CA1176204A - Bath for the electrolytic deposition of a palladium- nickel alloy - Google Patents
Bath for the electrolytic deposition of a palladium- nickel alloyInfo
- Publication number
- CA1176204A CA1176204A CA000397678A CA397678A CA1176204A CA 1176204 A CA1176204 A CA 1176204A CA 000397678 A CA000397678 A CA 000397678A CA 397678 A CA397678 A CA 397678A CA 1176204 A CA1176204 A CA 1176204A
- Authority
- CA
- Canada
- Prior art keywords
- palladium
- sodium
- nickel
- content
- pyridinium
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
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
ABSTRACT OF THE DISCLOSURE
An improved bath for the electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes is disclosed, comprising an aqueous solution of palladium- and nickel-ammines having a palladium content in the range 5 to 30 g/l, a nickel content in the range 5 to 30 g/l wherein the ratio of palladium to nickel is adjusted so that the alloy electrolytically deposited therefrom has a palladium content of 30 to 90% by weight, wherein the improvement is the addition, to improve mixed crystal formation, of one or more of the following:
sodium vinylsulphonate sodium allylsulphonate sodium propynesulphonate sodium methallylsulphonate N-pyridinium propylsulphobetaine N-pyridinium ethylsulphobetaine sodium N-benzylpyridinium-2-ethylsulphonate.
Coatings prepared from such baths have improved corrosion resistance and gloss.
An improved bath for the electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes is disclosed, comprising an aqueous solution of palladium- and nickel-ammines having a palladium content in the range 5 to 30 g/l, a nickel content in the range 5 to 30 g/l wherein the ratio of palladium to nickel is adjusted so that the alloy electrolytically deposited therefrom has a palladium content of 30 to 90% by weight, wherein the improvement is the addition, to improve mixed crystal formation, of one or more of the following:
sodium vinylsulphonate sodium allylsulphonate sodium propynesulphonate sodium methallylsulphonate N-pyridinium propylsulphobetaine N-pyridinium ethylsulphobetaine sodium N-benzylpyridinium-2-ethylsulphonate.
Coatings prepared from such baths have improved corrosion resistance and gloss.
Description
6Z~4 This invention relates to a bath for the electrolytic deposltion of a palladium-nickel alloy for decorative and/or technical finishes. A known electroplating bath consists of an aqueous solution of palladium- and nickel-ammines having a palladium content in the range 5 to 30 g/1, a nickel content in the range 5 to 30 g/1 and sulphonic acid salts as additives. In this aqueous solution the ratio of palladium to nickel is adjusted so that alloy electrolytically deposited therefrom has a palladium content of 30 to 90%
by weight. Electroplating produced by means of this type of bath is used as a substitute for gold.
In the known baths ~U.K. Patent Specification 1143178), sulphonic acids and/or their salts are added as brighteners. Substances specifically disclosed are the salts of naphthalene-sulphonic acid and aromatic ~ulphonamides as for example the sodium salt of naphthalene-1,5-disulphonic acid, the sodium salt of naphthalene-1,3,6-trisulphonic acid, saccharine (o-sulphobenzoic acid imide) and p-toluenesulphonamide. H~wever, it has been found by experience that electroplatings produced from this type of bath fail are unsatisfactory in respect of mechanical properties, and even the lustre is inadequate for many decorative purposes. According to the discoveries on which the present invention is based, these deficiencieæ arise from defective mixed crystal formation.
The present invention is an improvement in the aforementioned type of bath so that satisfactory mixed crystal formation is ensured.
According to the inventlon, to improve mixed crystal formation, one or more of the followlnB substances are added to the bath:
sodium vinylsulphonate sodium allylsulphonate sodium propynesulphonate sodium methallylsulphonate 11'76ZC~
N-pyridinium propylsulphobetaine N-pyridinium ethylsulphobetaine sodium N-benzylpyridinium-2-ethylsulphonate.
When the addltive is selected in accordance with the invention, electrolytic deposition ~rom the bath produces palladium-nickel finishes with outstandingly fine and uniform grain structure and satisfactory mixed crystal formation. This enhances the brightness, ductility and resistance to the widest variety of corrosive media. Moreover, the smoothing action is lmproved.
Preferably the concentration of the additive or mixture of additives will be in the range of 1 to 10 grams per litre.
The invention and the effects it achieves will now be described with reference to some typical embodiment~ thereof:
Example 1 (Addition of an aliphatic sulphonic acid salt):
An electrolyte was prepared from:
20 g palladium as (Pd(NH3)4)cl2 10 g nickel as (Ni(NH3)6)S04 50 g conductivity salt as (NH~)2S04 or NH4cl to give the electrolyte adequate conductivity NH40H to ad~ust the pH to 8.5 water to bring the volume to 1 litre
by weight. Electroplating produced by means of this type of bath is used as a substitute for gold.
In the known baths ~U.K. Patent Specification 1143178), sulphonic acids and/or their salts are added as brighteners. Substances specifically disclosed are the salts of naphthalene-sulphonic acid and aromatic ~ulphonamides as for example the sodium salt of naphthalene-1,5-disulphonic acid, the sodium salt of naphthalene-1,3,6-trisulphonic acid, saccharine (o-sulphobenzoic acid imide) and p-toluenesulphonamide. H~wever, it has been found by experience that electroplatings produced from this type of bath fail are unsatisfactory in respect of mechanical properties, and even the lustre is inadequate for many decorative purposes. According to the discoveries on which the present invention is based, these deficiencieæ arise from defective mixed crystal formation.
The present invention is an improvement in the aforementioned type of bath so that satisfactory mixed crystal formation is ensured.
According to the inventlon, to improve mixed crystal formation, one or more of the followlnB substances are added to the bath:
sodium vinylsulphonate sodium allylsulphonate sodium propynesulphonate sodium methallylsulphonate 11'76ZC~
N-pyridinium propylsulphobetaine N-pyridinium ethylsulphobetaine sodium N-benzylpyridinium-2-ethylsulphonate.
When the addltive is selected in accordance with the invention, electrolytic deposition ~rom the bath produces palladium-nickel finishes with outstandingly fine and uniform grain structure and satisfactory mixed crystal formation. This enhances the brightness, ductility and resistance to the widest variety of corrosive media. Moreover, the smoothing action is lmproved.
Preferably the concentration of the additive or mixture of additives will be in the range of 1 to 10 grams per litre.
The invention and the effects it achieves will now be described with reference to some typical embodiment~ thereof:
Example 1 (Addition of an aliphatic sulphonic acid salt):
An electrolyte was prepared from:
20 g palladium as (Pd(NH3)4)cl2 10 g nickel as (Ni(NH3)6)S04 50 g conductivity salt as (NH~)2S04 or NH4cl to give the electrolyte adequate conductivity NH40H to ad~ust the pH to 8.5 water to bring the volume to 1 litre
2.5 g sodium allylsulphonate The electrolyte temperature was 30C; the articles were kept gently ving; the cathode current density was 1 A/dm2; the deposition time was 10 min.
A lustrous palladium-nickel coating was produced on a brushed brass sheet, without significant smoothing or lnhibitive action.
To check the c~rrosion resistance, the aforementioned test sheet was immersed fo~ 60 s in dilute nitric acid at room temperature; the medium ~76ZC~4 contained equal parts of concentrated nitric acid and water. There was no visible evidence of corrosive attack.
If one follows the disclogure of U.K Patent Speclflcation 1143178 and adds 10 g of sodium naphthalene-1,3,6-trisulphonate to the electrolyte instead of sodium allylsulphonate, the resulting palladium-nickel coating corrodes seriously in the above nitric acid test. The cause lies in deficient ~lxed crystal formation~ X-ray examinations have detected the presence of free nickel, which constitutes the cause of corrosion.
Example 2 (Addition of an allphatic sulphonic acid salt combination);
An electrolyte was prepared from;
20 g palladium as (pd(NH3)4~cl2 iO g nickel as (Ni(NH3)6)S04 50 g conductivity salt as (NH4)2S04 or NH4cl to give the electrolyte adequate conductivity NH40H to ad~ust the pH to 8.5 water to bring the volume to 1 litre 2.5 g sodium allylsulphonate 0.25 g sodim propynesulphonate The electroplating temperature was 30C; the articles were kept gently moving;
the cathode current density was 1 A¦dm2; the deposition time was 10 min.
A more lustrous palladium-nickel coating was produced on a brushed brass sheet than that of Example 1, with no significant smoothing and no lnhibitive action. The costing easily withstood the nitrlc acid test as in Example 1.
Example 3 (Addition of a combinatlon of an aliphatic and a heterocyclic _ sulphonic acid salt):
An electrolyte was prepared from:
20 g palladium as (pd(NH3)4)so4 ~176ZC1 4 10 g nickel as (Ni(NH3)6)cl2 50 g conductivity salt a9 (NH4~2S04 or NH4Cl to give the electrolyte adequate conductivity NH40H to ad~ust the pH to 8.5 water to bring the volume to 1 litre 2.5 g sodim allylsulphonate 0.1 g N-pyridlnium propylsulphobetaine - The electroplating temperature was 30C; the articles were ~ept gently moving;
the cathode curre~t density was 1 A/dm2; the deposition time was 10 min.
A lustrous palladium-nickel coating was produced on a brushed brass sheet, with no detectable smoothing and no inhibitive action. The coating easily withstood the nitric acid test.
A lustrous palladium-nickel coating was produced on a brushed brass sheet, without significant smoothing or lnhibitive action.
To check the c~rrosion resistance, the aforementioned test sheet was immersed fo~ 60 s in dilute nitric acid at room temperature; the medium ~76ZC~4 contained equal parts of concentrated nitric acid and water. There was no visible evidence of corrosive attack.
If one follows the disclogure of U.K Patent Speclflcation 1143178 and adds 10 g of sodium naphthalene-1,3,6-trisulphonate to the electrolyte instead of sodium allylsulphonate, the resulting palladium-nickel coating corrodes seriously in the above nitric acid test. The cause lies in deficient ~lxed crystal formation~ X-ray examinations have detected the presence of free nickel, which constitutes the cause of corrosion.
Example 2 (Addition of an allphatic sulphonic acid salt combination);
An electrolyte was prepared from;
20 g palladium as (pd(NH3)4~cl2 iO g nickel as (Ni(NH3)6)S04 50 g conductivity salt as (NH4)2S04 or NH4cl to give the electrolyte adequate conductivity NH40H to ad~ust the pH to 8.5 water to bring the volume to 1 litre 2.5 g sodium allylsulphonate 0.25 g sodim propynesulphonate The electroplating temperature was 30C; the articles were kept gently moving;
the cathode current density was 1 A¦dm2; the deposition time was 10 min.
A more lustrous palladium-nickel coating was produced on a brushed brass sheet than that of Example 1, with no significant smoothing and no lnhibitive action. The costing easily withstood the nitrlc acid test as in Example 1.
Example 3 (Addition of a combinatlon of an aliphatic and a heterocyclic _ sulphonic acid salt):
An electrolyte was prepared from:
20 g palladium as (pd(NH3)4)so4 ~176ZC1 4 10 g nickel as (Ni(NH3)6)cl2 50 g conductivity salt a9 (NH4~2S04 or NH4Cl to give the electrolyte adequate conductivity NH40H to ad~ust the pH to 8.5 water to bring the volume to 1 litre 2.5 g sodim allylsulphonate 0.1 g N-pyridlnium propylsulphobetaine - The electroplating temperature was 30C; the articles were ~ept gently moving;
the cathode curre~t density was 1 A/dm2; the deposition time was 10 min.
A lustrous palladium-nickel coating was produced on a brushed brass sheet, with no detectable smoothing and no inhibitive action. The coating easily withstood the nitric acid test.
Claims (3)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bath for the electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes comprising an aqueous solution of palladium- and nickel-ammines having a palladium content in the range 5 to 30 g/l, a nickel content in the range 5 to 30 g/l wherein the ratio of palladium to nickel is adjusted so that the alloy electrolytically deposited therefrom has a palladium content of 30 to 90% by weight, the improvement comprising the addition, to improve mixed crystal formation, of one or more of the following:
sodium vinylsulphonate sodium allylsulphonate sodium propynesulphonate sodium methallylsulphonate N-pyridinium propylsulphobetaine N-pyridinium ethylsulphobetaine sodium N-benzylpyridinium-2-ethylsulphonate.
sodium vinylsulphonate sodium allylsulphonate sodium propynesulphonate sodium methallylsulphonate N-pyridinium propylsulphobetaine N-pyridinium ethylsulphobetaine sodium N-benzylpyridinium-2-ethylsulphonate.
2. The electrolytic bath according to claim 1 wherein the additive or mixture of additives is present in an amount of 1 to 10 grams per litre.
3. A method of electroplating using an electrolytic bath according to claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3108508A DE3108508C2 (en) | 1981-03-06 | 1981-03-06 | Bath for the electrodeposition of a palladium / nickel alloy |
| DEP3108508.3 | 1981-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1176204A true CA1176204A (en) | 1984-10-16 |
Family
ID=6126504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000397678A Expired CA1176204A (en) | 1981-03-06 | 1982-03-05 | Bath for the electrolytic deposition of a palladium- nickel alloy |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5816089A (en) |
| AT (1) | AT377013B (en) |
| AU (1) | AU535531B2 (en) |
| BE (1) | BE892344A (en) |
| BR (1) | BR8201157A (en) |
| CA (1) | CA1176204A (en) |
| CH (1) | CH649318A5 (en) |
| DE (1) | DE3108508C2 (en) |
| FR (1) | FR2501243B1 (en) |
| GB (1) | GB2094836B (en) |
| IT (1) | IT1150627B (en) |
| NL (1) | NL8200908A (en) |
| SE (1) | SE8201299L (en) |
| ZA (1) | ZA821367B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3443420A1 (en) * | 1984-11-26 | 1986-05-28 | Siemens AG, 1000 Berlin und 8000 München | Electroplating bath for the rapid deposition of palladium alloys |
| US4628165A (en) * | 1985-09-11 | 1986-12-09 | Learonal, Inc. | Electrical contacts and methods of making contacts by electrodeposition |
| DE3809139A1 (en) * | 1988-03-18 | 1989-09-28 | Lpw Chemie Gmbh | USE OF A PALLADIUM / NICKEL ALLOY LAYER AS AN INTERMEDIATE LAYER BETWEEN A NON-CORROSION-RESISTANT OR LESS-CORROSION-RESISTANT METAL BASE MATERIAL AND A COATING APPLIED BY THE PVD PROCESS |
| GB2242200B (en) * | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| US5415685A (en) * | 1993-08-16 | 1995-05-16 | Enthone-Omi Inc. | Electroplating bath and process for white palladium |
| EP0916747B1 (en) * | 1997-11-15 | 2002-10-16 | AMI Doduco GmbH | Electrolytic bath for the deposition of palladium and palladium alloys |
| CN113699565B (en) * | 2021-09-28 | 2023-07-04 | 万明电镀智能科技(东莞)有限公司 | High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2328243A (en) * | 1941-04-28 | 1943-08-31 | Posture Res Corp | Chair |
| US2800442A (en) * | 1955-10-04 | 1957-07-23 | Udylite Res Corp | Electrodeposition of nickel |
| JPS4733176B1 (en) * | 1967-01-11 | 1972-08-23 | ||
| US3730854A (en) * | 1971-10-29 | 1973-05-01 | Basf Ag | Stabilized aqueous solutions of unsaturated aliphatic sulfonic acids or salts thereof |
| CH572989A5 (en) * | 1973-04-27 | 1976-02-27 | Oxy Metal Industries Corp | |
| GB1553503A (en) * | 1976-05-14 | 1979-09-26 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| FR2364980A1 (en) * | 1976-09-17 | 1978-04-14 | Parker Ste Continentale | Electrodeposition of palladium alloys for jewellery - or protective coatings, using bath contg. organic cpds. and brighteners |
| DE2825966A1 (en) * | 1978-06-14 | 1980-01-03 | Basf Ag | ACID GALVANIC NICKEL BATH, WHICH CONTAINS SULFOBETAINE AS A GLOSSY AND LEVELING AGENT |
-
1981
- 1981-03-06 DE DE3108508A patent/DE3108508C2/en not_active Expired
-
1982
- 1982-02-18 GB GB8204857A patent/GB2094836B/en not_active Expired
- 1982-02-26 CH CH1184/82A patent/CH649318A5/en not_active IP Right Cessation
- 1982-03-02 ZA ZA821367A patent/ZA821367B/en unknown
- 1982-03-02 AU AU81049/82A patent/AU535531B2/en not_active Ceased
- 1982-03-03 SE SE8201299A patent/SE8201299L/en not_active Application Discontinuation
- 1982-03-03 BE BE2/59611A patent/BE892344A/en not_active IP Right Cessation
- 1982-03-03 JP JP57032483A patent/JPS5816089A/en active Granted
- 1982-03-03 AT AT0082182A patent/AT377013B/en not_active IP Right Cessation
- 1982-03-04 FR FR8203613A patent/FR2501243B1/en not_active Expired
- 1982-03-05 NL NL8200908A patent/NL8200908A/en not_active Application Discontinuation
- 1982-03-05 CA CA000397678A patent/CA1176204A/en not_active Expired
- 1982-03-05 IT IT19992/82A patent/IT1150627B/en active
- 1982-03-05 BR BR8201157A patent/BR8201157A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5816089A (en) | 1983-01-29 |
| IT8219992A0 (en) | 1982-03-05 |
| BE892344A (en) | 1982-07-01 |
| AU8104982A (en) | 1982-09-09 |
| FR2501243A1 (en) | 1982-09-10 |
| GB2094836B (en) | 1984-12-05 |
| ZA821367B (en) | 1983-01-26 |
| CH649318A5 (en) | 1985-05-15 |
| AU535531B2 (en) | 1984-03-29 |
| AT377013B (en) | 1985-01-25 |
| BR8201157A (en) | 1982-11-23 |
| SE8201299L (en) | 1982-09-07 |
| GB2094836A (en) | 1982-09-22 |
| FR2501243B1 (en) | 1988-05-27 |
| NL8200908A (en) | 1982-10-01 |
| DE3108508C2 (en) | 1983-06-30 |
| IT1150627B (en) | 1986-12-17 |
| ATA82182A (en) | 1984-06-15 |
| JPS6112038B2 (en) | 1986-04-05 |
| DE3108508A1 (en) | 1982-09-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |