CA1162505A - Process for high speed nickel and gold electroplate system - Google Patents
Process for high speed nickel and gold electroplate systemInfo
- Publication number
- CA1162505A CA1162505A CA000386447A CA386447A CA1162505A CA 1162505 A CA1162505 A CA 1162505A CA 000386447 A CA000386447 A CA 000386447A CA 386447 A CA386447 A CA 386447A CA 1162505 A CA1162505 A CA 1162505A
- Authority
- CA
- Canada
- Prior art keywords
- gold
- nickel
- acid
- electro
- salt
- 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
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
- C25D3/56—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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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)
- Electroplating Methods And Accessories (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Improved corrosion resistance of cobalt-hardened gold plating is achieved by the electrodeposition of a ductile, low-stress nickel coating on the substrate prior to the electrodeposition of the cobalt-hardened gold plating.
The resulting plated substrate or workpiece is also described and claimed.
Improved corrosion resistance of cobalt-hardened gold plating is achieved by the electrodeposition of a ductile, low-stress nickel coating on the substrate prior to the electrodeposition of the cobalt-hardened gold plating.
The resulting plated substrate or workpiece is also described and claimed.
Description
1 1625(~
FIELD OF THE INUENTION
~ he present invention relates to the electrodeposi-tion of gold on substrates. More particularly, the invention pertains to improving the corrosion resistance of cobalt-hardened gold coatings which are electrodeposited on varioussubstratesO
BACKGROUND OF_THE INVENTION
It is well known in the metallizing art to electro-deposit, also referred to as electrolytic deposition and electroplating,cobalt-hardened gold coatings on substrates.
In conventional procedures a deposition bath comprising ions of metal to be deposited and a suitable electrolyte is pro-vided, the article or object to be plated is immersed in or otherwise contacted with the bath while connected as the cathode to an external current source, and a metal electrode is connected as the anode to the same current source. During electroplating operations ions of the metal to be deposited are reduced in the bath to zero valent metal which plates out on the workpiece or substrate surface.
The use of cobalt to harden gold coatings is described, for example, in U.S. Patent No. 2,905,601 which will be discussed below in cJreater detail.
It has been found, however, that such conventional cobalt-hardened gold coatings do no'c have the high degree of corrosion resistance which is an important property for some commercial purposes. Thus, it would be desirable to provide a system or process for preparing special cobalt-hardened, gold electrodeposits with markealy improved corrosion resis--tance and cosmetic appearance such as brightness, smoothness.
In some instances it has been possible to achieve such desir-able results at substantially reduced thicknesses of metal.
-1- .~
SUMMARY OF THE INVENTION
In accordance wi~h the present invention it has now been found that cobalt-hardened gold coatings having improved corrosion resistance can be obtained by initially coating the workpiece or substrate with a ductile, stress-free nickel deposit.
Accordingly, the p~esent invention provides a process for obtàining an improved corrosion-resistant gold plating on a substrate, which comprises the following sequential plating steps:
(a) electrodepositing a ductile, stress-free nickel coating on the substrate from an electroplating bath contain-ing a nickel salt, an electrolyte selected from the group consisting of boric acid and citric acid, ortho-formyl benzene sulfonic acid, and as a wetting agent a blend of potassium perfluoroalkyl sulfonates, and (b) electrodepositing a base metal-hardened gold coating on the resulting ductile, stress-free nickel plated substrate from an electroplating bath containing a gold salt, an electrolyte selected from the group consisting of acetic acid, citric acid, formic acid and mixtures thereof, and a metal salt hardener selected from the group consisting of cobalt, indium, nickel zinc salts and mixtures thereof.
The invention is also directed to a substrate provided with a cobalt-hardened gold plating having improved corrosion resistance, as prepared by the above process.
The necessary nickel coating on the substrate is derived from a specially prepared electroplating bath which, preferably, can be utilized with insoluble anodes.
In general, the nickel electroplating baths will contain a nickel salt such as nickel sulfate, as a source of nickel ions, and boric acid or citric acid as the electrolyte.
Although other conventional additives may be employed, it has been found essential to use ortho-formyl benzene sulfonic acid as the brightener and a blend of potassium perfluoroalkyl sulfonates, sold under the trademark FC 98 by the 3M Company, as the wetting agent.
Following the electrodepositing of the ductile, stress-free nickel coating the workpiece is subjected to the electrodeposition of the outer coating comprising cobalt-hardened gold.
By practicing the foregoing sequential electro-deposition steps, the cobalt-hardened gold coating was characterized by a superior corrosion resistance as compared to the corrosion resistance of the same cobalt-hardened gold coating without the intermediate ductile, stress-free nickel coating~ On the other hand, the superior corrosion was not attained even with the intermediate ductile, stress-free nickel coating when the gold was hardened with, for example, iron rather than cobalt.
Corrosion resistance is measured by Western Electric's manufacturing specification WL 2316.
FIELD OF THE INUENTION
~ he present invention relates to the electrodeposi-tion of gold on substrates. More particularly, the invention pertains to improving the corrosion resistance of cobalt-hardened gold coatings which are electrodeposited on varioussubstratesO
BACKGROUND OF_THE INVENTION
It is well known in the metallizing art to electro-deposit, also referred to as electrolytic deposition and electroplating,cobalt-hardened gold coatings on substrates.
In conventional procedures a deposition bath comprising ions of metal to be deposited and a suitable electrolyte is pro-vided, the article or object to be plated is immersed in or otherwise contacted with the bath while connected as the cathode to an external current source, and a metal electrode is connected as the anode to the same current source. During electroplating operations ions of the metal to be deposited are reduced in the bath to zero valent metal which plates out on the workpiece or substrate surface.
The use of cobalt to harden gold coatings is described, for example, in U.S. Patent No. 2,905,601 which will be discussed below in cJreater detail.
It has been found, however, that such conventional cobalt-hardened gold coatings do no'c have the high degree of corrosion resistance which is an important property for some commercial purposes. Thus, it would be desirable to provide a system or process for preparing special cobalt-hardened, gold electrodeposits with markealy improved corrosion resis--tance and cosmetic appearance such as brightness, smoothness.
In some instances it has been possible to achieve such desir-able results at substantially reduced thicknesses of metal.
-1- .~
SUMMARY OF THE INVENTION
In accordance wi~h the present invention it has now been found that cobalt-hardened gold coatings having improved corrosion resistance can be obtained by initially coating the workpiece or substrate with a ductile, stress-free nickel deposit.
Accordingly, the p~esent invention provides a process for obtàining an improved corrosion-resistant gold plating on a substrate, which comprises the following sequential plating steps:
(a) electrodepositing a ductile, stress-free nickel coating on the substrate from an electroplating bath contain-ing a nickel salt, an electrolyte selected from the group consisting of boric acid and citric acid, ortho-formyl benzene sulfonic acid, and as a wetting agent a blend of potassium perfluoroalkyl sulfonates, and (b) electrodepositing a base metal-hardened gold coating on the resulting ductile, stress-free nickel plated substrate from an electroplating bath containing a gold salt, an electrolyte selected from the group consisting of acetic acid, citric acid, formic acid and mixtures thereof, and a metal salt hardener selected from the group consisting of cobalt, indium, nickel zinc salts and mixtures thereof.
The invention is also directed to a substrate provided with a cobalt-hardened gold plating having improved corrosion resistance, as prepared by the above process.
The necessary nickel coating on the substrate is derived from a specially prepared electroplating bath which, preferably, can be utilized with insoluble anodes.
In general, the nickel electroplating baths will contain a nickel salt such as nickel sulfate, as a source of nickel ions, and boric acid or citric acid as the electrolyte.
Although other conventional additives may be employed, it has been found essential to use ortho-formyl benzene sulfonic acid as the brightener and a blend of potassium perfluoroalkyl sulfonates, sold under the trademark FC 98 by the 3M Company, as the wetting agent.
Following the electrodepositing of the ductile, stress-free nickel coating the workpiece is subjected to the electrodeposition of the outer coating comprising cobalt-hardened gold.
By practicing the foregoing sequential electro-deposition steps, the cobalt-hardened gold coating was characterized by a superior corrosion resistance as compared to the corrosion resistance of the same cobalt-hardened gold coating without the intermediate ductile, stress-free nickel coating~ On the other hand, the superior corrosion was not attained even with the intermediate ductile, stress-free nickel coating when the gold was hardened with, for example, iron rather than cobalt.
Corrosion resistance is measured by Western Electric's manufacturing specification WL 2316.
-2(a)-DETAILED DESCRIPTION OF THE INVENTION
The nickel salt electroplating bath useful in the initial coating step of the present invention will have the following formulation:
Component Concentration q/l Nickel Salt 30 to 105 (as Ni) Electrolyte 20 to 100 0-formyl benzene sulfonic acid 0.25 to 3.0 FC 98 0.02 to 0.2 The preferred sources of the nickel metal are nickel sulfate, nickel citrate, nickel carbonate, and the like. These salts are preferably employed in an amount of from about 135 to 470 g/l to provide the desired nickel metal concentration.
Electrolytes which are most useful for the present purposes are boric acid, citric acid, and the like. The preferred amounts used in preparing the electroplating baths of this invention will range from about 22.5 to 45 g/l. The use of boric acid is especially preferred.
The organic components of the nickel bath are usually the brighteners and the wetting agents. In formulating the special electroplating bath of this invention the specific brightener employed is ortho-formyl benzene sulfonic acid. The required wetting agent is FC 98, a tradenamed product marketed by the Minnesota Minning & Manufacturing Company.
For most purposes the pH of the electroplating bath is adjusted to a range of about 2 to 5, preferably 2.5 to 4.5.
The compounds used to effect the pH adjustment include nickel c~rbonate, sulfuric acid, potassium citrate, or citric acid.
1 1625(~$
The baths of the present invention are operated at temperatures of about 46 to 57C. and at relatively high current density of up to about 1000 ASF, and preferably about 100 to 600 ASF. The ability to use such high current densities is another important advantage of the electroplating baths of the present invention.
~ ickel deposited on various substrates when utilizing the baths of this invention are characterized by being semi-bright, ductile, and low-stressed. Furthermore, it is possible to use insoluble anodes in carrying out both the initial and second coating steps. The insoluble anodes which can be employed include, for example, platinized titanium, platinized tantalum, platinized columbium (niobium) as well as a platinum metal anode itself. Additionally, titanium anodes having mixed oxide coatings, such as ruthenium dioxide - titanium dioxide coatings, may also be used.
The electroplating of hardened gold deposits can be carried out utilizing the baths and the processes described in U.S. Patent No. 2,905,601 Rinker and Duva (1959). Although cobalt-hardened gold outer coatings are preferred, it will be understood that other metal hardeners such as indium, or nickel may also be employed in the practice of the present process which involves the use of a high speed gold treating process following the application of a high speed nickel treating process to form the initial or intermediate coating on the substrate or workpiece.
me electroplating bath useful for the gold plating step will comprise (1) a weak, stable, organic acid (2) gold as a cyanide (po-tassium gold cyanide, for example), and (3) one or more base metal salts soluble in the bath.
Examples of acids which may be employed are formic, acetic, citric, tartaric, lactic, kojic, or similar acids and mixtures of these acids. The acid should be present in proportions of about 10 to 150 grams per liter and may be partially neutralized with ammonium or alkali hydroxide to give a pH of about 3-5. It is this weak organic acid and the procedure of maintaining the bath within a limited pH range that produces the desired effect of a gold alloy deposition.
The gold may be added as the double cyanide of gold and an alkali metal, potassium gold cyanide for example, and may be present in proportions of about 8 grams per liter to 26 grams per liter of gold, preferably 12.
Base metal salts which may be added comprise the sulfates, sulfamates, formates, acetates, citrates, lactates, tartrates, fluoborates, borates, phosphates, etc., of nickel, zinc, cobalt, indium, iron, manganese, antimony, copper, etc.
These metal salts are added in the proportion of from 0.5 to S grams per liter. Very satisfactory results are obtained when two of such base metal salts are included in the bath.
Although the addition of base metal salt is necessary, it does not matter which salt or mixture of salts is added as long as the added salts are soluble and compatible with all other bath ingredients.
The bath may be opera-ted at a current density of 1 to 100 amperes per square foot. Moderate to rapid agitation improves the operation. The bath may be operated at normal t ~ ¢25()~
room temperature (70F.) which is advantayeous in that no thermostatic regulation is necessary but hig~ler or lower temperatures of from 50 to 120F. may be employed. The maximum cathode/anode ratio should be about 4:1.
The prefered electroplating bath useful for the second coating step will have the following formulation:
Component Concentration (q/l) Acetic Acid and Sodiu~ Citrate lO0 to 300 Formic Acid lO to 50 mls/l lO Gold (as potassium gold cyanide) 12 to 26 ; Cobalt (as sulfate) 0.5 to 1.75 Water Remainder ~ he invention will be more fully understood by reference to the following illustrative embodiment:
EXAMPLE
A first electrolytic bath was prepared by dissolving the following components~
q/l Nickel (as sulfate) 75 20 Boric Acid 40 0-Formyl Benzene Sulfonic Acid 1.5 FC 98 0.1 Water Remainder A second electrolytic bath was prepared by dissolving the following components:
g/l Citric Acid (as potassium citrate) 200 Formic Acid 20 mls/l Gold (as potassium gold cyanide) 12 30 Cobalt (as sulfate) 1.5 Water Remainder ~ 16~5~)5 The pH of this bath is adjusted to about 4.8 to 5,2 by the addition of an alkali or acid.
Run A
.
The substrate, commercial copper plated circuit board, is first treated in the nickel electroplating bath to give a semi-bright, ductile, and stress-free nickel deposit having a thickness between about 2.5 to 5 ~u. The thus coated substrate is then treated in the second or gold electro-plating bath to give a bright, smooth, and hard gold deposit.
This coating has a thickness of from about 1 to 2 jU. The corrosion resistance of the resulting product, as measured in accordance with Western Electric's manufacturing specification WL 2316, is found to be outstanding.
Run B
When the step of electrodepositing the nickel coating is omitted, the resulting product's corrosion resistance is substantially reduced.
The nickel salt electroplating bath useful in the initial coating step of the present invention will have the following formulation:
Component Concentration q/l Nickel Salt 30 to 105 (as Ni) Electrolyte 20 to 100 0-formyl benzene sulfonic acid 0.25 to 3.0 FC 98 0.02 to 0.2 The preferred sources of the nickel metal are nickel sulfate, nickel citrate, nickel carbonate, and the like. These salts are preferably employed in an amount of from about 135 to 470 g/l to provide the desired nickel metal concentration.
Electrolytes which are most useful for the present purposes are boric acid, citric acid, and the like. The preferred amounts used in preparing the electroplating baths of this invention will range from about 22.5 to 45 g/l. The use of boric acid is especially preferred.
The organic components of the nickel bath are usually the brighteners and the wetting agents. In formulating the special electroplating bath of this invention the specific brightener employed is ortho-formyl benzene sulfonic acid. The required wetting agent is FC 98, a tradenamed product marketed by the Minnesota Minning & Manufacturing Company.
For most purposes the pH of the electroplating bath is adjusted to a range of about 2 to 5, preferably 2.5 to 4.5.
The compounds used to effect the pH adjustment include nickel c~rbonate, sulfuric acid, potassium citrate, or citric acid.
1 1625(~$
The baths of the present invention are operated at temperatures of about 46 to 57C. and at relatively high current density of up to about 1000 ASF, and preferably about 100 to 600 ASF. The ability to use such high current densities is another important advantage of the electroplating baths of the present invention.
~ ickel deposited on various substrates when utilizing the baths of this invention are characterized by being semi-bright, ductile, and low-stressed. Furthermore, it is possible to use insoluble anodes in carrying out both the initial and second coating steps. The insoluble anodes which can be employed include, for example, platinized titanium, platinized tantalum, platinized columbium (niobium) as well as a platinum metal anode itself. Additionally, titanium anodes having mixed oxide coatings, such as ruthenium dioxide - titanium dioxide coatings, may also be used.
The electroplating of hardened gold deposits can be carried out utilizing the baths and the processes described in U.S. Patent No. 2,905,601 Rinker and Duva (1959). Although cobalt-hardened gold outer coatings are preferred, it will be understood that other metal hardeners such as indium, or nickel may also be employed in the practice of the present process which involves the use of a high speed gold treating process following the application of a high speed nickel treating process to form the initial or intermediate coating on the substrate or workpiece.
me electroplating bath useful for the gold plating step will comprise (1) a weak, stable, organic acid (2) gold as a cyanide (po-tassium gold cyanide, for example), and (3) one or more base metal salts soluble in the bath.
Examples of acids which may be employed are formic, acetic, citric, tartaric, lactic, kojic, or similar acids and mixtures of these acids. The acid should be present in proportions of about 10 to 150 grams per liter and may be partially neutralized with ammonium or alkali hydroxide to give a pH of about 3-5. It is this weak organic acid and the procedure of maintaining the bath within a limited pH range that produces the desired effect of a gold alloy deposition.
The gold may be added as the double cyanide of gold and an alkali metal, potassium gold cyanide for example, and may be present in proportions of about 8 grams per liter to 26 grams per liter of gold, preferably 12.
Base metal salts which may be added comprise the sulfates, sulfamates, formates, acetates, citrates, lactates, tartrates, fluoborates, borates, phosphates, etc., of nickel, zinc, cobalt, indium, iron, manganese, antimony, copper, etc.
These metal salts are added in the proportion of from 0.5 to S grams per liter. Very satisfactory results are obtained when two of such base metal salts are included in the bath.
Although the addition of base metal salt is necessary, it does not matter which salt or mixture of salts is added as long as the added salts are soluble and compatible with all other bath ingredients.
The bath may be opera-ted at a current density of 1 to 100 amperes per square foot. Moderate to rapid agitation improves the operation. The bath may be operated at normal t ~ ¢25()~
room temperature (70F.) which is advantayeous in that no thermostatic regulation is necessary but hig~ler or lower temperatures of from 50 to 120F. may be employed. The maximum cathode/anode ratio should be about 4:1.
The prefered electroplating bath useful for the second coating step will have the following formulation:
Component Concentration (q/l) Acetic Acid and Sodiu~ Citrate lO0 to 300 Formic Acid lO to 50 mls/l lO Gold (as potassium gold cyanide) 12 to 26 ; Cobalt (as sulfate) 0.5 to 1.75 Water Remainder ~ he invention will be more fully understood by reference to the following illustrative embodiment:
EXAMPLE
A first electrolytic bath was prepared by dissolving the following components~
q/l Nickel (as sulfate) 75 20 Boric Acid 40 0-Formyl Benzene Sulfonic Acid 1.5 FC 98 0.1 Water Remainder A second electrolytic bath was prepared by dissolving the following components:
g/l Citric Acid (as potassium citrate) 200 Formic Acid 20 mls/l Gold (as potassium gold cyanide) 12 30 Cobalt (as sulfate) 1.5 Water Remainder ~ 16~5~)5 The pH of this bath is adjusted to about 4.8 to 5,2 by the addition of an alkali or acid.
Run A
.
The substrate, commercial copper plated circuit board, is first treated in the nickel electroplating bath to give a semi-bright, ductile, and stress-free nickel deposit having a thickness between about 2.5 to 5 ~u. The thus coated substrate is then treated in the second or gold electro-plating bath to give a bright, smooth, and hard gold deposit.
This coating has a thickness of from about 1 to 2 jU. The corrosion resistance of the resulting product, as measured in accordance with Western Electric's manufacturing specification WL 2316, is found to be outstanding.
Run B
When the step of electrodepositing the nickel coating is omitted, the resulting product's corrosion resistance is substantially reduced.
Claims (11)
1.- A process for obtaining an improved corrosion-resistant gold plating on a substrate which comprises the following sequential plating steps:
(a) electrodepositing a ductile, stress-free nickel coating on said substrate from an electroplating bath contain-ing a nickel salt, an electrolyte selected from the group consisting of boric acid and citric acid, ortho-formyl benzene sulfonic acid, and as a wetting agent a blend of potassium perfluoroalkyl sulfonates; and (b) electrodepositing a base metal-hardened gold coating on the resulting ductile, stess-free nickel plated substrate from an electroplating bath containing a gold salt, an electrolyte selected from the group consisting of acetic acid, citric acid, formic acid and mixtures thereof, and a metal salt hardener selected from the group consisting of cobalt, indium, nickel, zinc salts and mixtures thereof.
(a) electrodepositing a ductile, stress-free nickel coating on said substrate from an electroplating bath contain-ing a nickel salt, an electrolyte selected from the group consisting of boric acid and citric acid, ortho-formyl benzene sulfonic acid, and as a wetting agent a blend of potassium perfluoroalkyl sulfonates; and (b) electrodepositing a base metal-hardened gold coating on the resulting ductile, stess-free nickel plated substrate from an electroplating bath containing a gold salt, an electrolyte selected from the group consisting of acetic acid, citric acid, formic acid and mixtures thereof, and a metal salt hardener selected from the group consisting of cobalt, indium, nickel, zinc salts and mixtures thereof.
2.- The process of claim 1, wherein the nickel salt is nickel sulfate and the electrolyte is boric acid.
3.- The process of claim 1, wherein electroplating bath (a) is operated at a pH of 2 to 5.
4.- The process of claim 1, wherein the electro-deposition steps (a) and (b) are carried out with insoluble anodes.
5.- The process of claim 1, wherein the gold salt is a gold cyanide salt.
6.- The process of claim 5, wherein said electro-plating bath (b) comprises potassium gold cyanide.
7.- The process of claim 1, wherein said electro-plating bath (b) comprises acetic acid as the electrolyte.
8.- The process of claim 1, wherein said electro-plating bath (b) comprises cobalt sulfate as the base metal salt.
9.- The process of claim 1, wherein said electro-plating bath (b) comprises citric acid as the electrolyte.
10.- The process of claim 1, wherein said electro-plating bath (b) comprises formic acid and citric acid as the electrolyte.
11.- A substrate provided with a cobalt-hardened gold plating having improved corrosion resistance, as prepared by the process of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20241080A | 1980-10-31 | 1980-10-31 | |
| US202,410 | 1980-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1162505A true CA1162505A (en) | 1984-02-21 |
Family
ID=22749762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000386447A Expired CA1162505A (en) | 1980-10-31 | 1981-09-23 | Process for high speed nickel and gold electroplate system |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS6053120B2 (en) |
| AU (1) | AU530002B2 (en) |
| BE (1) | BE890947A (en) |
| BR (1) | BR8107041A (en) |
| CA (1) | CA1162505A (en) |
| DE (1) | DE3139815C2 (en) |
| DK (1) | DK422081A (en) |
| ES (1) | ES8206671A1 (en) |
| FR (1) | FR2493349A1 (en) |
| GB (1) | GB2086428B (en) |
| HK (1) | HK66886A (en) |
| IT (1) | IT1171616B (en) |
| NL (1) | NL8104859A (en) |
| SE (1) | SE8106386L (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2130602B (en) * | 1982-11-24 | 1986-04-16 | Stc Plc | Electroplating electrical contacts |
| EP0127857B1 (en) * | 1983-05-28 | 1987-07-29 | Masami Kobayashi | Solderable stainless steel article and method for making same |
| JPS607157A (en) * | 1983-06-25 | 1985-01-14 | Masami Kobayashi | Lead frame for ic |
| JPS6033363A (en) * | 1983-08-02 | 1985-02-20 | Nippon Dento Kogyo Kk | Noble metal plating method |
| GB2153386B (en) * | 1984-02-01 | 1987-08-26 | Omi Int Corp | Gold alloy plating bath |
| GB2168381B (en) * | 1984-12-12 | 1988-03-09 | Stc Plc | Gold plated electrical contacts |
| JP2693480B2 (en) * | 1988-04-28 | 1997-12-24 | シチズン時計株式会社 | Exterior parts for watch and manufacturing method thereof |
| JP2780506B2 (en) * | 1991-03-04 | 1998-07-30 | 戸田工業株式会社 | Electric Ni plating method |
| US9693672B2 (en) | 2011-09-22 | 2017-07-04 | Whirlpool Corporation | Dishwasher with sprayer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1124780B (en) * | 1960-10-08 | 1962-03-01 | Schering Ag | Electrolyte for the deposition of high-gloss nickel coatings |
| DE1496818C3 (en) * | 1964-03-12 | 1978-04-27 | Dr. Hesse & Cie, 4800 Bielefeld | Process for the electrolytic production of gold layers with a high, uniform gloss and good resistance to corrosion and tarnishing |
| US3334032A (en) * | 1964-05-08 | 1967-08-01 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
| GB1442325A (en) * | 1972-07-26 | 1976-07-14 | Oxy Metal Finishing Corp | Electroplating with gold and gold alloys |
| FR2309203A1 (en) * | 1975-04-30 | 1976-11-26 | Parant Sa | Dental cap based on stainless steel - which is electrolytically deposited with nickel and gold and finally coated with ceramic |
| DK422181A (en) * | 1980-10-23 | 1982-04-24 | Hooker Chemicals Plastics Corp | BATH AND METHOD FOR HIGH SPEED NICKEL ELECTROPLETING |
-
1981
- 1981-09-23 CA CA000386447A patent/CA1162505A/en not_active Expired
- 1981-09-24 DK DK422081A patent/DK422081A/en not_active Application Discontinuation
- 1981-09-25 AU AU75675/81A patent/AU530002B2/en not_active Ceased
- 1981-10-07 DE DE3139815A patent/DE3139815C2/en not_active Expired
- 1981-10-22 FR FR8119852A patent/FR2493349A1/en not_active Withdrawn
- 1981-10-24 JP JP56170635A patent/JPS6053120B2/en not_active Expired
- 1981-10-26 ES ES506573A patent/ES8206671A1/en not_active Expired
- 1981-10-27 NL NL8104859A patent/NL8104859A/en not_active Application Discontinuation
- 1981-10-29 SE SE8106386A patent/SE8106386L/en not_active Application Discontinuation
- 1981-10-29 IT IT49589/81A patent/IT1171616B/en active
- 1981-10-30 BR BR8107041A patent/BR8107041A/en unknown
- 1981-10-30 BE BE0/206412A patent/BE890947A/en not_active IP Right Cessation
- 1981-11-02 GB GB8132943A patent/GB2086428B/en not_active Expired
-
1986
- 1986-09-11 HK HK668/86A patent/HK66886A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2493349A1 (en) | 1982-05-07 |
| JPS5798694A (en) | 1982-06-18 |
| GB2086428A (en) | 1982-05-12 |
| ES506573A0 (en) | 1982-08-16 |
| DE3139815A1 (en) | 1982-06-16 |
| ES8206671A1 (en) | 1982-08-16 |
| JPS6053120B2 (en) | 1985-11-22 |
| AU7567581A (en) | 1982-05-06 |
| BE890947A (en) | 1982-04-30 |
| HK66886A (en) | 1986-09-18 |
| AU530002B2 (en) | 1983-06-30 |
| IT8149589A0 (en) | 1981-10-29 |
| IT1171616B (en) | 1987-06-10 |
| NL8104859A (en) | 1982-05-17 |
| DE3139815C2 (en) | 1986-05-22 |
| SE8106386L (en) | 1982-05-01 |
| BR8107041A (en) | 1982-07-20 |
| DK422081A (en) | 1982-05-01 |
| GB2086428B (en) | 1983-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3940319A (en) | Electrodeposition of bright tin-nickel alloy | |
| TWI439580B (en) | Pyrophosphate-based bath for plating of tin alloy layers | |
| US4411965A (en) | Process for high speed nickel and gold electroplate system and article having improved corrosion resistance | |
| US4384929A (en) | Process for electro-depositing composite nickel layers | |
| CA1162505A (en) | Process for high speed nickel and gold electroplate system | |
| US3691027A (en) | Method of producing corrosion resistant chromium plated articles | |
| US3620936A (en) | Electroplating a decorative chromium-plating resistant to corrosion | |
| US3500537A (en) | Method of making palladium coated electrical contacts | |
| US3183067A (en) | Metal having two coats of sulfurcontaining nickel and method of making same | |
| US4299671A (en) | Bath composition and method for electrodepositing cobalt-zinc alloys simulating a chromium plating | |
| EP0348043B1 (en) | Electroplating bath and process for depositing functional chromium | |
| US3615281A (en) | Corrosion-resistant chromium-plated articles | |
| EP0128358A1 (en) | Specular product of bronze-like tone | |
| CA2236933A1 (en) | Electroplating of low-stress nickel | |
| US4549942A (en) | Process for electrodepositing composite nickel layers | |
| CA1180677A (en) | Bath and process for high speed nickel electroplating | |
| US4411744A (en) | Bath and process for high speed nickel electroplating | |
| US4082621A (en) | Plating method with lead or tin sublayer | |
| US4244790A (en) | Composition and method for electrodeposition of black nickel | |
| US4435254A (en) | Bright nickel electroplating | |
| US3984291A (en) | Electrodeposition of tin-lead alloys and compositions therefor | |
| US3020217A (en) | Mirror bright gold alloy electroplating | |
| US2461933A (en) | Rhodium alloy coatings and method of making same | |
| GB2133040A (en) | Copper plating bath process and anode therefore | |
| US4428804A (en) | High speed bright silver electroplating bath and process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |