CA1180677A - Bath and process for high speed nickel electroplating - Google Patents
Bath and process for high speed nickel electroplatingInfo
- Publication number
- CA1180677A CA1180677A CA000386693A CA386693A CA1180677A CA 1180677 A CA1180677 A CA 1180677A CA 000386693 A CA000386693 A CA 000386693A CA 386693 A CA386693 A CA 386693A CA 1180677 A CA1180677 A CA 1180677A
- Authority
- CA
- Canada
- Prior art keywords
- nickel
- bath
- electroplating bath
- acid
- anodes
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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)
- Cosmetics (AREA)
Abstract
ABSTRACT
An electroplating bath suitable for use with insolu-ble anodes in the electrodeposition of nickel comprising a nickel salt, and electrolyte selected from the group consis-ting of boric acid and citric acid, ortho formyl benzene sulfonic acid as a brightener, and a wetting agent comprising a blend of potassium perfluoroalkyl sulfonates. The elec-troplating bath of the invention can be operated at relatively high speeds to produce nickel deposits which are semi-bright, ductile and relatively stress-free.
An electroplating bath suitable for use with insolu-ble anodes in the electrodeposition of nickel comprising a nickel salt, and electrolyte selected from the group consis-ting of boric acid and citric acid, ortho formyl benzene sulfonic acid as a brightener, and a wetting agent comprising a blend of potassium perfluoroalkyl sulfonates. The elec-troplating bath of the invention can be operated at relatively high speeds to produce nickel deposits which are semi-bright, ductile and relatively stress-free.
Description
BACKGROI~ND OF THE INVENTION
It is well known in the art pertaining to electro-lytic nickel systems to utilize soluble anodes. The use of soluble anodes was prescribed because experience has shown that organic additives in the bath break down in the presence of insoluble anodes. Furthermore, it is known that the stress of the nickel deposit is increased by the insoluble anodes and thus adversely affected. For various commercial reasons it would be highly desirable to use insoluble anodes in a nickel electroplating system without encountering additive break down or stressed nickel deposits.
Typical United States patents relating to nickel plating include U.S. Patents 2,228,991 (Freed), 2,409,119 (Freed), 2,409,120 (Freed et al), 2,485,149 (Freed et al); and
It is well known in the art pertaining to electro-lytic nickel systems to utilize soluble anodes. The use of soluble anodes was prescribed because experience has shown that organic additives in the bath break down in the presence of insoluble anodes. Furthermore, it is known that the stress of the nickel deposit is increased by the insoluble anodes and thus adversely affected. For various commercial reasons it would be highly desirable to use insoluble anodes in a nickel electroplating system without encountering additive break down or stressed nickel deposits.
Typical United States patents relating to nickel plating include U.S. Patents 2,228,991 (Freed), 2,409,119 (Freed), 2,409,120 (Freed et al), 2,485,149 (Freed et al); and
2,998,360 (Castellano). As far as can be determined, these patents involve the use of a conventional or modified consuma-ble anode. See, for example, page 2, column 2, lines 53 to 64, of U.S. Patent 2,228,991.
SUMMARY OF THE INVE~TIO~
The present invention relates to a new and improved electroplating bath for use with insoluble anodes and can be operated at relatively high speeds to produce nickel deposits which are also relatively stress-free. The insoluble anodes which can be employed in the process of this invention are, 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 bath of this invention contains certain prescribed additives which do not break down during operations carried out in the presence of insoluble anodes. In addition to a conventional nickel source, e.g. nickel sulfate, and a conducting agent such as boric acid, the electroplating bath will contain ortho-formyl ~enzene sulfonic acid as the brightener and a blend of potassium perfluoroalkyl sulfonates sold under the tradename designation of FC 98 as the wetting agent.
In accordance with the present invention, there is thus provided an electroplating bath suitable for use with insoluble anodes in the electrodeposition of semi-bright, ductile and stress-free nickel deposits, which bath comprises a nickel salt, an electrolyte selected from the group consis-ting of boric acid and citric acid, ortho formyl benzene sul-fonic acid as a brightener, and a wetting agent comprising a blend of potassium perfluoroalkyl sulfonates.
DETAILED DESCRIPTION OF T~E INVE~TIO~
In general, the electroplating baths of the present 20 invention will be formulated as follows:
Component Concentration (q/l) ~ickel Salt 30 to 105 tas ~i) Electrolyte 20 to 100 O-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 prèsent purpose are boric acid, citric acid, and the like. The prefer-red amounts used in preparing the electroplating baths of this 6~7 invention will range from about 22.5 to 45 g/l~ The use of boric acid is especially preferred.
The organic components of the 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 benæene sulfonic acid. The required wetting agent is FC 98, a tradenamed product marketed by the Minnesota Mining & 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 carbonate, sulfuric acid, potassium citrate, or citric acid.
The baths of the present invention are operated at temperatures of about 46 to 57C and at a relatively high cur-rent 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.
Nickel deposited on various substrates when utilizing the baths of this invention is characterized by being semi-bright, ductile, and low-stressed. Heretofore the obtention of such properties required consumable anodes in nic~el elec-troplating systems.
The invention will be more fully understood by reference to the following illustrative embodiment.
i7~
` EY~ PLE
An electroplating bath was formulated from the following ingredients:
Components Concentration ~/1 ~ickel Sulfate 75 (as Ni) Boric Acid 40 O-formyl benzene sulfonic acid 1.5 FC 98* 0.1 *Blend of potassium perfluoroalkyl sulfonates.Prior to use sufficient nickel carbonate was added to the ba.h to adjust 'the pH to about 2.5. The bath was used in a conventional electroplating bath with platinized titanium anodes to coat ;copper at 55C. and 500 ASF. The resulting nickel deposit was semi-bright and ductile. Further analysis indicated low-stre~
,;In utilizing this bath subs.antially no break down of the organic additives present in the bath was noted.
It will be understood that the illus~rative embodiment set forth above is subject to variations and modifications without departing from the broader aspects of the present invention.
SUMMARY OF THE INVE~TIO~
The present invention relates to a new and improved electroplating bath for use with insoluble anodes and can be operated at relatively high speeds to produce nickel deposits which are also relatively stress-free. The insoluble anodes which can be employed in the process of this invention are, 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 bath of this invention contains certain prescribed additives which do not break down during operations carried out in the presence of insoluble anodes. In addition to a conventional nickel source, e.g. nickel sulfate, and a conducting agent such as boric acid, the electroplating bath will contain ortho-formyl ~enzene sulfonic acid as the brightener and a blend of potassium perfluoroalkyl sulfonates sold under the tradename designation of FC 98 as the wetting agent.
In accordance with the present invention, there is thus provided an electroplating bath suitable for use with insoluble anodes in the electrodeposition of semi-bright, ductile and stress-free nickel deposits, which bath comprises a nickel salt, an electrolyte selected from the group consis-ting of boric acid and citric acid, ortho formyl benzene sul-fonic acid as a brightener, and a wetting agent comprising a blend of potassium perfluoroalkyl sulfonates.
DETAILED DESCRIPTION OF T~E INVE~TIO~
In general, the electroplating baths of the present 20 invention will be formulated as follows:
Component Concentration (q/l) ~ickel Salt 30 to 105 tas ~i) Electrolyte 20 to 100 O-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 prèsent purpose are boric acid, citric acid, and the like. The prefer-red amounts used in preparing the electroplating baths of this 6~7 invention will range from about 22.5 to 45 g/l~ The use of boric acid is especially preferred.
The organic components of the 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 benæene sulfonic acid. The required wetting agent is FC 98, a tradenamed product marketed by the Minnesota Mining & 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 carbonate, sulfuric acid, potassium citrate, or citric acid.
The baths of the present invention are operated at temperatures of about 46 to 57C and at a relatively high cur-rent 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.
Nickel deposited on various substrates when utilizing the baths of this invention is characterized by being semi-bright, ductile, and low-stressed. Heretofore the obtention of such properties required consumable anodes in nic~el elec-troplating systems.
The invention will be more fully understood by reference to the following illustrative embodiment.
i7~
` EY~ PLE
An electroplating bath was formulated from the following ingredients:
Components Concentration ~/1 ~ickel Sulfate 75 (as Ni) Boric Acid 40 O-formyl benzene sulfonic acid 1.5 FC 98* 0.1 *Blend of potassium perfluoroalkyl sulfonates.Prior to use sufficient nickel carbonate was added to the ba.h to adjust 'the pH to about 2.5. The bath was used in a conventional electroplating bath with platinized titanium anodes to coat ;copper at 55C. and 500 ASF. The resulting nickel deposit was semi-bright and ductile. Further analysis indicated low-stre~
,;In utilizing this bath subs.antially no break down of the organic additives present in the bath was noted.
It will be understood that the illus~rative embodiment set forth above is subject to variations and modifications without departing from the broader aspects of the present invention.
Claims (5)
1. An electroplating bath suitable for use with insolu-ble anodes in the electrodeposition of semi-bright, ductile and stress-free nickel deposits, said bath comprising a nickel salt; an electrolyte selected from the group consisting of boric acid and citric acid; ortho formyl benzene sulfonic acid as a brightener, and a wetting agent comprising a blend of potassium perfluoroalkyl sulfonates.
2. The electroplating bath of claim 1 wherein the nickel salt is nickel sulfate.
3. The electroplating bath of claim 1 wherein the electrolyte is boric acid.
4. The electroplating bath of claim 1 having a pH of 2.5 to 4.5.
5. A method for electrodepositing nickel on a substrate which comprises passing an electric current between a cathode and an insoluble anode through an electroplating bath as de-fined in claims 1, 2 or 3, for a period of time sufficient to deposit the desired thickness of nickel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19989480A | 1980-10-23 | 1980-10-23 | |
| US199,894 | 1980-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1180677A true CA1180677A (en) | 1985-01-08 |
Family
ID=22739453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000386693A Expired CA1180677A (en) | 1980-10-23 | 1981-09-25 | Bath and process for high speed nickel electroplating |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS6020475B2 (en) |
| AU (1) | AU527954B2 (en) |
| BE (1) | BE890836A (en) |
| BR (1) | BR8106819A (en) |
| CA (1) | CA1180677A (en) |
| CH (1) | CH649579A5 (en) |
| DE (1) | DE3139641C2 (en) |
| DK (1) | DK422181A (en) |
| ES (1) | ES506173A0 (en) |
| FR (1) | FR2492849A1 (en) |
| GB (1) | GB2085924B (en) |
| HK (1) | HK66786A (en) |
| IT (1) | IT1171598B (en) |
| NL (1) | NL8104808A (en) |
| SE (1) | SE8106250L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1162505A (en) * | 1980-10-31 | 1984-02-21 | Donald R. Rosegren | Process for high speed nickel and gold electroplate system |
| US4543166A (en) * | 1984-10-01 | 1985-09-24 | Omi International Corporation | Zinc-alloy electrolyte and process |
| JP4904933B2 (en) * | 2005-09-27 | 2012-03-28 | 日立電線株式会社 | Nickel plating solution and manufacturing method thereof, nickel plating method and copper foil for printed wiring board |
| KR102281132B1 (en) * | 2019-10-24 | 2021-07-26 | 일진머티리얼즈 주식회사 | Electrolytic Nickel Foil for Thin Film-type Capacitor and Production Method of the Same |
| CN112323096A (en) * | 2020-09-23 | 2021-02-05 | 河北东恩企业管理咨询有限公司 | Preparation method of sulfur-nickel-containing round cake |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334032A (en) * | 1964-05-08 | 1967-08-01 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
| US3697391A (en) * | 1970-07-17 | 1972-10-10 | M & T Chemicals Inc | Electroplating processes and compositions |
| ZA721964B (en) * | 1971-04-01 | 1972-12-27 | M & T Chemicals Inc | Nickel plating |
-
1981
- 1981-09-24 DK DK422181A patent/DK422181A/en not_active Application Discontinuation
- 1981-09-25 CA CA000386693A patent/CA1180677A/en not_active Expired
- 1981-09-25 AU AU75676/81A patent/AU527954B2/en not_active Ceased
- 1981-10-06 DE DE3139641A patent/DE3139641C2/en not_active Expired
- 1981-10-09 ES ES506173A patent/ES506173A0/en active Granted
- 1981-10-13 JP JP56163363A patent/JPS6020475B2/en not_active Expired
- 1981-10-21 IT IT49529/81A patent/IT1171598B/en active
- 1981-10-22 SE SE8106250A patent/SE8106250L/en unknown
- 1981-10-22 FR FR8119853A patent/FR2492849A1/en active Granted
- 1981-10-22 BE BE0/206326A patent/BE890836A/en not_active IP Right Cessation
- 1981-10-22 BR BR8106819A patent/BR8106819A/en not_active IP Right Cessation
- 1981-10-22 CH CH6755/81A patent/CH649579A5/en not_active IP Right Cessation
- 1981-10-23 GB GB8132066A patent/GB2085924B/en not_active Expired
- 1981-10-23 NL NL8104808A patent/NL8104808A/en not_active Application Discontinuation
-
1986
- 1986-09-11 HK HK667/86A patent/HK66786A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2492849A1 (en) | 1982-04-30 |
| AU7567681A (en) | 1982-04-29 |
| IT8149529A0 (en) | 1981-10-21 |
| AU527954B2 (en) | 1983-03-31 |
| SE8106250L (en) | 1982-04-24 |
| ES8302802A1 (en) | 1983-01-16 |
| DE3139641A1 (en) | 1982-09-30 |
| BR8106819A (en) | 1982-07-06 |
| IT1171598B (en) | 1987-06-10 |
| JPS5794589A (en) | 1982-06-12 |
| CH649579A5 (en) | 1985-05-31 |
| GB2085924B (en) | 1983-06-02 |
| ES506173A0 (en) | 1983-01-16 |
| FR2492849B1 (en) | 1984-11-23 |
| BE890836A (en) | 1982-04-22 |
| JPS6020475B2 (en) | 1985-05-22 |
| DE3139641C2 (en) | 1986-07-31 |
| DK422181A (en) | 1982-04-24 |
| GB2085924A (en) | 1982-05-06 |
| NL8104808A (en) | 1982-05-17 |
| HK66786A (en) | 1986-09-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |