US3373094A - Gold and gold alloy electroplating - Google Patents
Gold and gold alloy electroplating Download PDFInfo
- Publication number
- US3373094A US3373094A US497454A US49745465A US3373094A US 3373094 A US3373094 A US 3373094A US 497454 A US497454 A US 497454A US 49745465 A US49745465 A US 49745465A US 3373094 A US3373094 A US 3373094A
- Authority
- US
- United States
- Prior art keywords
- gold
- piperazine
- bright
- bath
- acid
- 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.)
- Expired - Lifetime
Links
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title description 29
- 238000009713 electroplating Methods 0.000 title description 17
- 229910001020 Au alloy Inorganic materials 0.000 title description 4
- 239000003353 gold alloy Substances 0.000 title description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 28
- 229910052737 gold Inorganic materials 0.000 description 28
- 239000010931 gold Substances 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000005282 brightening Methods 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 239000010953 base metal Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- -1 alkali metal gold cyanide Chemical class 0.000 description 8
- 150000004885 piperazines Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000012971 dimethylpiperazine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 125000004193 piperazinyl group Chemical group 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IPDWABJNXLNLRA-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(O)C(O)C(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O IPDWABJNXLNLRA-UHFFFAOYSA-N 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UTKBLLDLHPDWDU-ODZAUARKSA-N acetic acid;(z)-but-2-enedioic acid Chemical compound CC(O)=O.OC(=O)\C=C/C(O)=O UTKBLLDLHPDWDU-ODZAUARKSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SZXAQBAUDGBVLT-UHFFFAOYSA-H antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SZXAQBAUDGBVLT-UHFFFAOYSA-H 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- BDXBEDXBWNPQNP-UHFFFAOYSA-L copper;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron Chemical compound [Cu+2].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O BDXBEDXBWNPQNP-UHFFFAOYSA-L 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- This invention has to do with the electrodeposition of gold and more specifically with the electrodeposition of bright gold.
- Bright gold deposits can be obtained from gold electrolytes containing alkali metal gold cyanide at a pH of about 3.0 to about 5.0 by adding base metal compounds such as nickel citrate, cobalt sulfate, etc., to the bath (see U.S. 2,905,601).
- base metal compounds such as nickel citrate, cobalt sulfate, etc.
- One theory explains that such baths produce bright gold because they provide the base metal in the cathode film in a condition to codeposit with the gold.
- the plating specification calls for 24 karat gold, in other cases the base metal present may be deleterious to a solidstate device to be gold plated.
- Among the objects of the invention is to provide a process and electroplating bath for electroplating bright 24 karat gold without the codeposition of other metals with the gold.
- This invention is based on the discovery that excellent bright gold deposits can be obtained by adding small amounts of piperazine or piperazine substitution compounds to acid electrolytes containing alkali metal gold cyanide even in the absence of codepositing metals.
- substituted piperazine will be understood to include those fairly simple substitution compounds obtained by substituting alkyl groups for one or more of the hydrogens of the piperazine ring so that the compound does not lose its essential piperazine characteristics.
- Conducting salts which are preferably alkali metal or ammonium salts may be added to said baths as such or may be formed in the bath by the addition of the corresponding hydroxide or carbonate, etc., to react with a portion of the acid of said baths.
- Such salts also provide efiective buiiering for the solution, especially when the acids employed are weak acids.
- Table I indicates the acid used, which in each case was neutralized to the pH listed with KOH or NaOH to provide the conducting and buffer salts (since the acids employed in these examples are weak acids).
- citric acid When citric acid is added as the acid preferably 5-150 g./I. is employed.
- Bright panels were obtained in all cases.
- the standard practice being to plate 10 x 2.5 cm. brass panels between two platinum cathodes in a liter beaker.
- Current densities from 0.1 to 5 amp./dm. were used, depending upon the temperature selected and the degree of agitation employed.
- Example 10 A bath containing potassium gold cyanide, 12 g./l.; copper ethylenediamine tetraacetate, 4 g./l.; antimony tartrate, 3 g./l.; potassium dihydrogen phosphate, 50 g./l.; and ethylenediamine tetraacetic acid, 20 g./l.; adjusted to a pH of 5.0, yielded deposits with a slight haze at 15 a.s.f. Upon the addition of dimethyl piperazine the deposits were fully bright.
- An electroplating bath for producing bright gold deposits comprising an aqueous solution of alkali metal gold cyanide and as a brightening agent a compound selected from the group consisting of piperazine and alkyl substituted piperazine in an amount sufficient to produce a bright gold deposit, said bath having a pH below about 6.0.
- An electroplating bath according to claim 1 comprising in addition a suflicient amount of conducting salts to substantially lower the voltage required for deposition of the gold.
- An electroplating bath according to claim 4 in which at least one conducting salt is a buffer and is present in an amount sufficient to maintain a stable pH.
- An electroplating bath according to claim 1 containing in addition base metal compounds of such a nature that at least one base metal is present in the cathode film in the condition necessary to co-deposit with the gold.
- An electroplating bath for producing bright gold deposits comprising an aqueous solution of an alkali metal gold cyanide, at least one water soluble compound selected from the class consisting of alkali metal and ammonium salts of organic and inorganic acids to provide a pH below about 6 and as a brightening agent a compound selected from the group consistinng of piperazine and alkyl substituted piperazine in an amount suflicient to produce a bright gold deposit.
- water-soluble compounds are the alkali metal and ammonium salts selected from the class of acids consisting of weak, stable, organic and inorganic acids.
- a method of electrodepositing bright gold which comprises electrolyzing an aqueous solution consisting essentially of a soluble alkali metal gold cyanide and piperazine in the amount of 0.5 to 5.0 grams per liter, said bath having a pH of about 3.0 to 6.0.
- a method of electrodepositing bright gold which comprises electrolyzing at a current density of 0.1 to 5 I amp./dm. an aqueous solution comprising soluble alkali metal gold cyanide and as a brightening agent a compound selected from the group consisting of piperazine and alkyl substituted piperazine in a amount sutficient to produce a bright gold deposit, said bath having a pH of about 3 to 6.
- a method as claimed in claim 14 wherein said added brightening agent is dimethyl piperazine.
Landscapes
- 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)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US497454A US3373094A (en) | 1964-08-26 | 1965-10-18 | Gold and gold alloy electroplating |
| US373094D USB373094I5 (enrdf_load_html_response) | 1964-08-26 | 1965-10-18 | |
| CH1487766A CH468474A (fr) | 1964-08-26 | 1966-10-14 | Procédé de placage électrolytique pour produire des dépôts brillants d'alliages d'or ou d'or de 24 carats, et bain de placage pour la mise en oeuvre de ce procédé |
| DE19661521013 DE1521013A1 (de) | 1964-08-26 | 1966-10-17 | Verfahren und Elektrolytloesung zur Goldplattierung |
| BE688412D BE688412A (enrdf_load_html_response) | 1964-08-26 | 1966-10-18 | |
| FR976A FR1497810A (fr) | 1964-08-26 | 1966-10-18 | Procédé de placage électrolytique pour produire des dépôts brillants d'or de 24 carats, et bain de placage pour la mise en oeuvre de ce procédé |
| NL6614654A NL6614654A (enrdf_load_html_response) | 1964-08-26 | 1966-10-18 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39228664A | 1964-08-26 | 1964-08-26 | |
| US497454A US3373094A (en) | 1964-08-26 | 1965-10-18 | Gold and gold alloy electroplating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3373094A true US3373094A (en) | 1968-03-12 |
Family
ID=27013831
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US373094D Pending USB373094I5 (enrdf_load_html_response) | 1964-08-26 | 1965-10-18 | |
| US497454A Expired - Lifetime US3373094A (en) | 1964-08-26 | 1965-10-18 | Gold and gold alloy electroplating |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US373094D Pending USB373094I5 (enrdf_load_html_response) | 1964-08-26 | 1965-10-18 |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | USB373094I5 (enrdf_load_html_response) |
| BE (1) | BE688412A (enrdf_load_html_response) |
| CH (1) | CH468474A (enrdf_load_html_response) |
| DE (1) | DE1521013A1 (enrdf_load_html_response) |
| FR (1) | FR1497810A (enrdf_load_html_response) |
| NL (1) | NL6614654A (enrdf_load_html_response) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180209058A1 (en) * | 2017-01-23 | 2018-07-26 | Nitto Denko Corporation | Producing method of wired circuit board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2355581C3 (de) * | 1973-11-07 | 1979-07-12 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Galvanisches Glanzgoldbad mit hoher Abscheidungsgeschwindigkeit |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2724687A (en) * | 1952-05-08 | 1955-11-22 | Spreter Victor | Baths for the deposit of gold alloys by electroplating |
| US2765269A (en) * | 1954-11-19 | 1956-10-02 | Barnet D Ostrow | Bath for plating bright gold |
| US2812299A (en) * | 1949-05-05 | 1957-11-05 | Birle & Co K G | Electrolytic deposition of gold and gold alloys |
| US2905601A (en) * | 1957-08-13 | 1959-09-22 | Sel Rex Corp | Electroplating bright gold |
| US2967135A (en) * | 1960-06-08 | 1961-01-03 | Barnet D Ostrow | Electroplating baths for hard bright gold deposits |
-
1965
- 1965-10-18 US US373094D patent/USB373094I5/en active Pending
- 1965-10-18 US US497454A patent/US3373094A/en not_active Expired - Lifetime
-
1966
- 1966-10-14 CH CH1487766A patent/CH468474A/fr unknown
- 1966-10-17 DE DE19661521013 patent/DE1521013A1/de active Pending
- 1966-10-18 NL NL6614654A patent/NL6614654A/xx unknown
- 1966-10-18 FR FR976A patent/FR1497810A/fr not_active Expired
- 1966-10-18 BE BE688412D patent/BE688412A/xx unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2812299A (en) * | 1949-05-05 | 1957-11-05 | Birle & Co K G | Electrolytic deposition of gold and gold alloys |
| US2724687A (en) * | 1952-05-08 | 1955-11-22 | Spreter Victor | Baths for the deposit of gold alloys by electroplating |
| US2765269A (en) * | 1954-11-19 | 1956-10-02 | Barnet D Ostrow | Bath for plating bright gold |
| US2905601A (en) * | 1957-08-13 | 1959-09-22 | Sel Rex Corp | Electroplating bright gold |
| US2967135A (en) * | 1960-06-08 | 1961-01-03 | Barnet D Ostrow | Electroplating baths for hard bright gold deposits |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180209058A1 (en) * | 2017-01-23 | 2018-07-26 | Nitto Denko Corporation | Producing method of wired circuit board |
| US11091850B2 (en) * | 2017-01-23 | 2021-08-17 | Nitto Denko Corporation | Producing method of wired circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1497810A (fr) | 1967-10-13 |
| BE688412A (enrdf_load_html_response) | 1967-03-31 |
| USB373094I5 (enrdf_load_html_response) | |
| NL6614654A (enrdf_load_html_response) | 1967-04-19 |
| CH468474A (fr) | 1969-02-15 |
| DE1521013A1 (de) | 1969-08-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
| AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
| AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
| AS | Assignment |
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
|
| AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |