US3423295A - Gold plating - Google Patents
Gold plating Download PDFInfo
- Publication number
- US3423295A US3423295A US529262A US3423295DA US3423295A US 3423295 A US3423295 A US 3423295A US 529262 A US529262 A US 529262A US 3423295D A US3423295D A US 3423295DA US 3423295 A US3423295 A US 3423295A
- Authority
- US
- United States
- Prior art keywords
- gold
- acid
- grams
- potassium
- pyrophosphate
- 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
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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- the present invention relates to gold electroplating baths and more particularly to a gold plating solution for the electrodeposition of heavy, smooth ductile and pure gold deposits.
- Gold plating baths presently in commercial use are generally of two types: (1) alkaline baths containing gold in the form of potassium gold cyanide and substantial concentrations of uncombined potassium or sodium cyanide, and (2) so-called acid gold baths, operating in a pH range of about 3 to 6.5, which contain gold in the form of a cyanide complex and salts of organic acids such as citrates, acetates, lactates, tartrates, gluconates, etc.
- these baths contain complex organic chelating agents such as e-thylenediamine tetraacetic acid or other aminopolycarboxylic acids.
- organic complexing agents such as ethylenediamine, diethylenetriamine and other complex organic amines, or organic compounds such as triglycollamic acid.
- the alkaline baths containing free cyanide are disadvantageous in that carbonates accumulate and decomposition products due to oxidation and hydrolysis of the free cyanide build up and adversely affect the quality of the electrodeposited gold by occlusion of small quantities of these impurities in the gold plate.
- the present invention is intended to overcome such difficulties and disadvantages, it being among the objects hereof to provide a bath composition which permits obtaining heavy smooth deposits of gold free from organic decomposition products.
- Another object of the invention is the provision of a bath composition which is capable of obtaining deposits that are not only heavy and smooth but also are of a high degree of purity and highly ductile.
- arsenic compounds employed are critically in the trivalent state, since elemental arsenic and other multivalent com-pounds of arsenic, such as pentavalent arsenic compounds, e.g., arsenic pentoxide have little or no effect in providing gold deposits of good quality and of substantial thickness and smoothness.
- the advantages are particularly evident at relatively low temperatures in the range of ll5-120 F. This is a highly desirable factor particularly in the plating of circuit boards the plastic portion of which may not tolerate temperature above F.
- the presence of tri-valent arsenic in minute amounts appears to act catalytically or by exercising a depolarizing effect in extending the limiting current density and improving the smoothness and color of the electrodeposited gold.
- This invention consists in providing a bath composition using pyrophosphates as the essential conducting salts.
- Pyrophosphates by virtue of their complexing ability, have been found to be considerably advantageous over phosphate salts. Although it is known that the pyrophosphates revert slowly to orthophosphates, it has been observed that the gold plating results are not adversely affected probably because intermediate degradation products still possess complexing ability and the beneficial effects of pyrophosphates are evident even when relatively small amounts are present. Pyrophosphates appear also to have a stabilizing effect on baths containing organic acid salts such as citrates, tartrates, etc.
- Superphosphoric acid is a commercial product containing the highest percentage of pyrophosphoric acid (about 42%) of any of the phosphoric acids commercially available.
- adjustment of the bath pH with this acid effects replenishment of pyrophosphate ion to the solution to assure its presence in the bath in appreciable amount to counteract the tendency to reversion to orthophosphate.
- the pH may be adjusted with other suitable acids, phosphoric acid, polyphosphoric acid or acid salts such as ammonium citrate, monobasic potassium phosphate; boric acid, formic acid and tartaric acid.
- the concentration 6r potassium pyrophosphate may vary between about 10 grams per liter up to saturation without significantly "ice affecting the quality of the gold electrodeposit although the preferred range is 75 to 200 grams per liter. In practice, the saturation point is seldom reached because the drag-out increases with increased concentration of pyrophosphate and obviates against a point of saturation being reached.
- the electrolyte solution contemplated is an electrolyte solution for use in the electrodeposition of gold comprising essentially from about 4 to 50 grams of an alkali metal gold cyanide per liter, about 10 to 200 grams of an alkali metal pyrophosphate, 10 to 100 grams of a Superphosphoric acid per liter, or an acid or salt above-mentioned, and from 0.2 to 10 milligrams of a tri-va'lent arsenic compound such as arsenic trioxide, the pH of the solution being adjusted to a value in the range of from and 8.
- the solution may contain from 1 to 110 grams of the salt of an organic acid such as ammonium, potassium or sodium citrate.
- an alkali metal gold cyanide includes potassium gold cyanide and sodium gold cyanide.
- a potassium pyrophosphate includes potassium pyrophosphate and tetrapotassium pyrophosphate.
- Superphosphoric acid includes an acid containing pyrophosphoric acid as a major ingredient together with any other of the phosphoric acids.
- Example 1 An electrolyte was prepared as follows:
- the pH is adjusted to 5.5-6.0 using Superphosphoric acid to lower the pH.
- Potassium hydroxide, potassium pyrophosphate or ammonium hydroxide are employed to raise the pH.
- current densities over a range of 3-6 amperes per square foot, with moderate to vigorous agitation smooth, ductile and yellow 24K deposits are obtained.
- Example 2 50 grams potassium gold cyanide 200 grams potassium pyrophosphate 100 grams Superphosphoric acid 10 milligrams AS203 Water to make one liter.
- the pH of the solution is adjusted to 6.5-7.0 using Superphosphoric acid to lower the pH.
- Potassium pyrophosphate, potassium hydroxide or ammonium hydroxide are employed to raise the pH.
- temperatures of 60" C. and current densities over a range of 510 amperes per sq. ft., with moderate to vigorous agitation, smooth, ductile, yellow 24K gold deposits may be obtained up to thicknesses of 0.050.
- Example 3 4 grams potassium gold cyanide 10 grams ammonium citrate 10 grams potassium pyrophosphate 10 grams Superphosphoric acid 5 milligrams As O Water to make one liter.
- the pH is adjusted to 5.5-6.5 using Superphosphoric acid or ammonium citrate to lower the pH.
- Potassium pyrophosphate, potassium hydroxide or ammonium hydroxide are employed to raise the pH.
- a temperature of -65 C. and current density over a range of 3-6 ampers per square foot with moderate to rapid agitation, smooth, ductile and yellow gold 24K gold deposits are obtained.
- Example 4 20 grams potassium gold cyanide 50 grams potassium pyrophosphate 25 grams ammonium citrate 30 grams Superphosphoric acid 10 milligrams AS203 Water to make one liter.
- the pH is adjusted to 5.57.0 using Superphosphoric acid or ammonium citrate to lower the pH.
- Potassium pyrophosphate, potassium hydroxide or ammonium hydroxide are employed to raise the pH.
- temperatures of 45 -65 and current densities of 5-10 amperes per square foot, with moderate to strong agitation, smooth, ductile, yellow 24K deposits are obtained up to heavy thicknesses of the order of 010-040".
- Example 5 20 grams potassium gold cyanide grams ammonium or potassium citrate 8 milligrams AS203 Water to make one liter.
- the pH is adjusted to 5.56.5 using Superphosphoric acid or ammonium citrate to lower the pH. Potassium, sodium or ammonium hydroxide are employed to raise the pH. At temperatures of 4565 C. and current densities of 5-10 amperes per square foot, with modearte to strong agitation, smooth, ductile, yellow 24K deposits are readily obtained.
- An electrolyte solution for use in the electrodeposition of gold comprising essentially from about 4 to 50 grams of an alkali metal gold cyanide, about 10 to 200 grams of an alkali metal pyrophosphate, about 10 to grams of a pH adjusting acid, about 0.2 to 10 milligrams of a tri-valent arsenic compound and water to make one liter, the pH of the solution being adjusted to a value in the range of from 5 to 8.
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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52926266A | 1966-02-23 | 1966-02-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3423295A true US3423295A (en) | 1969-01-21 |
Family
ID=24109170
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US529262A Expired - Lifetime US3423295A (en) | 1966-02-23 | 1966-02-23 | Gold plating |
Country Status (8)
Country | Link |
---|---|
US (1) | US3423295A (de) |
BE (1) | BE694539A (de) |
CH (1) | CH485863A (de) |
DE (1) | DE1621068B2 (de) |
FR (1) | FR1508895A (de) |
GB (1) | GB1179017A (de) |
NL (1) | NL6700954A (de) |
SE (1) | SE313714B (de) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3520785A (en) * | 1969-04-14 | 1970-07-14 | Robert Duva | Electroplating gold and thiomalate electrolyte therefor |
US3770596A (en) * | 1972-07-21 | 1973-11-06 | Auric Corp | Gold plating bath for barrel plating operations |
US3833488A (en) * | 1971-08-20 | 1974-09-03 | Auric Corp | Gold electroplating baths and process |
US3879269A (en) * | 1973-04-26 | 1975-04-22 | Auric Corp | Methods for high current density gold electroplating |
US3897246A (en) * | 1971-12-15 | 1975-07-29 | Amp Inc | Novel electro deposited gold; electrolyte solution to obtain the same; method for producing said gold; and products |
US4075065A (en) * | 1975-07-07 | 1978-02-21 | Handy & Harman | Gold plating bath and process |
US4238300A (en) * | 1979-05-25 | 1980-12-09 | Bell Telephone Laboratories, Incorporated | Gold electroplating process |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3833487A (en) * | 1972-12-22 | 1974-09-03 | Bell Telephone Labor Inc | Electrolytic soft gold plating |
EP0028684A1 (de) * | 1979-09-06 | 1981-05-20 | Western Electric Company, Incorporated | Herstellung und Nachbehandlung eines mit Gold überzogenen Gegenstandes und so erhaltener Gegenstand |
EP0025220A1 (de) * | 1979-09-06 | 1981-03-18 | Western Electric Company, Incorporated | Zusatzfreie galvanische Hartgoldabscheidung und erhaltenes Produkt |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US744170A (en) * | 1899-08-26 | 1903-11-17 | Andre Darlay | Process of depositing metallic coatings on metallic objects. |
US823864A (en) * | 1905-09-29 | 1906-06-19 | James M Dunnigan | Steam-boiler. |
FR1027637A (fr) * | 1949-11-15 | 1953-05-13 | Heraeus Gmbh W C | Procédé de dépôt de revêtements galvaniques durs de métaux nobles |
US2967135A (en) * | 1960-06-08 | 1961-01-03 | Barnet D Ostrow | Electroplating baths for hard bright gold deposits |
CH354643A (fr) * | 1959-11-24 | 1961-05-31 | Mermillod Jean | Bain pour le dépôt galvanique d'alliage d'or brillant, procédé de préparation et utilisation dudit bain |
GB928088A (en) * | 1961-08-23 | 1963-06-06 | Sel Rex Corp | Bright gold plating |
US3149057A (en) * | 1959-04-27 | 1964-09-15 | Technic | Acid gold plating |
-
1966
- 1966-02-23 US US529262A patent/US3423295A/en not_active Expired - Lifetime
-
1967
- 1967-01-20 NL NL6700954A patent/NL6700954A/xx unknown
- 1967-01-25 FR FR92430A patent/FR1508895A/fr not_active Expired
- 1967-02-21 SE SE2399/67A patent/SE313714B/xx unknown
- 1967-02-21 GB GB8283/67A patent/GB1179017A/en not_active Expired
- 1967-02-22 CH CH258667A patent/CH485863A/de not_active IP Right Cessation
- 1967-02-22 DE DE19671621068 patent/DE1621068B2/de active Pending
- 1967-02-23 BE BE694539D patent/BE694539A/xx unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US744170A (en) * | 1899-08-26 | 1903-11-17 | Andre Darlay | Process of depositing metallic coatings on metallic objects. |
US823864A (en) * | 1905-09-29 | 1906-06-19 | James M Dunnigan | Steam-boiler. |
FR1027637A (fr) * | 1949-11-15 | 1953-05-13 | Heraeus Gmbh W C | Procédé de dépôt de revêtements galvaniques durs de métaux nobles |
US3149057A (en) * | 1959-04-27 | 1964-09-15 | Technic | Acid gold plating |
CH354643A (fr) * | 1959-11-24 | 1961-05-31 | Mermillod Jean | Bain pour le dépôt galvanique d'alliage d'or brillant, procédé de préparation et utilisation dudit bain |
US2967135A (en) * | 1960-06-08 | 1961-01-03 | Barnet D Ostrow | Electroplating baths for hard bright gold deposits |
GB928088A (en) * | 1961-08-23 | 1963-06-06 | Sel Rex Corp | Bright gold plating |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3520785A (en) * | 1969-04-14 | 1970-07-14 | Robert Duva | Electroplating gold and thiomalate electrolyte therefor |
US3833488A (en) * | 1971-08-20 | 1974-09-03 | Auric Corp | Gold electroplating baths and process |
US3897246A (en) * | 1971-12-15 | 1975-07-29 | Amp Inc | Novel electro deposited gold; electrolyte solution to obtain the same; method for producing said gold; and products |
US3770596A (en) * | 1972-07-21 | 1973-11-06 | Auric Corp | Gold plating bath for barrel plating operations |
US3879269A (en) * | 1973-04-26 | 1975-04-22 | Auric Corp | Methods for high current density gold electroplating |
US4075065A (en) * | 1975-07-07 | 1978-02-21 | Handy & Harman | Gold plating bath and process |
US4238300A (en) * | 1979-05-25 | 1980-12-09 | Bell Telephone Laboratories, Incorporated | Gold electroplating process |
Also Published As
Publication number | Publication date |
---|---|
DE1621068B2 (de) | 1972-11-16 |
GB1179017A (en) | 1970-01-28 |
DE1621068A1 (de) | 1971-04-15 |
BE694539A (de) | 1967-08-23 |
FR1508895A (fr) | 1968-01-05 |
CH485863A (de) | 1970-02-15 |
SE313714B (de) | 1969-08-18 |
NL6700954A (de) | 1967-08-24 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ENGELHARD CORPORATION 70 WOOD AVENUE SOUTH, METRO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PHIBRO CORPORATION, A CORP. OF DE;REEL/FRAME:003968/0801 Effective date: 19810518 |