EP2171131B1 - Method to electrodeposit metals using ionic liquids in the presence of an additive - Google Patents
Method to electrodeposit metals using ionic liquids in the presence of an additive Download PDFInfo
- Publication number
- EP2171131B1 EP2171131B1 EP08786597A EP08786597A EP2171131B1 EP 2171131 B1 EP2171131 B1 EP 2171131B1 EP 08786597 A EP08786597 A EP 08786597A EP 08786597 A EP08786597 A EP 08786597A EP 2171131 B1 EP2171131 B1 EP 2171131B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonium chloride
- group
- metal
- anion
- ionic liquid
- 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.)
- Not-in-force
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 78
- 239000002184 metal Substances 0.000 title claims abstract description 78
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 53
- 239000000654 additive Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000000996 additive effect Effects 0.000 title claims abstract description 22
- 150000002739 metals Chemical class 0.000 title description 3
- 239000002659 electrodeposit Substances 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 76
- 235000019270 ammonium chloride Nutrition 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 150000001450 anions Chemical class 0.000 claims description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 20
- -1 carboxylate anion Chemical class 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 20
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 15
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 15
- 239000003760 tallow Substances 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229960001231 choline Drugs 0.000 claims description 7
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 7
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229910052920 inorganic sulfate Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-M 1,1-dioxo-1,2-benzothiazol-3-olate Chemical compound C1=CC=C2C([O-])=NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-M 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- JMHWNJGXUIJPKG-UHFFFAOYSA-N CC(=O)O[SiH](CC=C)OC(C)=O Chemical compound CC(=O)O[SiH](CC=C)OC(C)=O JMHWNJGXUIJPKG-UHFFFAOYSA-N 0.000 claims description 3
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 3
- CBSOFSBFHDQRLV-UHFFFAOYSA-N N-methylbenzylamine hydrochloride Chemical compound [Cl-].C[NH2+]CC1=CC=CC=C1 CBSOFSBFHDQRLV-UHFFFAOYSA-N 0.000 claims description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 claims description 3
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 claims description 3
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims description 3
- RBRXPPLNXDVMKG-GMFCBQQYSA-M bis(2-hydroxyethyl)-methyl-[(z)-octadec-9-enyl]azanium;chloride Chemical compound [Cl-].CCCCCCCC\C=C/CCCCCCCC[N+](C)(CCO)CCO RBRXPPLNXDVMKG-GMFCBQQYSA-M 0.000 claims description 3
- SUZSZZWHCFLFSP-UHFFFAOYSA-M bis(2-hydroxyethyl)-methyl-octadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(CCO)CCO SUZSZZWHCFLFSP-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims description 3
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 3
- PTIUDKQYXMFYAI-UHFFFAOYSA-N methylammonium nitrate Chemical compound NC.O[N+]([O-])=O PTIUDKQYXMFYAI-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- FAGMGMRSURYROS-UHFFFAOYSA-M trihexadecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC FAGMGMRSURYROS-UHFFFAOYSA-M 0.000 claims description 3
- HVLUSYMLLVVXGI-USGGBSEESA-M trimethyl-[(z)-octadec-9-enyl]azanium;chloride Chemical compound [Cl-].CCCCCCCC\C=C/CCCCCCCC[N+](C)(C)C HVLUSYMLLVVXGI-USGGBSEESA-M 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 13
- 239000010962 carbon steel Substances 0.000 description 13
- 238000004070 electrodeposition Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 10
- 150000002431 hydrogen Chemical group 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 6
- 239000011636 chromium(III) chloride Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 4
- 235000019743 Choline chloride Nutrition 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 4
- 229960003178 choline chloride Drugs 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 235000007831 chromium(III) chloride Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 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
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-O dimethylaminium Chemical compound C[NH2+]C ROSDSFDQCJNGOL-UHFFFAOYSA-O 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- VPJDULFXCAQHRC-UHFFFAOYSA-N prop-2-enylurea Chemical compound NC(=O)NCC=C VPJDULFXCAQHRC-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- HRTKQUHFGZFPPF-UHFFFAOYSA-M tetraethylazanium;fluoride;dihydrate Chemical compound O.O.[F-].CC[N+](CC)(CC)CC HRTKQUHFGZFPPF-UHFFFAOYSA-M 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
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
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
Definitions
- the present invention relates to a method to electrodeposit a metal on a substrate using an ionic liquid as the electrolyte in the presence of an additive, and to the use of said additive to increase the layer thickness of the deposited metal layer.
- An ionic liquid is a salt in which the ions are poorly coordinated, which results in these solvents being liquid at temperatures below 100°C. Many are liquid even at room temperature. At least one ion in an ionic liquid has a delocalized charge and one component is organic, which prevents the formation of a stable crystal lattice. Ionic liquids generally have very low vapour pressure and thus, in contrast to many conventional solvents, produce virtually no hazardous vapours. It is known that, in general, ionic liquids may be used in many applications, e.g. as reaction solvents, extraction solvents, electrolytes in batteries and electrodeposition, catalysts, heat exchange fluids, as additives in coatings.
- Well-known systems include those formed from alkylpyridinium halides or dialkylimidazolium halides with an aluminium halide, and those based on choline chloride and a (hydrated) metal salt such as chromium(III) chloride. These systems have been utilized as electrolytes in electroplating, as described for example in EP 0 404 188 and EP 1 322 591 .
- WO 2002/026381 discloses ionic liquids (eutectic mixtures) of choline chloride and a (hydrated) metal salt such as chromium(III) chloride and the use thereof in electrodeposition and electropolishing.
- the mixtures consist of choline chloride and the (hydrated) metal salt in a ratio of ammonium to metal ion of between 1:1 and 1:2.5 and are specifically said to be suitable for depositing chromium, cobalt, zinc or silver on a metal substrate.
- PCT/EP/2007/051329 describes a method to electroplate or electropolish a metal on a substrate wherein an ionic liquid selected from the group of N + R 1 R 2 R 3 R 4 X - or N + R 5 R 6 R 7 R 8 Y - is employed as electrolyte, and a metal salt added to the ionic liquid is employed as the metal source or a metal anode is used as the metal source, wherein any one of R 1 to R 8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 , or OR 9 , at least one of R 5 to R 8 is a fatty alkyl chain, and one or more of R 5 to R 8 can be a (poly)oxyalkylene group wherein the alkylene
- ionic liquids as electrolytes in electrodeposition processes has several advantages.
- Conventional chromic acid plating processes are extremely hazardous because they mainly rely on hexavalent chromium, which is highly toxic and carcinogenic.
- Ionic liquids may eliminate the necessity to use hexavalent chromium and allow the use of trivalent chromium, which is considered to be far less dangerous.
- conventional chromium plating baths require the use of strong acids, which poses significant disposal problems, while the use of ionic liquids generally enables such disposal difficulties to be minimized or even eliminated.
- ionic liquids are non-volatile, so they do not cause atmospheric pollution.
- a drawback to the prior art electrodeposition processes wherein an ionic liquid is used as the electrolyte is that depositing metal layers of some metals thicker than 150-200 nm is difficult or even impossible.
- metal layers For some applications, such as decorative plating, having thin metal layers is acceptable. However, for applications where the metal layer needs to provide protection against wear or abrasion, or to improve hardness (functional plating), metal layers much thicker than 200 nm are required. More particularly, layers of several micrometers or even several tens of micrometers are desirable.
- the present invention relates to the use of amorphous silica, graphite powder, or a mixture thereof as additive in a process to electroplate or electropolish a metal on a substrate wherein an ionic liquid is employed as the electrolyte to increase metal layer thickness. Additionally, the invention relates to a method according to claim 7.
- Additives have been added to the ionic liquid comprising electrolyte for several reasons.
- US 7,196,221 discloses the use of brightening agents to improve the appearance of the coatings obtained in ionic liquid solvents/- electrolytes during metal plating and electropolishing processes, and in particular in chromium plating processes.
- the brightening agents include thiourea, saccharin, vanillin, allyl urea, nicotinic acid, citric acid, gelatin, 2-mercaptobenzothiazole, tetraethylammonium fluoride dihydrate or tetramethylammonium hydroxide pentahydrate.
- these additives have an adverse effect on the homogeneity of the deposited layer, or no effect at all.
- WO 2006/074523 relates to a process for the recovery of platinum group metal, which comprises electrodeposition of the platinum group metal from an ionic liquid wherein redox reagents, complexing agents, conductivity enhancers may be present.
- US 6,552,843 which is concerned with devices, such as adjustable mirrors, smart windows, optical attenuators, and displays, for controlling the reflectance and/or transmission of electromagnetic radiation, discloses a reversible electrodeposition optical modulation device employing an ionic liquid electrolyte.
- the ionic liquid electrolyte is comprised of a mixture of an ionic organic compound and the salt of an electrodepositable metal.
- the ionic organic compound comprises a heterocyclic cation such as N-alkylpyrrolidinium, pyrrolidinium, 1-alkyl-3-methylimidazolium, N-alkylpyridinium, 2-alkyl-1-pyrrolinium, 1-alkylimidazolium.
- the electrodepositable metal is silver, copper, tin, zinc, palladium, bismuth, cadmium, mercury, indium, lead, antimony, thallium, and alloys thereof. It is mentioned that said ionic liquid electrolyte may be rendered more viscous, semi-solid or solid by addition of organic or inorganic gelling agents. Inorganic or organic materials, including suspended carbon and dissolved dyes, may be added to the electrolyte to impart a desired colour or to reduce background reflection.
- electrodeposition in this application should be understood to include both electroplating and electropolishing.
- electroplating is meant the process of using electrical current to coat an electrically conductive object with a layer of metal. The preferred result is a thin, smooth, even coat of metal on the object.
- the primary application of electroplating is to deposit a layer of a metal having some desired property (e.g., abrasion and wear resistance, corrosion protection, lubricity, improvement of aesthetic qualities, etc.) onto a surface lacking that property.
- Another application uses electroplating to build up thickness on undersized parts.
- electropolishing is meant smoothing and enhancing the appearance of an originally rough or uneven metal surface by coating it with a relatively thin metal layer.
- the additive used according to the present invention to increase the thickness of the deposited metal layer is amorphous silica, graphite powder, or a mixture thereof.
- amorphous silica is meant to include colloidal silica particles in any form, where the colloidal silica particles, which are also referred to as silica sols, may be derived from e.g. precipitated silica, silica gels, pyrogenic silica (fumed silica), micro silica (silica fume) or mixtures thereof.
- Colloidal silica according to the present invention may be modified and can contain other elements such as amines, aluminium and/or boron, which can be present in the particles and/or the continuous phase.
- the colloidal silica particles can be dispersed in a substantially aqueous solvent, suitably in the presence of stabilizing cations such as K + , Na + , Li + , NH 4 + , organic cations, primary, secondary, tertiary, and quaternary amines, and mixtures thereof, so as to form an aqueous silica sol.
- stabilizing cations such as K + , Na + , Li + , NH 4 + , organic cations, primary, secondary, tertiary, and quaternary amines, and mixtures thereof.
- organic solvents e.g. lower alcohols, acetone or mixtures thereof, also denoted as organo-silica sols
- the silica content in the sol is from about 5 to about 80% by weight.
- Aqueous silica sols suitable for use according to the present invention are e.g. commercially available from Akzo Nobel.
- Suitable organo-silica sols are e.g. commercially available from Nissan Chemical Industries.
- graphite powder finely divided carbon powder or carbon black, e.g. commercially available from Degussa.
- the additive is preferably used in a quantity of at least 0.01 wt%, more preferably of at least 0.05 wt%, and most preferably of at least 0.1 wt%, based on the total weight of the electrolyte.
- no more than 5 wt%, more preferably no more than 3 wt%, and most preferably no more than 1 wt% of additive is used, based on the total weight of the electrolyte.
- electrolyte stands for the total electrolyte mixture, i.e. including dissolved metal salts and additives.
- the layer thickness can be increased at least 10 times, more preferably at least 20 times, and most preferably at least 40 times, when compared to electrodeposition without said additive(s).
- the ionic liquid employed as electrolyte is preferably selected from the group consisting of N + R 1 R 2 R 3 R 4 X - , N + R 5 R 6 R 7 R 8 Y - , and mixtures thereof, wherein any one of R 1 to R 8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 , or OR 9 , wherein at least one of R 1 to R 4 is an, optionally branched, fatty alkyl chain, wherein R 2 can be a (C 2 -C 6 alkyl)-N + R 16 R 17 R 18 group with R 16 , R 17 , R 18 being similar to R 1 , R 3 , R 4 , respectively, or a C 1 to C 4 alkyl chain, and wherein one
- X- is selected from the group of F - , Cl - , Br - , I - ; the group of R 10 COO - anions wherein R 10 may be hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; the group of R 11 SO 4 - anions wherein R 11 may be absent, in which case the cation is divalent, hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; the group of R 12 SO 3 - anions wherein R 12 may be absent, in which case the cation is divalent, hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; the group of R 13 CO 3 - anions wherein R 13 may be absent, in which case the cation is divalent, hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; and the group of R 14 -N - -SO 2 -R 15 anions wherein R 14 and/
- a fatty alkyl chain is meant to include saturated and/or unsaturated chains and contains 8 to 22 carbon atoms; preferably, it contains 10 to 22 carbon atoms, most preferably 12 to 20 carbon atoms.
- an ionic liquid of the formula N + R 1 R 2 R 3 R 4 X - is used with R 1 , R 3 , and R 4 being as mentioned above and with R 2 being a (C 2 -C 6 alkyl)-N + R 16 R 17 R 18 group.
- R 16 , R 17 , and R 18 are identical to R 1 , R 2 and R 4 , respectively, with at least one of them being an, optionally branched, fatty alkyl chain, resulting in a gemini-type structure (i.e. a symmetrical diquaternary ammonium compound).
- Y - is based on a compound known as a sweetener.
- N + R 5 R 6 R 7 R 8 is an amine wherein the groups R 5 to R 8 are hydrogen or an alkyl or cycloalkyl, optionally substituted with OH or Cl; more preferably, at least three thereof are an alkyl, more preferably a C 1 to C 4 alkyl.
- the ionic liquid is selected from any one of choline saccharinate, choline acesulphamate, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, cocotrimethyl ammonium chloride, tallowtrimethyl ammonium chloride, hydrogenated tallowtrimethyl ammonium chloride, hydrogenated palmtrimethyl ammonium chloride, oleyltrimethyl ammonium chloride, soyatrimethyl ammonium chloride, cocobenzyldimethyl ammonium chloride, C12-16-alkylbenzyldimethyl ammonium chloride, hydrogenated tallowbenzyldimethyl ammonium chloride, dioctyldimethyl ammonium chloride, didecyldimethyl ammonium chloride, dicocodimethyl ammonium nitrite, dicocodimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammonium chloride
- ionic liquids suitable for use according to the present invention can be prepared by a simple reaction of salts, for example by a metathesis reaction of choline chloride and sodium saccharinate (acesulphamate) to form a choline saccharinate (acesulphamate) ionic liquid, or by quaternization of the corresponding amines.
- the molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt is preferably between 1,000:1 and 3:1. More preferred is a molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt of between 500:1 and 5:1, most preferred is a molar ratio between 100:1 and 7:1, this providing a good-quality metal layer, excellent dissolution of the metal in the ionic liquid, and a good balance between the cost of the process and the appearance of the plated substrate product.
- one of the metals chromium, aluminium, titanium, zinc or copper, or an alloy thereof is deposited. More preferably, chromium or aluminium is deposited, most preferably chromium.
- This metal deposition can be done from a metal salt dissolved in the electrolyte, for example a metal halide, preferably, but not limited to, a metal chloride. It can also be performed using a pure metal which is applied as anode (i.e. a chromium, aluminium, titanium, zinc, or copper anode). In the embodiment where a metal anode is used, the anode may be in the form of metal pieces, chunks, chips or any other suitable form known to the skilled person.
- the substrate which can be electroplated or electropolished according to the present invention can be any conductive object.
- it is an object which is solid metal, such as a carbon steel object, or it comprises conductive elements such as a composite material object.
- the present invention furthermore relates to a method to electroplate or electropolish a metal on a metal substrate wherein an ionic liquid ionic liquid is selected from the group consisting of N + R 1 R 2 R 3 R 4 X - , N + R 5 R 6 R 7 R 8 Y - , and mixtures thereof, wherein any one of R 1 to R 8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 , or OR 9 , wherein at least one of R 1 to R 4 is an, optionally branched, fatty alkyl chain, wherein R 2 can be a (C 2 -C 6 alkyl)-N + R 16 R 17 R 18 group with R 16 , R 17 , R 18 being similar to R 1 , R 3
- the additive is preferably used in the quantities as described above.
- the electrodeposition is preferably performed at temperatures below 90°C and more preferably at room temperature, in open electrodeposition vessels, but electrodeposition is not limited to these conditions.
- Comparative Example 1 Electroplating of chromium from CrCl 3 hexahydrate salt onto carbon steel in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride with no additives
- Chromium (III) chloride hexahydrate salt was added to cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid containing 0.2 wt% of water and the mixture was agitated at a temperature of about 50°C until the solid salt dissolved. In the prepared solution the concentration of chromium (III) chloride hexahydrate was 75 g/kg.
- Platinized titanium plate was applied as the anode and connected to the positive terminal of a DC power source, whereas carbon steel plate was used as the cathode (substrate) and connected to the negative terminal.
- the substrate plate Prior to introduction into the bath, the substrate plate was cleaned with a commercial scouring powder, washed in demineralized water, in acetone and after that in ethanol, and finally in a 4 M-HCl aqueous solution. When both plates were connected and introduced into the cell, the voltage difference was set to 30 V. The current flow was monitored on a meter connected in series.
- the cathode was disconnected from the power source and taken out of the cell.
- the plate was washed in water and acetone and then dried.
- Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate was performed. It confirmed deposition of chromium onto the carbon steel.
- the deposited layer thickness was measured using a thickness measurement device obtained from Fischer, Germany. The thickness was found to be lower than 0.5 ⁇ m.
- Example 2 Electroplating of chromium from CrCl 3 hexahydrate salt onto carbon steel in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride with addition of 0.2 wt% amorphous silica
- Example 2 To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 was added an amorphous silica aqueous colloidal solution which contained 8 wt% of active compound.
- Example 2 The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
- the cathode was disconnected from the power source and taken out of the cell.
- the plate was washed in water and acetone and then dried.
- Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate.
- the deposited layer thickness measured using a thickness measurement device (Fischer, Germany), was found to be as high as 8 ⁇ m in certain regions of the substrate, which was significantly thicker than when no additive was used. As is typical for the Hull cell experiments, the layer thickness varied with the position on the substrate - in this case from 1 ⁇ m to 8 ⁇ m. To confirm these measurements a cross-cut metallographic analysis was also done. The sample of the substrate was embedded in epoxy resin and the deposit was evaluated under the microscope. The layer thickness determined in this way was in agreement with the thickness measurement device results.
- Example 3 Electroplating of chromium from CrCl 3 hexahydrate salt onto carbon steel in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride with addition of 0.4 wt% amorphous silica
- Example 2 To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 was added an amorphous silica aqueous colloidal solution which contained 8 wt% of active compound. The concentration of the amorphous silica in the prepared solution, expressed as the quantity of the active compound, was 4 g/kg.
- Example 2 The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
- the cathode was disconnected from the power source and taken out of the cell.
- the plate was washed in water and acetone and then dried.
- Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate.
- the deposited layer thickness measured using a thickness measurement device (Fischer, Germany) and by cross-cut metallographic analysis, was found to be ranging from 1 to 9 ⁇ m.
- Example 4 Electroplating of chromium from CrCl 3 hexahydrate salt onto carbon steel in coco alkyl methyl [polyoxyethylene(15)] ammonium chloride with addition of 1 wt% of carbon black
- Example 2 The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
- the cathode was disconnected from the power source and taken out of the cell.
- the plate was washed in water and acetone and then dried.
- Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate.
- the deposited layer thickness measured using a thickness measurement device (Fischer, Germany), was found to be ranging from 1 to 7 ⁇ m. The same thickness values were found by cross-cut metallographic analysis of the substrate samples.
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Abstract
The present invention pertains to the use of an additive selected from the group consisting of amorphous silica, graphite powder, and a mixture thereof in a process to electroplate or electropolish a metal on a substrate using an ionic liquid as the electrolyte to increase metal layer thickness. It furthermore pertains to a method to electroplate or electropolish a metal on a metal substrate wherein an ionic liquid is employed as electrolyte, wherein a metal salt added to said ionic liquid or a metal anode is employed as metal source, and wherein said ionic liquid comprises said additive.
Description
- The present invention relates to a method to electrodeposit a metal on a substrate using an ionic liquid as the electrolyte in the presence of an additive, and to the use of said additive to increase the layer thickness of the deposited metal layer.
- An ionic liquid is a salt in which the ions are poorly coordinated, which results in these solvents being liquid at temperatures below 100°C. Many are liquid even at room temperature. At least one ion in an ionic liquid has a delocalized charge and one component is organic, which prevents the formation of a stable crystal lattice. Ionic liquids generally have very low vapour pressure and thus, in contrast to many conventional solvents, produce virtually no hazardous vapours. It is known that, in general, ionic liquids may be used in many applications, e.g. as reaction solvents, extraction solvents, electrolytes in batteries and electrodeposition, catalysts, heat exchange fluids, as additives in coatings.
- Well-known systems include those formed from alkylpyridinium halides or dialkylimidazolium halides with an aluminium halide, and those based on choline chloride and a (hydrated) metal salt such as chromium(III) chloride. These systems have been utilized as electrolytes in electroplating, as described for example in
EP 0 404 188 andEP 1 322 591 . - Further,
WO 2002/026381 discloses ionic liquids (eutectic mixtures) of choline chloride and a (hydrated) metal salt such as chromium(III) chloride and the use thereof in electrodeposition and electropolishing. The mixtures consist of choline chloride and the (hydrated) metal salt in a ratio of ammonium to metal ion of between 1:1 and 1:2.5 and are specifically said to be suitable for depositing chromium, cobalt, zinc or silver on a metal substrate. - Moreover,
PCT/EP/2007/051329
N+R1R2R3R4 X- or
N+R5R6R7R8 Y-
is employed as electrolyte, and a metal salt added to the ionic liquid is employed as the metal source or a metal anode is used as the metal source, wherein any one of R1 to R8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH2, CN, NO2, COOR9, CHO, COR9, or OR9, at least one of R5 to R8 is a fatty alkyl chain, and one or more of R5 to R8 can be a (poly)oxyalkylene group wherein the alkylene is a C1 to C4 alkylene and the total number of oxyalkylene units can be from 1 to 50 oxyalkylene units, and at least one of R1 to R8 is a C1 to C4 alkyl chain, R9 is an alkyl or cycloalkyl group, X- is an anion having an N-acyl sulphonylimide anion (-CO-N--SO2-) functionality, Y- is an anion compatible with the N+R5R6R7R8 ammonium cation, such as a halogenide anion, a carboxylate anion, a sulphate (both organic and inorganic sulphate), sulphonate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, or sulphonylimide anion. - The use of ionic liquids as electrolytes in electrodeposition processes has several advantages. Conventional chromic acid plating processes, for example, are extremely hazardous because they mainly rely on hexavalent chromium, which is highly toxic and carcinogenic. Ionic liquids, on the other hand, may eliminate the necessity to use hexavalent chromium and allow the use of trivalent chromium, which is considered to be far less dangerous. Also, conventional chromium plating baths require the use of strong acids, which poses significant disposal problems, while the use of ionic liquids generally enables such disposal difficulties to be minimized or even eliminated. Moreover, ionic liquids are non-volatile, so they do not cause atmospheric pollution. However, a drawback to the prior art electrodeposition processes wherein an ionic liquid is used as the electrolyte is that depositing metal layers of some metals thicker than 150-200 nm is difficult or even impossible.
- For some applications, such as decorative plating, having thin metal layers is acceptable. However, for applications where the metal layer needs to provide protection against wear or abrasion, or to improve hardness (functional plating), metal layers much thicker than 200 nm are required. More particularly, layers of several micrometers or even several tens of micrometers are desirable.
- Hence, there is a need for improved ionic liquid-based electrodeposition systems with which metal layers of increased thickness are deposited.
- Surprisingly, it has been found that by adding a particular additive to the ionic liquid-based plating baths, thicker metal layers are deposited. In more detail, the present invention relates to the use of amorphous silica, graphite powder, or a mixture thereof as additive in a process to electroplate or electropolish a metal on a substrate wherein an ionic liquid is employed as the electrolyte to increase metal layer thickness. Additionally, the invention relates to a method according to claim 7.
- Additives have been added to the ionic liquid comprising electrolyte for several reasons.
US 7,196,221 , for example, discloses the use of brightening agents to improve the appearance of the coatings obtained in ionic liquid solvents/- electrolytes during metal plating and electropolishing processes, and in particular in chromium plating processes. The brightening agents include thiourea, saccharin, vanillin, allyl urea, nicotinic acid, citric acid, gelatin, 2-mercaptobenzothiazole, tetraethylammonium fluoride dihydrate or tetramethylammonium hydroxide pentahydrate. However, these additives have an adverse effect on the homogeneity of the deposited layer, or no effect at all. -
WO 2006/074523 relates to a process for the recovery of platinum group metal, which comprises electrodeposition of the platinum group metal from an ionic liquid wherein redox reagents, complexing agents, conductivity enhancers may be present. -
US 6,552,843 , which is concerned with devices, such as adjustable mirrors, smart windows, optical attenuators, and displays, for controlling the reflectance and/or transmission of electromagnetic radiation, discloses a reversible electrodeposition optical modulation device employing an ionic liquid electrolyte. The ionic liquid electrolyte is comprised of a mixture of an ionic organic compound and the salt of an electrodepositable metal. The ionic organic compound comprises a heterocyclic cation such as N-alkylpyrrolidinium, pyrrolidinium, 1-alkyl-3-methylimidazolium, N-alkylpyridinium, 2-alkyl-1-pyrrolinium, 1-alkylimidazolium. The electrodepositable metal is silver, copper, tin, zinc, palladium, bismuth, cadmium, mercury, indium, lead, antimony, thallium, and alloys thereof. It is mentioned that said ionic liquid electrolyte may be rendered more viscous, semi-solid or solid by addition of organic or inorganic gelling agents. Inorganic or organic materials, including suspended carbon and dissolved dyes, may be added to the electrolyte to impart a desired colour or to reduce background reflection. - None of these documents teaches how to obtain thicker metal layers in electrodeposition processes with ionic liquid comprising electrolytes.
- The term electrodeposition in this application should be understood to include both electroplating and electropolishing. By electroplating is meant the process of using electrical current to coat an electrically conductive object with a layer of metal. The preferred result is a thin, smooth, even coat of metal on the object. The primary application of electroplating is to deposit a layer of a metal having some desired property (e.g., abrasion and wear resistance, corrosion protection, lubricity, improvement of aesthetic qualities, etc.) onto a surface lacking that property. Another application uses electroplating to build up thickness on undersized parts. By electropolishing is meant smoothing and enhancing the appearance of an originally rough or uneven metal surface by coating it with a relatively thin metal layer.
- The additive used according to the present invention to increase the thickness of the deposited metal layer is amorphous silica, graphite powder, or a mixture thereof.
- The term amorphous silica is meant to include colloidal silica particles in any form, where the colloidal silica particles, which are also referred to as silica sols, may be derived from e.g. precipitated silica, silica gels, pyrogenic silica (fumed silica), micro silica (silica fume) or mixtures thereof. Colloidal silica according to the present invention may be modified and can contain other elements such as amines, aluminium and/or boron, which can be present in the particles and/or the continuous phase.
- The colloidal silica particles can be dispersed in a substantially aqueous solvent, suitably in the presence of stabilizing cations such as K+, Na+, Li+, NH4 +, organic cations, primary, secondary, tertiary, and quaternary amines, and mixtures thereof, so as to form an aqueous silica sol. However, also dispersions comprising organic solvents, e.g. lower alcohols, acetone or mixtures thereof, also denoted as organo-silica sols, may be used. Preferably, the silica content in the sol is from about 5 to about 80% by weight.
- Aqueous silica sols suitable for use according to the present invention are e.g. commercially available from Akzo Nobel. Suitable organo-silica sols are e.g. commercially available from Nissan Chemical Industries.
- By graphite powder is meant finely divided carbon powder or carbon black, e.g. commercially available from Degussa.
- The additive is preferably used in a quantity of at least 0.01 wt%, more preferably of at least 0.05 wt%, and most preferably of at least 0.1 wt%, based on the total weight of the electrolyte. Preferably, no more than 5 wt%, more preferably no more than 3 wt%, and most preferably no more than 1 wt% of additive is used, based on the total weight of the electrolyte. It is noted that the term electrolyte stands for the total electrolyte mixture, i.e. including dissolved metal salts and additives.
- With the present invention, i.e. with the addition of the described additive(s), the layer thickness can be increased at least 10 times, more preferably at least 20 times, and most preferably at least 40 times, when compared to electrodeposition without said additive(s).
- The ionic liquid employed as electrolyte is preferably selected from the group consisting of N+R1R2R3R4 X-, N+R5R6R7R8 Y-, and mixtures thereof, wherein any one of R1 to R8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH2, CN, NO2, COOR9, CHO, COR9, or OR9, wherein at least one of R1 to R4 is an, optionally branched, fatty alkyl chain, wherein R2 can be a (C2-C6 alkyl)-N+R16R17R18 group with R16, R17, R18 being similar to R1, R3, R4, respectively, or a C1 to C4 alkyl chain, and wherein one or more of R1 to R8 can be a (poly)oxyalkylene group wherein the alkylene is a C1 to C4 alkylene and the total number of oxyalkylene units can be from 1 to 50 oxyalkylene units, and wherein at least one of R1 to R8 is a C1 to C4 alkyl chain, wherein R9 is an alkyl or cycloalkyl group, wherein X- is an anion compatible with the N+R1R2R3R4 ammonium cation, such as a halogenide anion, a carboxylate anion, a sulphate (both organic and inorganic sulphate), sulphonate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, saccharinate anion, or sulphonylimide anion, and wherein Y- is an anion having a sulfonylimide anion or an N-acyl sulphonylimide anion (-CO-N--SO2-) functionality.
- In one embodiment, X- is selected from the group of F-, Cl-, Br-, I-; the group of R10COO- anions wherein R10 may be hydrogen, a C1-C22 alkyl, alkenyl or aromatic group; the group of R11SO4 - anions wherein R11 may be absent, in which case the cation is divalent, hydrogen, a C1-C22 alkyl, alkenyl or aromatic group; the group of R12SO3 - anions wherein R12 may be absent, in which case the cation is divalent, hydrogen, a C1-C22 alkyl, alkenyl or aromatic group; the group of R13CO3 - anions wherein R13 may be absent, in which case the cation is divalent, hydrogen, a C1-C22 alkyl, alkenyl or aromatic group; and the group of R14-N--SO2-R15 anions wherein R14 and/or R15 independently may be hydrogen, a C1-C22 alkyl, alkenyl or aromatic group, and R14 may be linked to the nitrogen atom with a carbonyl group.
- A fatty alkyl chain is meant to include saturated and/or unsaturated chains and contains 8 to 22 carbon atoms; preferably, it contains 10 to 22 carbon atoms, most preferably 12 to 20 carbon atoms.
- In another embodiment, an ionic liquid of the formula N+R1R2R3R4 X- is used with R1, R3, and R4 being as mentioned above and with R2 being a (C2-C6alkyl)-N+R16R17R18 group. Preferably, R16, R17, and R18 are identical to R1, R2 and R4, respectively, with at least one of them being an, optionally branched, fatty alkyl chain, resulting in a gemini-type structure (i.e. a symmetrical diquaternary ammonium compound).
- In another embodiment, Y- is based on a compound known as a sweetener. In another embodiment, N+R5R6R7R8 is an amine wherein the groups R5 to R8 are hydrogen or an alkyl or cycloalkyl, optionally substituted with OH or Cl; more preferably, at least three thereof are an alkyl, more preferably a C1 to C4 alkyl.
- In a preferred embodiment, the ionic liquid is selected from any one of choline saccharinate, choline acesulphamate, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, cocotrimethyl ammonium chloride, tallowtrimethyl ammonium chloride, hydrogenated tallowtrimethyl ammonium chloride, hydrogenated palmtrimethyl ammonium chloride, oleyltrimethyl ammonium chloride, soyatrimethyl ammonium chloride, cocobenzyldimethyl ammonium chloride, C12-16-alkylbenzyldimethyl ammonium chloride, hydrogenated tallowbenzyldimethyl ammonium chloride, dioctyldimethyl ammonium chloride, didecyldimethyl ammonium chloride, dicocodimethyl ammonium nitrite, dicocodimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammonium chloride, di(hydrogenated tallow)benzylmethyl ammonium chloride, ditallowdimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, hydrogenated tallow(2-ethylhexyl)dimethyl ammonium chloride, hydrogenated tallow(2-ethylhexyl)dimethyl ammonium methylsulphate, trihexadecylmethyl ammonium chloride, octadecylmethylbis(2-hydroxyethyl) ammonium chloride, cocobis(2-hydroxyethyl)methyl ammonium nitrate, cocobis(2-hydroxyethyl)methyl ammonium chloride, cocobis(2-hydroxyethyl)benzyl ammonium chloride, oleylbis(2-hydroxyethyl)methyl ammonium chloride, coco[polyoxyethylene(15)]methyl ammonium chloride, coco[polyoxyethylene(15)]methyl ammonium methylsulphate, coco[polyoxyethylene(17)]methyl ammonium chloride, octadecyl-[polyoxyethylene(15)]methyl ammonium chloride, hydrogenated tallow[polyoxyethylene(15)]methyl ammonium chloride, tris(2-hydroxyethyl)tallow ammonium acetate, tallow-1,3-propane pentamethyl diammonium dichloride.
- Many of the above-indicated ionic liquids suitable for use according to the present invention can be prepared by a simple reaction of salts, for example by a metathesis reaction of choline chloride and sodium saccharinate (acesulphamate) to form a choline saccharinate (acesulphamate) ionic liquid, or by quaternization of the corresponding amines.
- The molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt, which comes from the dissolved salt or from the metal anode, is preferably between 1,000:1 and 3:1. More preferred is a molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt of between 500:1 and 5:1, most preferred is a molar ratio between 100:1 and 7:1, this providing a good-quality metal layer, excellent dissolution of the metal in the ionic liquid, and a good balance between the cost of the process and the appearance of the plated substrate product.
- Preferably, one of the metals chromium, aluminium, titanium, zinc or copper, or an alloy thereof is deposited. More preferably, chromium or aluminium is deposited, most preferably chromium. This metal deposition can be done from a metal salt dissolved in the electrolyte, for example a metal halide, preferably, but not limited to, a metal chloride. It can also be performed using a pure metal which is applied as anode (i.e. a chromium, aluminium, titanium, zinc, or copper anode). In the embodiment where a metal anode is used, the anode may be in the form of metal pieces, chunks, chips or any other suitable form known to the skilled person.
- The substrate which can be electroplated or electropolished according to the present invention can be any conductive object. Preferably, it is an object which is solid metal, such as a carbon steel object, or it comprises conductive elements such as a composite material object.
- The present invention furthermore relates to a method to electroplate or electropolish a metal on a metal substrate wherein an ionic liquid ionic liquid is selected from the group consisting of N+R1R2R3R4 X-, N+R5R6R7R8 Y-, and mixtures thereof, wherein any one of R1 to R8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH2, CN, NO2, COOR9, CHO, COR9, or OR9, wherein at least one of R1 to R4 is an, optionally branched, fatty alkyl chain, wherein R2 can be a (C2-C6 alkyl)-N+R16R17R18 group with R16, R17, R18 being similar to R1, R3, R4, respectively, or a C1 to C4 alkyl chain, and wherein one or more of R1 to R8 can be a (poly)oxyalkylene group wherein the alkylene is a C1 to C4 alkylene and the total number of oxyalkylene units can be from 1 to 50 oxyalkylene units, and wherein at least one of R1 to R8 is a C1 to C4 alkyl chain, wherein R9 is an alkyl or cycloalkyl group, wherein X- is an anion compatible with the N+R1R2R3R4 ammonium cation, such as a halogenide anion, a carboxylate anion, a sulphate (both organic and inorganic sulphate), sulphonate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, saccharinate anion, or sulphonylimide anion, and wherein Y- is an anion having a sulfonylimide anion or an N-acyl sulphonylimide anion (-CO-N--SO2-) functionality,
wherein a metal salt added to said ionic liquid or a metal anode is employed as metal source, and
wherein said ionic liquid comprises at least 0.01 wt%, based on the total weight of electrolyte, of an additive selected from the group consisting of amorphous silica, graphite powder, and of a mixture thereof. - The additive is preferably used in the quantities as described above.
- The electrodeposition is preferably performed at temperatures below 90°C and more preferably at room temperature, in open electrodeposition vessels, but electrodeposition is not limited to these conditions.
- The process according to the present invention is further illustrated by the following examples.
- Chromium (III) chloride hexahydrate salt was added to cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid containing 0.2 wt% of water and the mixture was agitated at a temperature of about 50°C until the solid salt dissolved. In the prepared solution the concentration of chromium (III) chloride hexahydrate was 75 g/kg.
- About 250 ml of that solution was poured into the Hull cell equipped with an electrical heating element which had a length of 65 mm on the anode side and 102 mm on the cathode side, a 48 mm shortest anode-cathode distance, a 127 mm longest anode-cathode distance, and a depth of 65 mm. The cell was heated and the temperature was maintained at about 80°C. The liquid was agitated using a centrally positioned top-entering impeller.
- Platinized titanium plate was applied as the anode and connected to the positive terminal of a DC power source, whereas carbon steel plate was used as the cathode (substrate) and connected to the negative terminal. Prior to introduction into the bath, the substrate plate was cleaned with a commercial scouring powder, washed in demineralized water, in acetone and after that in ethanol, and finally in a 4 M-HCl aqueous solution. When both plates were connected and introduced into the cell, the voltage difference was set to 30 V. The current flow was monitored on a meter connected in series.
- After several hours of electroplating, the cathode was disconnected from the power source and taken out of the cell. The plate was washed in water and acetone and then dried. Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate was performed. It confirmed deposition of chromium onto the carbon steel. The deposited layer thickness was measured using a thickness measurement device obtained from Fischer, Germany. The thickness was found to be lower than 0.5 µm.
- To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 was added an amorphous silica aqueous colloidal solution which contained 8 wt% of active compound. The concentration of the amorphous silica in the prepared solution, expressed as the quantity of the active compound, was 1.6 g/kg.
- About 250 ml of that solution was poured into the Hull cell described in Example 1. The cell was heated to a temperature of about 80°C.
- The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
- After several hours of submission to the current, the cathode was disconnected from the power source and taken out of the cell. The plate was washed in water and acetone and then dried. Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate. The deposited layer thickness, measured using a thickness measurement device (Fischer, Germany), was found to be as high as 8 µm in certain regions of the substrate, which was significantly thicker than when no additive was used. As is typical for the Hull cell experiments, the layer thickness varied with the position on the substrate - in this case from 1 µm to 8 µm. To confirm these measurements a cross-cut metallographic analysis was also done. The sample of the substrate was embedded in epoxy resin and the deposit was evaluated under the microscope. The layer thickness determined in this way was in agreement with the thickness measurement device results.
- To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 was added an amorphous silica aqueous colloidal solution which contained 8 wt% of active compound. The concentration of the amorphous silica in the prepared solution, expressed as the quantity of the active compound, was 4 g/kg.
- About 250 ml of that solution was poured into the Hull cell described in Example 1. The cell was heated to a temperature of about 80°C.
- The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
- After several hours of submission to the current, the cathode was disconnected from the power source and taken out of the cell. The plate was washed in water and acetone and then dried. Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate. The deposited layer thickness, measured using a thickness measurement device (Fischer, Germany) and by cross-cut metallographic analysis, was found to be ranging from 1 to 9 µm.
- To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 carbon black was added. The concentration of the carbon black in the prepared mixture was 10 g/kg.
- About 250 ml of that mixture was poured into the Hull cell described in Example 1. The cell was heated to a temperature of about 70°C.
- The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
- After several hours of submission to the current, the cathode was disconnected from the power source and taken out of the cell. The plate was washed in water and acetone and then dried. Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate. The deposited layer thickness, measured using a thickness measurement device (Fischer, Germany), was found to be ranging from 1 to 7 µm. The same thickness values were found by cross-cut metallographic analysis of the substrate samples.
Claims (10)
- Use of an additive selected from the group consisting of amorphous silica, graphite powder, and a mixture thereof in a process to electroplate or electropolish a metal on a substrate using an ionic liquid as the electrolyte to increase metal layer thickness.
- Use of the additive according to claim 1 wherein the ionic liquid is selected from the group consisting of N+R1R2R3R4 X-, N+R5R6R7R8 Y-, and mixtures thereof, wherein any one of R1 to R8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH2, CN, NO2, COOR9, CHO, COR9, or OR9, wherein at least one of R1 to R4 is an, optionally branched, fatty alkyl chain, wherein R2 can be a (C2-C6 alkyl)-N+R16R17R18 group with R16, R17, R18 being similar to R1, R3, R4, respectively, or a C1 to C4 alkyl chain, and wherein one or more of R1 to R8 can be a (poly)oxyalkylene group wherein the alkylene is a C1 to C4 alkylene and the total number of oxyalkylene units can be from 1 to 50 oxyalkylene units, and wherein at least one of R1 to R8 is a C1 to C4 alkyl chain, wherein R9 is an alkyl or cycloalkyl group, wherein X- is an anion compatible with the N+R1R2R3R4 ammonium cation, such as a halogenide anion, a carboxylate anion, a sulphate (both organic and inorganic sulphate), sulphonate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, saccharinate anion, or sulphonylimide anion, and wherein Y- is an anion having a sulfonylimide anion or an N-acyl sulphonylimide anion (-CO-N--SO2-) functionality.
- Use of the additive according to claim 1 or 2 wherein the metal which is electroplated or electropolished on the substrate originates from a metal source either being a metal salt selected from the group consisting of chromium, aluminium, titanium, zinc and copper salts, or an anode selected from the group consisting of chromium, aluminium, titanium, zinc, and copper anodes.
- Use of the additive according to any one of the preceding claims wherein the molar ratio of the cation of the ionic liquid to the metal cation of the metal salt or derived from the metal anode is between 1,000 : 1 and 3 :1, preferably between 100:1 and 7:1.
- Use of the additive according to claim 4 in an amount of between 0.1 wt% and 5 wt%, based on the total weight of electrolyte.
- Use of the additive according to any one of the preceding claims wherein the ionic liquid is selected from the group consisting of choline saccharinate, choline acesulphamate, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, cocotrimethyl ammonium chloride, tallowtrimethyl ammonium chloride, hydrogenated tallowtrimethyl ammonium chloride, hydrogenated palmtrimethyl ammonium chloride, oleyltrimethyl ammonium chloride, soyatrimethyl ammonium chloride, cocobenzyldimethyl ammonium chloride, C12-16-alkylbenzyldimethyl ammonium chloride, hydrogenated tallowbenzyldimethyl ammonium chloride, dioctyldimethyl ammonium chloride, didecyldimethyl ammonium chloride, dicocodimethyl ammonium nitrite, dicocodimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammonium chloride, di(hydrogenated tallow)benzylmethyl ammonium chloride, ditallowdimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, hydrogenated tallow(2-ethylhexyl)dimethyl ammonium chloride, hydrogenated tallow(2-ethylhexyl)dimethyl ammonium methylsulphate, trihexadecylmethyl ammonium chloride, octadecylmethylbis(2-hydroxyethyl) ammonium chloride, cocobis(2-hydroxyethyl)methyl ammonium nitrate, cocobis(2-hydroxyethyl)methyl ammonium chloride, cocobis(2-hydroxyethyl)benzyl ammonium chloride, oleylbis(2-hydroxyethyl)methyl ammonium chloride, coco[polyoxyethylene(15)]methyl ammonium chloride, coco[polyoxyethylene(15)]methyl ammonium methylsulphate, coco[polyoxyethylene(17)]methyl ammonium chloride, octadecyl[polyoxyethylene(15)]methyl ammonium chloride, hydrogenated tallow[polyoxyethylene(15)]methyl ammonium chloride, tris(2-hydroxyethyl)tallow ammonium acetate, tallow-1,3-propane pentamethyl diammonium dichloride.
- A method to electroplate or electropolish a metal on a metal substrate wherein an ionic liquid is selected from the group consisting of N+R1R2R3R4 X-, N+R5R6R7R8 Y-, and mixtures thereof, wherein any one of R1 to R8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH2, CN, NO2, COOR9, CHO, COR9, or OR9, wherein at least one of R1 to R4 is an, optionally branched, fatty alkyl chain, wherein R2 can be a (C2-C6 alkyl)-N+R16R17R18 group with R16, R17, R18 being similar to R1, R3, R4, respectively, or a C1 to C4 alkyl chain, and wherein one or more of R1 to R8 can be a (poly)oxyalkylene group wherein the alkylene is a C1 to C4 alkylene and the total number of oxyalkylene units can be from 1 to 50 oxyalkylene units, and wherein at least one of R1 to R8 is a C1 to C4 alkyl chain, wherein R9 is an alkyl or cycloalkyl group, wherein X- is an anion compatible with the N+R1R2R3R4 ammonium cation, such as a halogenide anion, a carboxylate anion, a sulphate (both organic and inorganic sulphate), sulphonate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, saccharinate anion, or sulphonylimide anion, and wherein Y- is an anion having a sulfonylimide anion or an N-acyl sulphonylimide anion (-CO-N--SO2-) functionality; wherein a metal salt added to said ionic liquid or a metal anode is employed as metal source; and wherein said ionic liquid comprises at least 0.01 wt%, based on the total weight of electrolyte, of an additive selected from the group consisting of amorphous silica, graphite powder, and of a mixture thereof.
- A method according to claim 7 wherein the metal which is electroplated or electropolished on the substrate originates from a metal source either being a metal salt selected from the group consisting of chromium, aluminium, titanium, zinc and copper salts, or an anode selected from the group consisting of chromium, aluminium, titanium, zinc, and copper anodes.
- A method according to claim 7 or 8 wherein the molar ratio of the cation of the ionic liquid to the metal cation of the metal salt or derived from the metal anode is between 1,000 : 1 and 3 :1, and preferably between 100:1 and 7:1.
- A method according to any one of claims 7-9 wherein the ionic liquid is selected from the group consisting of choline saccharinate, choline acesulphamate, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, cocotrimethyl ammonium chloride, tallowtrimethyl ammonium chloride, hydrogenated tallowtrimethyl ammonium chloride, hydrogenated palmtrimethyl ammonium chloride, oleyltrimethyl ammonium chloride, soyatrimethyl ammonium chloride, cocobenzyldimethyl ammonium chloride, C12-16-alkylbenzyldimethyl ammonium chloride, hydrogenated tallowbenzyldimethyl ammonium chloride, dioctyldimethyl ammonium chloride, didecyldimethyl ammonium chloride, dicocodimethyl ammonium nitrite, dicocodimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammonium chloride, di(hydrogenated tallow)benzylmethyl ammonium chloride, ditallowdimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, hydrogenated tallow(2-ethylhexyl)dimethyl ammonium chloride, hydrogenated tallow(2-ethylhexyl)dimethyl ammonium methylsulphate, trihexadecylmethyl ammonium chloride, octadecylmethylbis(2-hydroxyethyl) ammonium chloride, cocobis(2-hydroxyethyl)methyl ammonium nitrate, cocobis(2-hydroxyethyl)methyl ammonium chloride, cocobis(2-hydroxyethyl)benzyl ammonium chloride, oleylbis(2-hydroxyethyl)methyl ammonium chloride, coco[polyoxyethylene(15)]methyl ammonium chloride, coco[polyoxyethylene(15)]methyl ammonium methylsulphate, coco[polyoxyethylene(17)]methyl ammonium chloride, octadecyl[polyoxyethylene(15)]methyl ammonium chloride, hydrogenated tallow[polyoxyethylene(15)]methyl ammonium chloride, tris(2-hydroxyethyl)tallow ammonium acetate, tallow-1,3-propane pentamethyl diammonium dichloride.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL08786597T PL2171131T3 (en) | 2007-08-02 | 2008-07-30 | Method to electrodeposit metals using ionic liquids in the presence of an additive |
| EP08786597A EP2171131B1 (en) | 2007-08-02 | 2008-07-30 | Method to electrodeposit metals using ionic liquids in the presence of an additive |
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| EP07113717 | 2007-08-02 | ||
| US95443407P | 2007-08-07 | 2007-08-07 | |
| PCT/EP2008/059962 WO2009016189A1 (en) | 2007-08-02 | 2008-07-30 | Method to electrodeposit metals using ionic liquids in the presence of an additive |
| EP08786597A EP2171131B1 (en) | 2007-08-02 | 2008-07-30 | Method to electrodeposit metals using ionic liquids in the presence of an additive |
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| EP2171131B1 true EP2171131B1 (en) | 2010-12-29 |
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| WO2010105299A1 (en) * | 2009-03-17 | 2010-09-23 | Commonwealth Scientific And Industrial Research Organisation | Electrorecovery of metals |
| DE102009035660A1 (en) * | 2009-07-30 | 2011-02-03 | Ewald Dörken Ag | Process for the electrochemical coating of a workpiece |
| US20120189778A1 (en) * | 2011-01-26 | 2012-07-26 | Riewe Curtis H | Coating method using ionic liquid |
| CN102888630B (en) * | 2011-07-20 | 2015-11-18 | 中国科学院过程工程研究所 | A kind of ionic liquid/additive system Low-temperature electro-deposition prepares the method for nano aluminum or nano aluminum coating |
| US9758884B2 (en) * | 2012-02-16 | 2017-09-12 | Stacey Hingley | Color control of trivalent chromium deposits |
| DE102012104707A1 (en) * | 2012-05-31 | 2013-12-05 | Benteler Automobiltechnik Gmbh | Method for producing an exhaust gas heat exchanger |
| DK2859138T3 (en) | 2012-06-08 | 2017-02-27 | Onderzoekscentrum Voor Aanwending Van Staal N V | Process for making a metal coating |
| CN102839403B (en) * | 2012-09-10 | 2015-02-25 | 太原理工大学 | Method for electroplating aluminum in ionic liquid |
| CN103484900A (en) * | 2013-09-18 | 2014-01-01 | 湖南工业大学 | Method for preparing crystalline nanocrystal micro-crack-free chromium coating in ionic liquid in direct electro-deposition mode |
| WO2015088876A1 (en) | 2013-12-10 | 2015-06-18 | Lei Chen | Nickel-chromium-aluminum composite by electrodeposition |
| EP3080321B1 (en) | 2013-12-10 | 2019-07-31 | United Technologies Corporation | Method for electrodepositing a nickel-chromium alloy |
| US10378118B2 (en) * | 2013-12-11 | 2019-08-13 | United Technologies Corporation | Electroformed nickel-chromium alloy |
| CN104294327B (en) * | 2014-10-20 | 2016-07-13 | 中国科学院过程工程研究所 | A kind of ionic liquid electrolytic solution and the method for preparing bright aluminum coating with the electrolytic solution |
| CN105220216B (en) * | 2015-09-28 | 2017-08-25 | 中国科学院兰州化学物理研究所 | A kind of aluminum or aluminum alloy electrochemical polishing method |
| TWI662162B (en) * | 2016-11-15 | 2019-06-11 | 財團法人工業技術研究院 | Electroplating method and system thereof |
| JP7072796B2 (en) * | 2018-02-19 | 2022-05-23 | 国立大学法人 名古屋工業大学 | Dimming member |
| US20210156041A1 (en) * | 2019-11-22 | 2021-05-27 | Hamilton Sundstrand Corporation | Metallic coating and method of application |
| US12050389B2 (en) | 2020-10-23 | 2024-07-30 | The Regents Of The University Of Colorado, A Body Corporate | Electrolyte additive for controlling morphology and optics of reversible metal films |
| CN118028962B (en) * | 2024-02-23 | 2024-12-10 | 广东倍亮科技有限公司 | Application of ionic liquids in electrolytic polishing of metal solids |
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| JPS5265120A (en) * | 1975-11-26 | 1977-05-30 | Sony Corp | Electro plating method of aluminium or aluminium alloy |
| JPH01132571A (en) * | 1987-11-18 | 1989-05-25 | Aguro Kanesho Kk | Agricultural and horticultural fungicide |
| GB0023706D0 (en) * | 2000-09-27 | 2000-11-08 | Scionix Ltd | Ionic liquids |
| GB0023708D0 (en) * | 2000-09-27 | 2000-11-08 | Scionix Ltd | Hydrated salt mixtures |
| US6552843B1 (en) * | 2002-01-31 | 2003-04-22 | Innovative Technology Licensing Llc | Reversible electrodeposition device with ionic liquid electrolyte |
| US20050205425A1 (en) * | 2002-06-25 | 2005-09-22 | Integran Technologies | Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents |
| US6721080B1 (en) * | 2002-09-27 | 2004-04-13 | D Morgan Tench | Optimum switching of a reversible electrochemical mirror device |
| US6798556B2 (en) * | 2003-01-31 | 2004-09-28 | Rockwell Scientific Licensing, Llc. | Locally-switched reversible electrodeposition optical modulator |
| DE102004059520A1 (en) * | 2004-12-10 | 2006-06-14 | Merck Patent Gmbh | Electrochemical deposition of tantalum and / or copper in ionic liquids |
| US7320832B2 (en) * | 2004-12-17 | 2008-01-22 | Integran Technologies Inc. | Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate |
| JP2007070698A (en) * | 2005-09-07 | 2007-03-22 | Kyoto Univ | Metal electrodeposition method |
| EP1984541A2 (en) * | 2006-02-15 | 2008-10-29 | Akzo Nobel N.V. | Method to electrodeposit metals using ionic liquids |
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- 2008-07-30 CN CN2008801010499A patent/CN101765681B/en not_active Expired - Fee Related
- 2008-07-30 DE DE602008004255T patent/DE602008004255D1/en active Active
- 2008-07-30 US US12/671,830 patent/US20100252446A1/en not_active Abandoned
- 2008-07-30 JP JP2010518655A patent/JP2010535283A/en active Pending
- 2008-08-01 TW TW097129448A patent/TWI359880B/en not_active IP Right Cessation
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2010
- 2010-10-13 HK HK10109690.2A patent/HK1143194A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP2171131A1 (en) | 2010-04-07 |
| CN101765681B (en) | 2013-03-20 |
| CA2695488A1 (en) | 2009-02-05 |
| HK1143194A1 (en) | 2010-12-24 |
| WO2009016189A1 (en) | 2009-02-05 |
| TW200925334A (en) | 2009-06-16 |
| DE602008004255D1 (en) | 2011-02-10 |
| ES2358967T3 (en) | 2011-05-17 |
| US20100252446A1 (en) | 2010-10-07 |
| PL2171131T3 (en) | 2011-05-31 |
| JP2010535283A (en) | 2010-11-18 |
| CN101765681A (en) | 2010-06-30 |
| ATE493523T1 (en) | 2011-01-15 |
| TWI359880B (en) | 2012-03-11 |
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