US3795592A - Nickel electroplating composition and process - Google Patents
Nickel electroplating composition and process Download PDFInfo
- Publication number
- US3795592A US3795592A US00336588A US3795592DA US3795592A US 3795592 A US3795592 A US 3795592A US 00336588 A US00336588 A US 00336588A US 3795592D A US3795592D A US 3795592DA US 3795592 A US3795592 A US 3795592A
- Authority
- US
- United States
- Prior art keywords
- nickel
- coumarin
- bath
- leveling
- amounts
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
-
- 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
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
Definitions
- This invention relates to an improved composition and process for the electrodeposition of metal and more particularly, it relates to improved composition and process for the formation of semi-bright electrodeposits of nickel and nickel alloys.
- coumarin as an additive in Watts type nickel electroplating baths, to produce soft, ductile, lustrous deposits with excellent leveling is well known. It is further known that the degree of leveling obtained is, in general, proportional to the concentration of coumarin in the plating bath, at least within concentration ranges of about 0.05 to 0.3 grams/liter.
- the invention relates to an improved composition and process for the electrodeposition of metal. More particularly, it relates to an improved composition and process for the formation of semi-bright electrodeposits of nickel and nickel alloys.
- the present invention is directed to a plating bath for the electrodeposition of nickel, which comprises an aqueous solution of at least one nickel salt, a coumarin compound and brightening and leveling amounts of a l-propynoxy sulfonate compound.
- the present invention is directed to electroplating baths 7 which are aqueous acidic solutions containing one or more nickel salts.
- such baths may be prepared by dissolving nickel chloride and/or nickel sulfate and boric acid in water.
- Other nickel electroplating baths are those based on nickel formate, nickel sulfamate, nickel fluoroborate, or the like, as the nickel salt dissolved in the aqueous acidic solvent, may also be used.
- the electroplating baths of the present invention may also contain one or more cobalt salts, of the same or similar type as the nickel salts have been indicated above. Where the electroplating baths used contain cobalt salts in addition to the nickel salts, the relative amount of these should be such that the resulting nickel-cobalt alloy electroplate produced contains at least about 80% nickel.
- the nickel electroplating baths will contain effective brightening and/or leveling amounts of a l-propynoxy sulfonate compound.
- the sulfonate will contain at least the following structure:
- R is a saturated alkylene or a hydroxy substituted saturated alkylene; R is a saturated alkylene, hydroxy substituted alkylene, or
- the sulfonate preferred is present in the electroplating baths in very minute amounts within the range of 1 to about milligrams/liter, with the range from about 1 to 10 milligrams/ liter being preferred.
- the above brightening and leveling compound will be employed in order to carry the degradation products of coumarin or coumarin derivatives.
- coumarin compound or material in addition to coumarin itself, which is the most preferred, various substituted coumarins may also be used, such as 3-chlorocoumarin; 6- chlorocoumarin; 3-bromocoumarin, 3-acetyl coumarin; 7- hydroxy ethyl coumarin; S-methoxy coumarin; 7-ethoxycoumarin; 4,8-dimethyl coumarin; coumarin, 7-oxy propane sulfonic acid; and the like.
- the coumarin or substituted coumarin compounds are present in the electroplating baths in amounts within the range of about 0.025 to 0.5 grams/liter, with amounts within the range of about 0.05 to 0.3 grams/ liter being preferred.
- the combination of the propargyl sulfonate compound with the coumarin compound overcomes the adverse elfects with the coumarin degradation products, and results in a consistently semi-bright deposit, it has been found that as the electroplating bath is used over extended periods of time, there is a gradual decrease in the leveling properties, for a givenconcentration of coumarin. This decrease in leveling is minimized by also including butyne diol in the bath, as an additional additive. In this manner, without increasing the coumarin concentration, a semibright nickel electrodeposit, having excellent leveling is consistently produced. Accordingly, in its most preferred embodiment, the electroplating bath of the present invention will typically contain from about 3 to 60 milligrams/ liter butyne diol, with amounts of from about 10 to 40 milligrams/liter being preferred.
- an aqueous acidic solution is formed containing the desired nickel or nickel and cobalt salts.
- these electroplating baths will have a pH within the range of about 3 to 4.5 and, depending upon the particular nickel salts used, will contain the nickel salts in amounts within the range of about 200 to 400 grams/liter.
- cobalt salts are also present in the electroplating baths, these will typically be present in amounts within the range of about 10 to grams/liter, depending upon the particular salts used as well as the amount of the nickel salt which is present.
- this material is desirable present in amounts within the range of about 30 to 60 grams/liter.
- the additive components are included in the electroplating bath in the amounts which have been indicated hereinabove.
- the electroplating solutions will typically be used at a temperature within the range of about 45 to 63 degrees centrigrade.
- agitation of the solution either by air agitation, cathode rod agitation, mechanical agitation or the like, is preferred.
- semi-bright nickel electrodeposits are obtained over a wide current density range,
- the typical average current densities used. in the operation of the process are within the range of about 25 to 50 amps per square foot, with plating times of from about 10 to 60 minutes.
- the coumarin degradation products will decrease the brightness and leveling obtained from a given concentration of coumarin, in a proportion to themelilotic acid concentration, thus requiring the use of greater amounts of coumarin to maintain the leveling, by the use of these two additional additives the concentration of coumarin may be maintained at a consistent level even when appreciable amounts of melilotic acid are present, while still obtaining excellent brightness and leveling results.
- Example A nickel plating bath was prepared containing the following components; nickel chloride 5.5 ounces per gallon; nickel sulfate 40 ounces per gallon; boric acid 5.5 ounces per gallon, melilotic acid, 3 grams/liter, pH 4.0; temperature F. with air agitation:
- the l-propynoxy sulfonates of the present application can be prepared in a number of ways. Some ways are: Propargyl alcohol may be reacted with a sultone resulting in an alkylenegroup attached to the oxygen of the propargyl alcohol and a terminal sulfonate group attached to the alkylene group.
- the reaction can be described as follows: Propargyl alcohol can be reacted with equal molar amounts of propane sultone giving the following reaction:
- Butyne diol reacted with concentrated Do.
- An aqueous acidic nickel electroplating bath comprising a coumarin compound and an effective leveling and brightening amount of a bath soluble l-propynoxy sulfonate compound effective to carry the degradation product of coumarin.
- R is independently selected from the group consisting of saturated alkylene and hydroxy substituted saturated alkylene
- R is independently selected from the group consisting of saturated alkylene, hydroxy substituted saturated alkylene and wherein R is a hydroxy substituted alkylene or a saturated alkylene; M is a bath soluble cation; and x is'from 0 to 3 inclusive.
- R is a saturated alkylene of up to 3 carbon atoms.
- a method of producing semi-bright nickel electrodeposits comprising passing an electric current from an anode to a cathode through an aqueous acidic solution of claim 1 for a period of time sufficient to form a semibright nickel deposit.
- 'R is a hydroxy substituted alkylene or a saturated alkylene
- M is a bath soluble cation
- x is from 0 to 3 inclusive.
- R is a saturated alkylene of up to 3 carbon atoms.
- R is hydroxy substituted saturated alkylene of up to 3 carbon atoms.
- butyne diol is present in an amount ranging from 10 to 40 mg./l.
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)
Abstract
Description
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US9734670A | 1970-12-11 | 1970-12-11 | |
US33658873A | 1973-02-28 | 1973-02-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3795592A true US3795592A (en) | 1974-03-05 |
Family
ID=26793147
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00097346A Expired - Lifetime US3719568A (en) | 1970-12-11 | 1970-12-11 | Nickel electroplating composition and process |
US00336588A Expired - Lifetime US3795592A (en) | 1970-12-11 | 1973-02-28 | Nickel electroplating composition and process |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00097346A Expired - Lifetime US3719568A (en) | 1970-12-11 | 1970-12-11 | Nickel electroplating composition and process |
Country Status (7)
Country | Link |
---|---|
US (2) | US3719568A (en) |
AU (1) | AU454350B2 (en) |
CA (1) | CA993832A (en) |
DE (2) | DE2147257C3 (en) |
FR (2) | FR2117877B1 (en) |
GB (2) | GB1338688A (en) |
NL (2) | NL7116879A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4062738A (en) * | 1974-10-04 | 1977-12-13 | E. I. Du Pont De Nemours And Company | Acid nickel electroplating additive therefor and method of making said additive |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3719568A (en) * | 1970-12-11 | 1973-03-06 | Oxy Metal Finishing Corp | Nickel electroplating composition and process |
DE3067275D1 (en) * | 1979-09-13 | 1984-05-03 | M & T Chemicals Inc | Bright nickel plating bath and process and composition therefor |
US4439284A (en) * | 1980-06-17 | 1984-03-27 | Rockwell International Corporation | Composition control of electrodeposited nickel-cobalt alloys |
US20030178314A1 (en) * | 2002-03-21 | 2003-09-25 | United States Steel Corporation | Stainless steel electrolytic coating |
US6856212B2 (en) * | 2002-12-16 | 2005-02-15 | Com Dev Ltd. | Incomplete mechanical contacts for microwave switches |
EP3956498A1 (en) | 2019-04-15 | 2022-02-23 | Atotech Deutschland GmbH & Co. KG | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or semi-bright nickel alloy coating |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2841602A (en) * | 1955-10-04 | 1958-07-01 | Udylite Res Corp | Alkynoxy acids |
US3366557A (en) * | 1958-07-22 | 1968-01-30 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
US3111466A (en) * | 1959-03-11 | 1963-11-19 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
FR1250864A (en) * | 1959-03-11 | 1961-01-13 | Hanson Van Winkle Munning Co | Nickel electroplating process |
US3719568A (en) * | 1970-12-11 | 1973-03-06 | Oxy Metal Finishing Corp | Nickel electroplating composition and process |
-
1970
- 1970-12-11 US US00097346A patent/US3719568A/en not_active Expired - Lifetime
-
1971
- 1971-09-22 DE DE2147257A patent/DE2147257C3/en not_active Expired
- 1971-09-27 CA CA123,811A patent/CA993832A/en not_active Expired
- 1971-09-29 AU AU34014/71A patent/AU454350B2/en not_active Expired
- 1971-11-02 GB GB5091671A patent/GB1338688A/en not_active Expired
- 1971-11-23 FR FR7141897A patent/FR2117877B1/fr not_active Expired
- 1971-12-09 NL NL7116879A patent/NL7116879A/xx unknown
-
1973
- 1973-02-28 US US00336588A patent/US3795592A/en not_active Expired - Lifetime
-
1974
- 1974-01-23 NL NL7400921A patent/NL7400921A/xx unknown
- 1974-01-31 DE DE2404614A patent/DE2404614A1/en active Pending
- 1974-02-28 FR FR7406858A patent/FR2219241B1/fr not_active Expired
- 1974-02-28 GB GB910774A patent/GB1456583A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4062738A (en) * | 1974-10-04 | 1977-12-13 | E. I. Du Pont De Nemours And Company | Acid nickel electroplating additive therefor and method of making said additive |
Also Published As
Publication number | Publication date |
---|---|
FR2117877A1 (en) | 1972-07-28 |
NL7400921A (en) | 1974-08-30 |
FR2117877B1 (en) | 1976-02-13 |
AU6408874A (en) | 1975-07-03 |
FR2219241A1 (en) | 1974-09-20 |
GB1456583A (en) | 1976-11-24 |
GB1338688A (en) | 1973-11-28 |
DE2404614A1 (en) | 1974-09-05 |
NL7116879A (en) | 1972-06-13 |
DE2147257C3 (en) | 1978-03-23 |
AU3401471A (en) | 1973-04-05 |
DE2147257B2 (en) | 1977-07-28 |
AU454350B2 (en) | 1974-10-31 |
DE2147257A1 (en) | 1972-06-22 |
US3719568A (en) | 1973-03-06 |
CA993832A (en) | 1976-07-27 |
FR2219241B1 (en) | 1978-01-13 |
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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 |