acid chloride Chemical compound [Cl-].C(CCC)[N+]1(C(CC(CC1)C)C(=O)O)C PBTCBBZWZPKYBX-UHFFFAOYSA-N 0.000 description 1
- ZEBBGNBICSORIQ-UHFFFAOYSA-N 1-butylpyridin-1-ium-3-carboxylic acid bromide Chemical compound [Br-].C(CCC)[N+]1=CC(=CC=C1)C(=O)O ZEBBGNBICSORIQ-UHFFFAOYSA-N 0.000 description 1
- MWRDCUUIIPAPQE-UHFFFAOYSA-N 1-hexyl-6-(3-hydroxypropyl)pyridin-1-ium-3-carboxylic acid chloride Chemical compound [Cl-].CCCCCC[N+]1=CC(=CC=C1CCCO)C(O)=O MWRDCUUIIPAPQE-UHFFFAOYSA-N 0.000 description 1
- VMMUYTHNTBOVTJ-UHFFFAOYSA-N 1-hexyl-6-hydroxypyridin-1-ium-3-carboxylic acid chloride Chemical compound [Cl-].CCCCCC[N+]1=CC(=CC=C1O)C(O)=O VMMUYTHNTBOVTJ-UHFFFAOYSA-N 0.000 description 1
- CVDBEMKNUVJKHL-UHFFFAOYSA-N 1-methoxy-6-methylpyridin-1-ium-3-carboxylic acid chloride Chemical compound [Cl-].CO[N+]1=CC(=CC=C1C)C(O)=O CVDBEMKNUVJKHL-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- IQDSVYJPQZRDMZ-UHFFFAOYSA-N 2-(1-benzylpyridin-1-ium-3-yl)acetic acid chloride Chemical compound [Cl-].OC(=O)CC1=CC=C[N+](CC2=CC=CC=C2)=C1 IQDSVYJPQZRDMZ-UHFFFAOYSA-N 0.000 description 1
- CBSMYUKNBLDHEP-UHFFFAOYSA-N 2-(1-butyl-3-methylimidazol-1-ium-4-yl)acetic acid bromide Chemical compound [Br-].C(CCC)[N+]1=CN(C(=C1)CC(=O)O)C CBSMYUKNBLDHEP-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
- LBNNZKQHIBEBBR-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl-ethylamino]ethanol Chemical compound CCN(CC)CCN(CC)CCO LBNNZKQHIBEBBR-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- OOYATKQQGVPYQR-UHFFFAOYSA-N 3-(chloromethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CCl)=C1 OOYATKQQGVPYQR-UHFFFAOYSA-N 0.000 description 1
- IIVBUJGYWCCLNG-UHFFFAOYSA-N 3-(dimethylamino)propylurea Chemical compound CN(C)CCCNC(N)=O IIVBUJGYWCCLNG-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 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
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ZMLDXWLZKKZVSS-UHFFFAOYSA-N palladium tin Chemical compound [Pd].[Sn] ZMLDXWLZKKZVSS-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 150000003918 triazines Chemical class 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
-
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/67—Electroplating to repair workpiece
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0642—Anodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Definitions
- the present invention relates to a method and system for electroplating an article with metal. Specifically, the present invention relates to an electroplating method and system in which decomposition of an organic compound additive added to a plating bath comprising metal ions is suppressed.
- Zinc plating is used as a relatively inexpensive anti-corrosive plating, and its alkaline plating bath comprises an organic compound such as a quaternary amine polymer as an additive.
- organic compound such as a quaternary amine polymer as an additive.
- Zinc alloy plating has corrosion resistance superior to zinc plating and therefore is widely used for automobile parts and so on.
- alkaline zinc-nickel alloy plating is used for fuel system parts required to have high corrosion resistance and engine parts to be placed under a high temperature environment.
- An alkaline zinc-nickel alloy plating bath is obtained by dissolving nickel by using an amine-based chelating agent suitable for a nickel co-deposition ratio, and is for forming a plating film in which zinc and nickel are co-deposited.
- the alkaline zinc-nickel alloy plating bath has a problem that during current application, the amine-based chelating agent is oxidatively decomposed on the surface of the anode to generate oxalic acid and sodium carbonate.
- Patent Literatures 1 and 2 describe a so-called anode cell system partitioned such that an anolyte is placed in a cell covered with a diaphragm and that a plating bath is out of contact with an anode plate, thereby making it possible to suppressing decomposition of an organic compound additive. Since oxalic acid and sodium carbonate generated in the plating bath migrate from the plating solution into the anode cell in this anode cell system, this system is expected to produce an effect of removing the decomposed products in the plating bath. On the other hand, the anode cell system requires many ancillary facilities such as an anode cell body, piping, and a pump. In addition, it is necessary to control the concentration of the anolyte, and to renew the anolyte every time a certain amount of current is applied.
- Patent Literature 3 teaches that decomposition of an organic compound additive is suppressed by applying a coating to the surface of a conductive substrate of an anode. In this case, there is no need for ancillary facilities or anolyte control, but the cost for manufacturing the anode is a problem.
- Patent Literature 4 also teaches that a coating is applied to the surface of a conductive substrate of an anode, but further improvement is required.
- Patent Literature 5 teaches that a metal oxide film can be formed by heat-treating a metal film formed by electroplating, and an iron oxide film has high water repellency while a nickel oxide film has low water repellency.
- Patent Literature 6 and Non Patent Literatures 1 and 2 teach that an electrode having a film layer formed of iron nitride or oxide of nickel and iron is used for oxygen generation reaction by water electrolysis.
- none of Patent Literatures 1 to 6 and Non Patent Literatures 1 and 2 teaches that a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof is used as an electrode for electroplating.
- the object of the present invention is to provide a method and system for electroplating without requiring ancillary facilities or anolyte control, while using an anode which can be relatively easily produced without requiring an expensive metal or special metal.
- the present inventors found that, when electroplating an article with metal, decomposition of an organic compound additive in a plating bath can be suppressed by using, as an anode, a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof, and completed the present invention.
- the present invention provides the following method and system for electroplating an article with metal.
- the present invention it is possible to suppress decomposition of an organic compound additive in a plating bath in electroplating an article with metal by using, as an anode, a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof.
- Nickel and iron are metals available at relatively low prices, and no complicated processes are required to form a layer comprising oxide of these metals. Therefore, it is possible to perform metal plating such as zinc plating or zinc alloy plating with low manufacturing cost.
- the present invention relates to a method for electroplating an article with metal.
- the metal is not particularly limited as long as it is usable for electroplating.
- the metal may comprise zinc, nickel, iron, copper, cobalt, tin, manganese, and the like.
- the metal consists of zinc only, a zinc film is formed on the article.
- the metal comprises zinc and another metal, a zinc alloy film is formed on the article.
- the other metal is not particularly limited as long as it can form the zinc alloy film, but may be at least one selected from the group consisting of, for example, nickel, iron, cobalt, tin, manganese, and the like.
- the zinc alloy film may be, but not particularly limited to, zinc-nickel alloy plating, zinc-iron alloy plating, zinc-cobalt alloy plating, zinc-manganese alloy plating, zinc-tin alloy plating, or the like, and is preferably zinc-nickel alloy plating.
- the article is an article to be plated, and any article commonly used in this technical field can be employed without particular limitation.
- the article may be made of any of various metals such as iron, nickel, copper, zinc, and aluminum and alloys of them.
- its shape is not particularly limited.
- any of various articles including: plate-shaped articles such as a steel plate and a plated steel plate; and shaped articles such as a rectangular parallelepiped article, a columnar article, a cylindrical article, and a spherical article are exemplified.
- shaped articles include: fastening parts such as bolts, nuts, and washers; pipe parts such as fuel pipes; cast iron parts such as brake calipers and common rails; and various articles such as connectors, plugs, housings, bases or mouthpieces, and seatbelt anchors.
- the method of the present invention comprises the step of applying current in a plating bath comprising ions of a metal to be plated and an organic compound additive, wherein the plating bath comprises the article as a cathode, and comprises, as an anode, a conductive substrate having a layer comprising oxide or nitride of nickel and iron on a surface thereof.
- the plating bath may be, but not particularly limited to, any of acidic or neutral plating baths such as a sulfuric acid bath, a boron fluoride bath, and an organic acid bath, and alkaline plating baths such as a cyanide bath, a zincate bath, and a pyrophosphate bath, and is preferably an alkaline plating bath.
- the conductive substrate is not particularly limited as long as it can conduct electricity, but may be, for example, an iron, nickel, stainless steel, carbon, titanium, zirconium, niobium, tantalum, platinum, platinum-plated titanium, or palladium-tin alloy substrate, a substrate coated with any of them, or the like, and is preferably a substrate comprising at least one of nickel and iron.
- the layer comprising the oxide or nitride of nickel and iron is formed on a liquid contact portion of the conductive substrate.
- the organic compound additive is oxidatively decomposable in the vicinity of the anode, and thus the layer comprising the oxide or nitride of nickel and iron suppresses decomposition of the organic compound additive by functioning as a catalyst for an oxygen evolution reaction due to electrolysis of water, and thereby making the oxygen evolution reaction more dominant than the oxidative decomposition reaction in the vicinity of the anode.
- a method for forming the layer comprising the oxide or nitride is not particularly limited.
- the layer comprising the oxide or nitride may be formed by oxidation or nitridation of a conductive substrate having a plating film comprising nickel and iron, a conductive substrate comprising iron and having a plating film comprising nickel, a conductive substrate comprising nickel and having a plating film comprising iron, or a conductive substrate comprising nickel and iron.
- the conductive substrate may be plated with nickel and iron, and the film comprising nickel and iron may be treated with thermal oxidation to oxidize a part or all of the film.
- an alloy of nickel and iron may be used as the conductive substrate and the alloy may be treated with thermal oxidation to oxidize the surface of the alloy.
- the conductive substrate In the case where the conductive substrate is plated with nickel and iron and only the surface of the film is oxidized, the conductive substrate would have, on its surface, two layers, that is, a layer comprising oxide of nickel and iron and a film layer comprising nickel and iron.
- the plating film comprising nickel and iron, the plating film comprising nickel, and the plating film comprising iron for use to form the layer comprising the oxide or nitride of nickel and iron can be formed by a plating method commonly used in this technical field.
- the plating film comprising nickel and iron, the plating film comprising nickel, or the plating film comprising iron may be formed by using a plating bath comprising saccharin or a salt thereof, or preferably using a plating bath comprising sodium saccharin.
- an anode comprising the layer comprising the oxide or nitride of nickel and iron derived from the plating film formed in the plating bath comprising the saccharin or the salt thereof makes it possible to further improve the effect of suppressing decomposition of the organic compound additive.
- concentration of the saccharin or the salt thereof in the plating bath is not particularly limited, but may be, for example, about 0.1 to about 2.0 g/L, and is preferably about 0.5 to about 1.9 g/L.
- the amounts of nickel (Ni) and iron (Fe) constituting the layer comprising the oxide are not particularly limited.
- the atomic percent of Ni in the layer comprising the oxide may be about 0.5% to about 45%, and is preferably about 1% to about 15%
- the atomic percent of Fe in the oxide-comprising layer may be about 5% to about 45%, and is preferably about 30% to about 40%.
- the thickness of the layer comprising the oxide is not particularly limited, but may be, for example, about 0.5 ⁇ m to about 10 ⁇ m, and is preferably about 1.5 ⁇ m to about 4 ⁇ m. When the thickness of the layer comprising the oxide is within the above range, it is possible to maintain the good performance of the anode and exert the effect of suppressing the decomposition of the organic compound additive more satisfactorily.
- the layer comprising the oxide or nitride of nickel and iron further contains phosphorus atoms or boron atoms.
- a phosphorus compound or a boron compound may be added to the plating bath used therein.
- organic compound additive refers to an organic compound to be added to a plating bath for electroplating.
- a type of the organic compound additive is not particularly limited.
- the organic compound additive may be at least one selected from the group consisting of brightening agents, auxiliary additives (such as smoothing agents), defoamers, and the like.
- the organic compound additive may be at least one selected from the group consisting of amine-based chelating agents, brightening agents, auxiliary additives (such as smoothing agents), defoamers, and the like.
- the organic compound additive comprises a brightening agent in a preferred embodiment.
- any agent commonly used in this technical field may be employed without particular limitation.
- the brightening agent include: (1) nonionic surfactants such as polyoxyethylene polyoxypropylene block polymer and acetylene glycol EO adduct, and anionic surfactants such as polyoxyethylene lauryl ether sulfate and alkyldiphenyl ether disulfonate; (2) polyamine compounds: such as polyallylamines such as copolymer of diallyldimethylammonium chloride and sulfur dioxide; polyepoxypolyamines such as condensation polymer of ethylenediamine and epichlorohydrin, condensation polymer of dimethylaminopropylamine and epichlorohydrin, condensation polymer of imidazole and epichlorohydrin, condensation polymer of an imidazole derivative such as 1-methylimidazole or 2-methylimidazole with epichlorohydrin, and condensation polymer of epichlorohydrin with heterocyclic amine including a tri
- the brightening agent comprises a quaternary ammonium salt or an aromatic aldehyde.
- the above brightening agents may be used alone or used in combination of two or more.
- the concentration of the brightening agent in the plating bath is not particularly limited.
- the concentration of the brightening agent may be about 1 to about 500 mg/L, and is preferably about 5 to about 100 mg/L, and in the other cases, the concentration may be about 0.01 to about 10 g/L, and is preferably about 0.02 to about 5 g/L.
- the brightening agent may comprise a nitrogen-containing heterocycle quaternary ammonium salt in addition to the quaternary ammonium salt not having a nitrogen-containing heterocycle.
- the nitrogen-containing heterocycle quaternary ammonium salt is a nitrogen-containing heterocycle quaternary ammonium salt having a carboxyl group and/or a hydroxy group.
- the nitrogen-containing heterocycle in the nitrogen-containing heterocycle quaternary ammonium salt is not particularly limited, but may be, for example, pyridine ring, piperidine ring, imidazole ring, imidazoline ring, pyrrolidine ring, pyrazole ring, quinoline ring, or morpholine ring, and is preferably pyridine ring. More preferably, the nitrogen-containing heterocycle quaternary ammonium salt is a quaternary ammonium salt of nicotinic acid or a derivative thereof.
- the carboxyl group and/or the hydroxy group may be directly bonded to the nitrogen-containing heterocycle, or may be bonded via another substituent as in a carboxymethyl group.
- the nitrogen-containing heterocycle quaternary ammonium salt may contain an additional substituent such as, for example, an alkyl group, in addition to the carboxyl group and the hydroxy group.
- N substituent forming a heterocyclic quaternary ammonium cation is not particularly limited as long as it does not impair the effect as the brightening agent, but may be, for example, a substituted or unsubstituted alkyl, aryl, or alkoxy group.
- the counter anion forming the salt is not particularly limited, but may be, for example, a compound containing halogen anion, oxyanion, borate anion, sulfonate anion, phosphate anion, imide anion, or the like, and is preferably halogen anion.
- Such a quaternary ammonium salt is preferable because it contains both a quaternary ammonium cation and an oxyanion in its molecule, and also behaves as an anion.
- nitrogen-containing heterocycle quaternary ammonium salt is N-benzyl-3-carboxypyridinium chloride, N-phenethyl-4-carboxypyridinium chloride, N-butyl-3-carboxypyridinium bromide, N-chloromethyl-3-carboxypyridinium bromide, N-hexyl-6-hydroxy-3-carboxypyridinium chloride, N-hexyl-6-3-hydroxypropyl-3-carboxypyridinium chloride, N-2-hydroxyethyl-6-methoxy-3-carboxypyridinium chloride, N-methoxy-6-methyl-3-carboxypyridinium chloride, N-propyl-2-methyl-6-phenyl-3-carboxypyridinium chloride, N-propyl-2-methyl-6-phenyl-3-carboxypyridinium chloride, N-propyl-2-methyl-6-phenyl-3-carboxypyridinium chloride, N
- the nitrogen-containing heterocycle quaternary ammonium salts may be used alone or used in combination of two or more.
- concentration of the nitrogen-containing heterocycle quaternary ammonium salt in the plating bath is not particularly limited, but may be, for example, about 0.01 to about 10 g/L and is preferably 0.02 to 5 g/L.
- the auxiliary additive any additive commonly used in this technical field may be employed without particular limitation.
- the auxiliary additive may comprise organic acid, silicate, or a mercapto compound and these may be used as a smoothing agent.
- the auxiliary additives may be used alone or used in combination of two or more.
- the concentration of the auxiliary additive in the plating bath is not particularly limited, but may be, for example, about 0.01 to about 50 g/L.
- the defoamer any defoamer commonly used in this technical field may be employed without particular limitation.
- the defoamer may be a surfactant or the like.
- the defoamers may be used alone or used in combination of two or more.
- the concentration of the defoamer in the plating bath is not particularly limited, but may be, for example, about 0.01 to about 5 g/L.
- the amine-based chelating agent may comprise: alkyleneamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; alkylene oxide adducts of the above alkyleneamines such as ethylene oxide adducts and propylene oxide adducts; amino alcohols such as ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, ethylenediaminetetra-2-propanol, N-(2-aminoethyl)ethanolamine, and 2-hydroxyethylaminopropylamine; alkanolamine compounds such as N-(2-hydroxyethyl)-N,N',N'-triethylethylenediamine, N,N'-di(2-hydroxyethyl)-N
- the amine-based chelating agent comprises at least one selected from the group consisting of alkyleneamine compounds, their alkylene oxide adducts, and alkanolamine compounds.
- the amine-based chelating agents may be used alone or used in combination of two or more.
- the concentration of the amine-based chelating agent in the plating bath is not particularly limited, but may be, for example, about 5 to about 200 g/L, and is preferably about 30 to about 100 g/L.
- the plating bath particularly the alkaline plating bath, comprises zinc ions.
- any ion source commonly used in this technical field may be employed without particular limitation.
- the ion source may be Na 2 [Zn(OH) 4 ], K 2 [Zn(OH) 4 ], or ZnO.
- the zinc ion sources may be used alone or used in combination of two or more.
- the concentration of the zinc ions in the alkaline plating bath is not particularly limited, but may be, for example, about 2 to about 20 g/L, and is preferably about 4 to about 12 g/L.
- the plating bath particularly the alkaline plating bath, further comprises another kind of metal ions for forming the zinc alloy film in addition to the zinc ions.
- the other kind of metal ions is not particularly limited as long as it can form the zinc alloy film, but may be at least one kind selected from the group consisting of nickel ions, iron ions, cobalt ions, tin ions, manganese ions, and the like, and is preferably nickel ions.
- An ion source for producing the other kind of metal ions is not particularly limited, but may be, for example, nickel sulfate, iron(II) sulfate, cobalt sulfate, tin(II) sulfate, manganese sulfate, or the like.
- the ion sources for the other kinds of metal ions may be used alone or used in combination of two or more.
- the total concentration of the other kinds of metal ions in the alkaline plating bath is not particularly limited, but may be, for example, about 0.4 to about 4 g/L, and is preferably about 1 to about 3 g/L.
- the plating bath may comprise caustic alkali.
- the caustic alkali is not particularly limited, but may be, for example, sodium hydroxide, potassium hydroxide, or the like. More specifically, the plating bath may comprise sodium hydroxide when the plating bath is an alkaline plating bath or may comprise potassium hydroxide when the plating bath is an acidic plating bath.
- the concentration of the caustic alkali in the alkaline plating bath is not particularly limited, but may be, for example, about 60 to about 200 g/L, and is preferably about 100 to about 160 g/L.
- Conditions for the current application step are not particularly limited as long as zinc or zinc alloy plating can be applied.
- the current may be applied at a temperature of about 15°C to about 40°C and preferably about 25°C to about 35°C, or the current may be applied with a cathode current density of about 0.1 to 20 A/dm 2 and preferably 0.2 to 10 A/dm 2 .
- the method of the present invention may further comprise any step commonly used in this technical field as long as the step will not impair the object of the present invention.
- the method of the present invention may further comprise a step of washing the article before the current application step, a step of washing the article after the current application step, and so on.
- the present invention relates to a system for electroplating an article with metal.
- the system of the present invention comprises a plating bath comprising the metal ions and an organic compound additive, and the plating bath comprises the article as a cathode and a conductive substrate having a layer comprising oxide or nitride of nickel and iron on a surface thereof as an anode.
- the system of the present invention may further comprise any facility commonly used in this technical field as long as the facility will not impair the object of the present invention.
- the present invention relates to a method for producing an electrode comprising a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof.
- the production method of the present invention comprises a step of performing oxidation treatment or nitridation treatment on a conductive substrate having a plating film comprising nickel and iron, a conductive substrate comprising iron and having a plating film comprising nickel, a conductive substrate comprising nickel and having a plating film comprising iron, or a conductive substrate comprising nickel and iron, thereby forming a layer comprising oxide or nitride of nickel and iron on a surface of the conductive substrate.
- the production method of the present invention may further comprise a step of forming the plating film comprising nickel and iron, the plating film comprising nickel, or the plating film comprising iron by using a plating bath comprising saccharin or a salt thereof.
- the production method of the present invention may further comprise any step commonly used in this technical field as long as the step will not impair the object of the present invention.
- the present invention relates to a method for repairing an electrode comprising a conductive substrate with a surface having a layer comprising oxide of nickel and iron formed on a surface thereof, in which electrode the layer comprising the oxide is partly damaged on the surface.
- the repairing method of the present invention comprises a step of heating the electrode in an ambient atmosphere or oxidizing atmosphere.
- the conductive substrate has a plating film comprising nickel and iron under the layer comprising the oxide of nickel and iron, or comprises iron and has a plating film comprising nickel under the layer comprising the oxide of nickel and iron, or comprises nickel and has a plating film comprising iron under the layer comprising the oxide of nickel and iron, or contains nickel and iron.
- An anode having a coating on a surface thereof has been heretofore known, but in the case where the coating is damaged, it is necessary to remove all the coating once and perform the coating process again.
- the repairing method of the present invention without peeling off the partly damaged layer, it is possible to restore the oxide in the damaged part only by heating the electrode having the layer.
- a heating unit for the heating step is not particularly limited, and the heating may be performed by, for example, a burner, a muffle furnace such as an electric furnace or gas furnace, a heater such as a ceramic heater or an infrared heater, an electromagnetic induction heater, a laser heating device, or the like.
- Conditions for the heating step are not particularly limited as long as the oxide in the damaged parts in the layer comprising the oxide can be regenerated, and may be adjusted as appropriate depending on the size of the electrode and the number and size of the damaged parts.
- the electrode may be repaired by heating with a burner for about 5 to 30 minutes or may be repaired by heating in a muffle furnace for about 30 to 90 minutes.
- the electrode can be repaired effectively with indirect heating avoiding direct exposure of the damaged parts to the flame, or with heating in an apparatus such as a muffle furnace that does not emit a flame.
- the electrode can be repaired any number of times by applying the repairing method of the present invention again.
- An iron plate (64 ⁇ 64 ⁇ 2.3 mm) was degreased and activated with hydrochloric acid by conventional methods. Then, the iron plate was plated under the conditions of 4 A/dm 2 , 50°C, and 20 minutes using a plating bath having each of compositions specified in Table 1 below, thereby fabricating the iron plate with Ni-Fe plating.
- Table 1 Composition of Plating Bath [g/L] Component
- Example 1 NiSO 4 ⁇ 6H 2 O 250 250 NiCl 2 ⁇ 6H 2 O 40 40 FeSO 4 ⁇ 7H 2 O 7.2 7.2 H 3 BO 3 30 30 Malonic Acid 5.2 5.2 Saccharin Na 0 0.5
- the iron plate with Ni-Fe plating was washed, dried in room temperature, and then heated by using a muffle furnace at 650°C for one hour. After that, the iron plate was slowly cooled down to room temperature for about one hour to fabricate an iron plate electrode. A surface and a cross-section of this iron plate electrode were observed with a scanning electron microscope (SEM) and elemental mapping was performed with an energy dispersive X-ray spectrometer (EDS).
- Figs. 1A to 1D and Fig. 2 show the results of the iron plate electrode in Example 1.
- Ni-Fe oxide layer a layer comprising oxide of nickel and iron (Ni-Fe oxide layer) was formed on the surface of the iron plate electrode (Table 2).
- X-ray diffraction analysis of this Ni-Fe oxide layer revealed that NiO, Fe 2 O 3 , and NiFe 2 O 4 were contained in both the electrodes.
- the element concentrations in the plated part of each of the iron plate electrodes were measured by EDS before and after the heat treatment, the element concentrations of nickel atoms (Ni), iron atoms (Fe), and oxygen atoms (O) were obtained as shown in Table 2 below.
- Example 2 Ni Fe O Ni Fe O Before Heat Treatment (After Plating) 84.9 15.1 Not Detected 88.4 11.6 Not Detected After Heat Treatment 7.0 35.3 57.7 10.1 34.7 55.2
- Alkaline zinc-nickel plating using the iron plate electrode with the Ni-Fe oxide layer of Example 1 or 2 as the anode and using an ordinary iron plate electrode (electrode degreased and activated with hydrochloric acid) as a cathode was performed in 500 mL of a plating bath having the composition specified in Table 3 below.
- Table 3 Composition of Plating Bath Component Concentration ZnO 10 g/L (8 g/L in terms of Zn ions) NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions) Caustic Soda 130 g/L IZ-250YB ⁇ 1 60 g/L IZ-250YR1 ⁇ 2 0.6 mL/L (polyamine 0.1 g/L) IZ-250YR2 ⁇ 3 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L) ⁇ 1 Amine-based chelating agent (ethylene oxide adduct of alkyleneamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
- ZnO 10 g/L 8 g/L in terms of Zn ions
- NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions)
- Brightening agent (polyamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
- Brightening agent (quaternary ammonium salt of nicotinic acid) manufactured by DIPSOL CHEMICALS Co., Ltd.
- the temperature of the plating bath was set to 25°C and controlled by cooling to keep a constant temperature during current application.
- An anode current density was set to 8 A/dm 2 and a cathode current density was set to 2.56 A/dm 2 .
- a cathode iron plate was replaced every application of 5.1 Ah/L during the current application.
- the ion concentrations in the plating bath were maintained during the current application in such a way that metallic zinc was immersed in the plating bath for replenishment of the zinc ion concentration and IZ-250YNi (nickel replenisher manufactured by DIPSOL CHEMICALS Co., Ltd) was added for replenishment of the nickel ion concentration.
- the concentration of the caustic soda was periodically measured and was kept constant during the current application with replenishment with the caustic soda.
- IZ-250YB was replenished at 80 mL/kAh.
- IZ-250YR1 and IZ-250YR2 were replenished at 15 mL/kAh.
- Table 4 Test Results [g/L] IZ-250YB Oxalic Acid Na 2 CO 3 Before Current application 60 Not Detected Not Detected After Current Application with Anode in Example 1 53 0.2 3.9 After Current Application with Anode in Example 2 60 0.1 3.2
- Iron plate electrodes with Ni-Fe oxide layers in Examples 3 to 8 were fabricated in the same way as in Preparation Example 1 except that the iron plate was plated under the conditions of 4 A/dm 2 , 50°C, and 20 minutes using a plating bath having each of compositions specified in Table 5 below. Then, a plated portion of each of the iron plate electrodes was measured by EDS and the element concentration of iron atoms (Fe) was checked (Table 6).
- Table 5 Composition of Plating Bath [g/L] Component Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 NiSO 4 ⁇ 6H 2 O 250 250 250 250 250 250 250 250 NiCl 2 ⁇ 6H 2 O 40 40 40 40 40 40 40 FeSO 4 ⁇ 7H 2 O 1.5 2.3 7.2 4.8 7.2 18 H 3 BO 3 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30
- the iron plate electrode with the Ni-Fe oxide layer in each of Examples 3 to 8 was set as the anode, a satin steel plate of SPCC was set as the cathode, and 160 mL of an electrolytic liquid with the composition specified in Table 7 below was added. Then, current application was started with a current value of 2.6 A. The anode current density at that time was 8.1 A/dm 2 .
- Table 7 Composition of Electrolytic Liquid Component Concentration NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions) Caustic Soda 130 g/L IZ-250YB ⁇ 1 60 g/L IZ-250YR1 ⁇ 2 0.5 mL/L (polyamine 0.1 g/L) IZ-250YR2 ⁇ 3 1.0 mL/L (quaternary ammonium salt of nicotinic acid 0.4 g/L) ⁇ 1 Amine-based chelating agent (ethylene oxide adduct of alkyleneamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
- NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions)
- Brightening agent (polyamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
- Brightening agent (quaternary ammonium salt of nicotinic acid) manufactured by DIPSOL CHEMICALS Co., Ltd.
- the current application was continued for 7 hours 42 minutes, and the temperature of the electrolytic liquid was adjusted at 25°C during the current application. Then, in the electrolytic liquid before and after the current application, the concentrations of IZ-250YB and the oxalic acid were measured by ion chromatography, the concentration of the quaternary ammonium salt of nicotinic acid was measured by capillary electrophoresis, and the concentration of the sodium carbonate (Na 2 CO 3 ) was measured by titration. The results are shown in Table 8.
- Table 8 Test Results [g/L] IZ-250YB Quaternary Ammonium Salt of Nicotinic Acid Oxalic Acid Na 2 CO 3 Before Current Application 60 0.4 Not Detected Not Detected After Current Application With Iron Plate Electrode with Ni-Fe Oxide Layer Produced without Using Saccharin Electrode in Example 3 48 0.24 0.1 Not Detected Electrode in Example 4 43 0.2 0.2 4.2 Electrode in Example 5 50 0.24 0.2 3.2 After Current Application With Iron Plate Electrode with Ni-Fe Oxide Layer Produced by Using Saccharin Electrode in Example 6 46 0.2 0.3 5.6 Electrode in Example 7 52 0.24 0.1 Not Detected Electrode in Example 8 55 0.28 0.2 Not Detected
- the amine-based chelating agent (IZ-250YB) and the brightening agent (IZ-250YR2) are decomposed during current application (see Comparative Test Example below).
- the iron plate electrode with the Ni-Fe oxide layer was used as the anode, the decomposition of the amine-based chelating agent (IZ-250YB) and the brightening agent (IZ-250YR2) during the current application was suppressed.
- the oxalic acid and the sodium carbonate that tend to increase along with current application, the increases in their concentrations were suppressed by use of the iron plate electrode with the Ni-Fe oxide layer.
- Each of a nickel plate (64 ⁇ 64 ⁇ 2.3 mm) and an iron plate (64 ⁇ 64 ⁇ 2.3 mm) was placed in a muffle furnace, was heated at 650°C for 30 minutes, and then was slowly cooled down to room temperature for about one hour, thereby fabricating electrodes for comparison (the nickel plate with a nickel oxide layer and the iron plate with an iron oxide layer).
- An iron plate electrode with a Ni-Fe oxide layer was fabricated in the same manner as in Example 3 of Preparation Example 2. Using this iron plate electrode as an anode, alkaline zinc-nickel plating was performed according to the method described in Test Example 1 to consume the anode. Then, after 300 hours, the anode was taken out and current application was performed for 7 hours and 42 minutes according to the method described in Test Example 2. The concentrations of the amine-based chelating agent (IZ-250YB), the brightening agent (quaternary ammonium salt of nicotinic acid; IZ-250YR2), the oxalic acid, and the sodium carbonate in the electrolytic liquid were measured.
- IZ-250YB the amine-based chelating agent
- the brightening agent quaternary ammonium salt of nicotinic acid
- oxalic acid oxalic acid
- the anode consumed by the alkaline zinc-nickel plating was repaired by heating with a gas burner. Specifically, four places on the side of the anode that was unconsumed due to contact with the inner surface of the electrolytic cell during the current application were each heated for 5 minutes, then allowed to stand at room temperature and cooled. Then, for the repaired anode, the current application was also performed for 7 hours and 42 minutes according to the method described in Test Example 2, and the concentrations of the amine-based chelating agent (IZ-250YB), the brightening agent (quaternary ammonium salt of nicotinic acid; IZ-250YR2), the oxalic acid, and the sodium carbonate in the electrolytic liquid were measured.
- IZ-250YB the amine-based chelating agent
- the brightening agent quaternary ammonium salt of nicotinic acid
- oxalic acid oxalic acid
- the anode repaired after the current application for 300 hours was consumed by being further used for additional current application for 100 hours. Then, this consumed electrode was repaired by heating with the burner in the same manner as in the case of the current application for 300 hours.
- the current application was also performed for 7 hours and 42 minutes according to the method described in Test Example 2, and the concentrations of the amine-based chelating agent (IZ-250YB), the brightening agent (quaternary ammonium salt of nicotinic acid; IZ-250YR2), the oxalic acid, and the sodium carbonate in the electrolytic liquid were measured. The results of all the measurements are presented in Table 10.
- Table 10 Test Results [g/L] IZ-250YB Quaternary Ammonium Salt of Nicotinic Acid Oxalic Acid Na 2 CO 3 Before Current Application 60 0.4 Not Detected Not Detected After Current Application with Unconsumed Anode 49 0.24 0.1 Not Detected Consumption with Current Application for 300 Hours After Current Application with Unrepaired Anode 39 0.2 0.6 9.3 After Current Application with Repaired Anode 49 0.24 0.2 Not Detected Consumption with Additional Current Application for 100 Hours After Current Application with Unrepaired Anode 45 0.24 0.4 6.6 After Current Application with Repaired Anode 48 0.36 0.2 2.0
- the anode As the time of the current application was increased, the anode was consumed more, and the effects of suppressing the decomposition of the organic compound additive and suppressing the increases in the electrolyte aging products in the plating bath were decreased. On the other hand, these effects were recovered by heating the consumed anodes. The same recovery effect was also confirmed by heating the consumed anode in the muffle furnace at 650°C for one hour. In addition, even when the repaired anode was consumed, the effects of suppressing the decomposition of the organic compound additive and suppressing the increases in the electrolyte aging products in the plating bath were recovered by heating the anode again.
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