US3878066A - Bath for galvanic deposition of gold and gold alloys - Google Patents
Bath for galvanic deposition of gold and gold alloys Download PDFInfo
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- US3878066A US3878066A US394959A US39495973A US3878066A US 3878066 A US3878066 A US 3878066A US 394959 A US394959 A US 394959A US 39495973 A US39495973 A US 39495973A US 3878066 A US3878066 A US 3878066A
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- United States
- Prior art keywords
- bath
- gold
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- per liter
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- Prior art date
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- 229910001020 Au alloy Inorganic materials 0.000 title claims abstract description 12
- 239000003353 gold alloy Substances 0.000 title claims abstract description 12
- 239000010931 gold Substances 0.000 title abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title abstract description 17
- 229910052737 gold Inorganic materials 0.000 title abstract description 17
- 230000008021 deposition Effects 0.000 title abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- -1 ALKALI METAL SALT Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002065 alloy metal Inorganic materials 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229940000488 arsenic acid Drugs 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000002344 gold compounds Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- 150000001495 arsenic compounds Chemical class 0.000 abstract description 6
- 229940093920 gynecological arsenic compound Drugs 0.000 abstract description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract description 6
- 150000002830 nitrogen compounds Chemical class 0.000 abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000009499 grossing Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 150000001447 alkali salts Chemical class 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 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
- 239000002932 luster Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 2
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229940083542 sodium Drugs 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- GSMCZRMXOTVCGF-UHFFFAOYSA-N 2-bromo-1-(5-methyl-1,2-oxazol-3-yl)ethanone Chemical compound CC1=CC(C(=O)CBr)=NO1 GSMCZRMXOTVCGF-UHFFFAOYSA-N 0.000 description 1
- AQBIULJUXYJEEP-UHFFFAOYSA-N 6-ethoxyhexan-1-amine Chemical compound CCOCCCCCCN AQBIULJUXYJEEP-UHFFFAOYSA-N 0.000 description 1
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 229940097322 potassium arsenite Drugs 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- HEQWEGCSZXMIJQ-UHFFFAOYSA-M potassium;oxoarsinite Chemical compound [K+].[O-][As]=O HEQWEGCSZXMIJQ-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- the invention relates to a bath for the galvanic deposition of gold coatings and gold alloy coatings, containing a combination of organic compounds on a base of aldehydes and nitrogen compounds with arsenic compounds.
- an object of the present invention to avoid the disadvantages of the known electrolytes and to provide galvanic baths from which smooth coatings of gold and the alloys can be deposited.
- a bath which is characterized by a content of t A. at least one compound of the general formula R CHO in which R signifies hydrogen, methyl or the group -CHO, or one of its addition compounds and B. at least one compound of the general formula in which the radicals R are identical or different and represent hydrogen, possibly alkyl substituted by hydroxy groups with preferably 1 to 4 carbon atoms or aryl and R alkylidene radicals with preferably 1 to 5 carbon atoms, in and n being or representing integers from 1 to 3, or one of their salts and C. at least one alkali salt of arsenic or arsenous acid,
- radicals R signify for example methyl, ethyl, propyl, butyl or isobutyl
- the radicals R signify methylene, ethylidene, propylidene, butylidene, pentylidene and the like, the alkyl radicals being preferably substituted with up to 2 hydroxy groups.
- the components (A), (B) and (C) seem to influence each other synergistically in the bath, for when used alone they are completely ineffective.
- concentrations required for a high-gloss gold deposition or a chromatic gold alloy deposition are, for the aldehydes, i.e., component A, about 0.005 to 50 g/liter, for the nitrogen compounds, i.e., component B, about 0.1 to 50 g/liter, and for the arsenic compounds, i.e., component C, about 0.001 to g/liter.
- aldehyde components there are suitable preferably formaldehyde, acetaldehyde and glyoxal, which can be used per se or in the form of their addition compounds, i.e., as bisulfites.
- Nitrogen compounds that are especially suitable are hydrazine or methyl hydrazine, which are to be used according to invention either by themselves or in the form of their salts, such as the chlorides or sulfates, or alone or in a mixture with one another.
- hydrazine or methyl hydrazine which are to be used according to invention either by themselves or in the form of their salts, such as the chlorides or sulfates, or alone or in a mixture with one another.
- prropyl hydrazine as well as phenyl hydrazine and the substitution products thereof and their salts have proved to be suitable.
- nitrogen compounds that may be used according to the invention are, for example, N-(3-propy1- 5 l,2-diol)-diethylene triamine, triethylene tetramine,
- ethylene diamine, diethylene triamine, triethylenetetramine and tetraethylene pentamine of which the first two in particular have been found to be very favorable with respect to their smoothing action.
- these compounds can be used by themselves as such, as well as in the form of their salts, for example, the chlorides or acetates.
- Suitable arsenic compounds that are effective are the alkali salts of arsenic and arsenous acid, such as sodium and potassium arsenate or arsenite.
- an aqueous solution which contains a water-soluble gold salt, preferably a complex compound of gold, in particular potassium dicyanoaurate (I), in concentrations of about 1 to 50 g/liter.
- a water-soluble gold salt preferably a complex compound of gold, in particular potassium dicyanoaurate (I), in concentrations of about 1 to 50 g/liter.
- 1f gold alloy coatings are to be deposited, there are added to the bath the alloy metals silver, copper, zinc, cadmium, manganese, cobalt, nickel, palladium, indium, antimony 'or tin, in the form of their watersoluble compounds, preferably in the form of the complex compounds, such as the chelate or the cyano complexes, in total concentrations of about 0.01 to 200 g/liter.
- the alloy metals silver, copper, zinc, cadmium, manganese, cobalt, nickel, palladium, indium, antimony 'or tin, in the form of their watersoluble compounds, preferably in the form of the complex compounds, such as the chelate or the cyano complexes, in total concentrations of about 0.01 to 200 g/liter.
- the complex compounds such as the chelate or the cyano complexes
- the bath contains boric acid and a polyvalent alcohol, preferably ethylene glycol, namely more particularly in a ratio by weight of about 1:1 to 1:2 and in a concentration of about to 200 g/liter of boric acid or of about 10 to 2000 g/liter of alcohol.
- a polyvalent alcohol preferably ethylene glycol
- the bath may contain common conducting salts, for example ammonium sulfate or alkali salts of sulfuric acid, nitric acid or hydrochloric acid, pH-regulating substances, appropriately the organic and/or inorganic buffer mixtures commonly used for this purpose such as, mixtures of citric acid and potassium citrate or sodium hydrophosphate and sodium dihydrophosphate as well as surface-active substances, such as ethylhexylsu lfate and N- ethoxyhexylamine.
- common conducting salts for example ammonium sulfate or alkali salts of sulfuric acid, nitric acid or hydrochloric acid, pH-regulating substances, appropriately the organic and/or inorganic buffer mixtures commonly used for this purpose such as, mixtures of citric acid and potassium citrate or sodium hydrophosphate and sodium dihydrophosphate as well as surface-active substances, such as ethylhexylsu lfate and N- ethoxyhexylamine.
- the pH value of the bath may .be from about 5 to 10, preferably 6.8 to 7.5. It is operated appropriately at temperatures of about to 70 C, preferably at temperatures between to C, current densities from about 0.1 to 5 amp.dm being used.
- the bath according to the invention is suitable in particular for the galvanic deposition of high-gloss gold coatings and chromatic gold alloy coatings with excellent smoothing appearance.
- Another advantage of the invention consists in the extraordinary adhesion of the coatings, which, surprisingly, far exceeds that of the coatings produced by the usual, known methods.
- the lead containing brass alloy which is very difficult to galvanize or plate, can be gold plated directly without the previous deposition of an intermediate layer by means of the bath according to this invention resulting in a substantial saving of material and time.
- bath of the invention permits the use of high current densities and at good current efficiency shorter exposure times, whence special advantages result for the practice.
- pH value 6.8 which is adjusted with sulfuric acid
- Applicable current density from 0.1 to maximum 2.0 amp.dm Temperature: to 70 C
- This electrolyte composition according to the invention is suitable for the deposition of nearly 24 carat gold.
- the coatings deposited from this electrolyte are of high luster, saturated gold color, and have a hardness of about 170 microvickers.
- lead containing brass With the electrolyte, lead containing brass can be proviced, without an intermediate layer, with a gold coating which is of high luster from about 8 micron on.
- EXAMPLE 2 g/liter Potassium dicyanoaurate (l), K(Au(CN) 12.0 Ammonium sulfate, (NHQ SO 70.0 Boric acid, H 30 40.0 Ethylene glycol, HOCH -CH OH 80.0 Copper sulfate, CuSO '5 H O 8.0 Ethylene diamine tetraceticacid dipotassium salt 9.5 Formaldehyde, CH O 5.0 Hydrazine hydrate N H 'H O 12.0 Sodium arsenite, Na ASO 0.045
- carat coatings By means of this electrolyte, about 18 carat coatings can be deposited, which have the color of rolled gold.
- the coatings are of high gloss and tarnish resistant.
- Applicable current density From 0.1 to 1.5 amp/dm Temperature: 20 to 60 C Rate of deposition at l amp.dm 1 micron in 4 minutes. Intensive agitation of electrolyte or cathode is effected.
- Thiselectrolyte furnishes light yellow, about 20 carat coatings.
- the coatings deposited from this electrolyte are high gloss and tarnish resistant.
- Applicable current density from 0.2 to 1.0 amp/dm Temperature: 20 to C
- the rate of deposition at l amp/dm is 1 micron in 8 minutes.
- This electrolyte furnishes almost white, high-gloss coatings.
- the deposited alloy is approximately 16 carat.
- EXAMPLE 5 g/liter Potassium dicyanoaurate (l), K(Au(CN 15.0 Ammonium sulfate, (NH SO 80.0 Boric acid, H BO 50.0 Ethylene glycol, HOCH CH OH 100.0 Cobalt sulfate, CoSo '7H- O 3.0 Nickel sulfate NiSO '7l-l O 2.0 lndium sulfate, ln (SO.,);, 0.5 Methyl hydrazine CH -NHNH 0.1 Ethylene diamine tetracetic acid dipotassium salt 6.0 Formaldehyde, CH O 3.0 Sodium arsenite, Na;,AsO 0.3
- Applicable current density from 0.1 to 2.5 amp/dm Temperature: 20 to 35 C Rate of deposition at 2 amp/dm: 1 micron in 2 minutes According to the invention an alloy of good electrical properties and excellent abrasive strength can be deposited with this bath.
- the coatings are of high gloss and have a fineness of 23 carat.
- the current efficiency is 40 to 60%.
- the content of alloy metals can be greatly influenced by varying the current density and the speed of goods or by electrolyte agitation. From a layer thickness of about 5 micron on, a smoothing effect can already be observed.
- An aqueous bath for the electrodeposition of gold or gold alloys having a high gloss said bath having a pH of from about 5 to 10 and an amount of components,-
- A, B and C to provide a coating having high gloss and extraordinary adhesion said bath comprising A. from about 0.005 to 50 grams per liter of at least one compound of the general formula RCHO wherein R is selected from the group consisting of hydrogen, methyl, and the group CH0, and an aldehyde bisulfite addition compound thereof, and B. from about 0.1 to 50 grams per liter of at least one compound of the general formula R N(R'NR- ),,,--(R),,- NR in which each R is selected from the group consisting of hydrogen, alkyl having from 1 to 5 carbon atoms and hydroxy-substituted alkyl having from 1 to 5 carbon atoms, in and n is 0 or an integer from 1 to 3, and C. from about 0.001 to 5 grams per liter of at least one alkali metal salt of a member of the group consisting of arsenic acid and arsenious acid, and
- a bath adding to claim 1 which contains about ID to 200 grams per liter of boric acid and about to 200 grams per liter of a polyvalent alcohol, the ratio of boric acid to polyvalent alcohol being from about lzl to about 1:2, by weight.
- a bath according to claim 2 wherein the polyvalent alcohol is ethylene glycol.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrolytic Production Of Metals (AREA)
- Physical Vapour Deposition (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2244434A DE2244434C3 (de) | 1972-09-06 | 1972-09-06 | Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3878066A true US3878066A (en) | 1975-04-15 |
Family
ID=5855965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US394959A Expired - Lifetime US3878066A (en) | 1972-09-06 | 1973-08-29 | Bath for galvanic deposition of gold and gold alloys |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US3878066A (sv) |
| JP (1) | JPS5421820B2 (sv) |
| AT (1) | AT322935B (sv) |
| AU (1) | AU469094B2 (sv) |
| BE (1) | BE804544A (sv) |
| CA (1) | CA1019276A (sv) |
| CH (1) | CH594746A5 (sv) |
| DD (1) | DD106060A5 (sv) |
| DE (1) | DE2244434C3 (sv) |
| FR (1) | FR2197997B1 (sv) |
| GB (1) | GB1438521A (sv) |
| IE (1) | IE38198B1 (sv) |
| IT (1) | IT995275B (sv) |
| NL (1) | NL7312310A (sv) |
| SE (1) | SE387372B (sv) |
| SU (1) | SU549089A3 (sv) |
| ZA (1) | ZA737128B (sv) |
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| US4062736A (en) * | 1974-11-15 | 1977-12-13 | Oxy Metal Industries Corporation | Gold and gold alloy deposition |
| US4207149A (en) * | 1974-12-04 | 1980-06-10 | Engelhard Minerals & Chemicals Corporation | Gold electroplating solutions and processes |
| US5024733A (en) * | 1989-08-29 | 1991-06-18 | At&T Bell Laboratories | Palladium alloy electroplating process |
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| FR2828889A1 (fr) * | 2001-08-24 | 2003-02-28 | Engelhard Clal Sas | Bain electrolytique pour le depot electrochimique de l'or et de ses alliages |
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| US20080264774A1 (en) * | 2007-04-25 | 2008-10-30 | Semitool, Inc. | Method for electrochemically depositing metal onto a microelectronic workpiece |
| US20100024930A1 (en) * | 2006-10-03 | 2010-02-04 | The Swatch Group Research And Development Ltd. | Electroforming method and part or layer obtained via the method |
| US20100206739A1 (en) * | 2007-09-21 | 2010-08-19 | The Swatch Group Research And Development Ltd. | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids |
| US20110089040A1 (en) * | 2009-10-15 | 2011-04-21 | The Swatch Group Research And Development Ltd | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials |
| ITFI20120103A1 (it) * | 2012-06-01 | 2013-12-02 | Bluclad Srl | Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni. |
| US11618951B2 (en) | 2020-05-27 | 2023-04-04 | Global Circuit Innovations Incorporated | Chemical evaporation control system |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH626410A5 (en) * | 1977-09-07 | 1981-11-13 | Metaux Precieux Sa | Bath for the electrolytic deposition of gold or gold alloys and use of this bath |
| DE2800817C2 (de) * | 1978-01-10 | 1982-11-04 | Oxy Metal Industries Corp., 48089 Warren, Mich. | Aldehydfreies wässriges Bad für die galvanische Abscheidung von Gold und dessen Legierungen sowie ein Verfahren zur Herstellung von Gold- und Goldlegierungsabscheidungen unter Verwendung dieses Bades |
| DE3020765A1 (de) * | 1980-05-31 | 1981-12-10 | Degussa Ag, 6000 Frankfurt | Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten |
| JP5707912B2 (ja) * | 2010-12-08 | 2015-04-30 | 東ソー株式会社 | Ｎ−（ジヒドロキシアルキル）ジエチレントリアミン類の組成物、及びそれを用いた２−ヒドロキシ（アルキル）トリエチレンジアミン類の製造方 |
| JP5687667B2 (ja) * | 2012-08-21 | 2015-03-18 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | シアン系金−パラジウム合金めっき液及びめっき方法 |
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- 1973-08-13 GB GB3824873A patent/GB1438521A/en not_active Expired
- 1973-08-16 CH CH1182673A patent/CH594746A5/xx not_active IP Right Cessation
- 1973-08-28 FR FR7331051A patent/FR2197997B1/fr not_active Expired
- 1973-08-29 AU AU59770/73A patent/AU469094B2/en not_active Expired
- 1973-08-29 US US394959A patent/US3878066A/en not_active Expired - Lifetime
- 1973-09-04 IE IE1571/73A patent/IE38198B1/xx unknown
- 1973-09-04 IT IT28551/73A patent/IT995275B/it active
- 1973-09-05 SE SE7312093A patent/SE387372B/sv unknown
- 1973-09-05 SU SU1959161A patent/SU549089A3/ru active
- 1973-09-05 AT AT770573A patent/AT322935B/de not_active IP Right Cessation
- 1973-09-06 BE BE135388A patent/BE804544A/xx not_active IP Right Cessation
- 1973-09-06 JP JP10071973A patent/JPS5421820B2/ja not_active Expired
- 1973-09-06 CA CA180,445A patent/CA1019276A/en not_active Expired
- 1973-09-06 ZA ZA737128*A patent/ZA737128B/xx unknown
- 1973-09-06 NL NL7312310A patent/NL7312310A/xx not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| FR2197997A1 (sv) | 1974-03-29 |
| FR2197997B1 (sv) | 1976-11-19 |
| AU5977073A (en) | 1975-03-06 |
| DE2244434A1 (de) | 1974-03-21 |
| IE38198L (en) | 1974-03-06 |
| SE387372B (sv) | 1976-09-06 |
| ZA737128B (en) | 1974-08-28 |
| DD106060A5 (sv) | 1974-05-20 |
| AU469094B2 (en) | 1976-02-05 |
| CA1019276A (en) | 1977-10-18 |
| CH594746A5 (sv) | 1978-01-31 |
| IE38198B1 (en) | 1978-01-18 |
| DE2244434B2 (de) | 1981-02-19 |
| GB1438521A (en) | 1976-06-09 |
| BE804544A (fr) | 1974-03-06 |
| AT322935B (de) | 1975-06-10 |
| IT995275B (it) | 1975-11-10 |
| SU549089A3 (ru) | 1977-02-28 |
| NL7312310A (sv) | 1974-03-08 |
| JPS5421820B2 (sv) | 1979-08-02 |
| JPS4967842A (sv) | 1974-07-01 |
| DE2244434C3 (de) | 1982-02-25 |
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