GB2094836A - A bath for the electrolytic deposition of a palladium-nickel alloy - Google Patents

A bath for the electrolytic deposition of a palladium-nickel alloy Download PDF

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Publication number
GB2094836A
GB2094836A GB8204857A GB8204857A GB2094836A GB 2094836 A GB2094836 A GB 2094836A GB 8204857 A GB8204857 A GB 8204857A GB 8204857 A GB8204857 A GB 8204857A GB 2094836 A GB2094836 A GB 2094836A
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United Kingdom
Prior art keywords
palladium
sodium
nickel
bath
content
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Granted
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GB8204857A
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GB2094836B (en
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Langbein Pfanhauser Werke AG
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Langbein Pfanhauser Werke AG
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Publication of GB2094836A publication Critical patent/GB2094836A/en
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Publication of GB2094836B publication Critical patent/GB2094836B/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/562Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/567Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals

Abstract

A bath for the electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes having outstandingly fine and uniform grain structure and satisfactory mixed crystal formation, which enhances brightness, ductility and resistance to the widest variety of corrosive media, and which may improve smoothness, consists of an aqueous solution of palladium- and nickel-amines having a palladium content in the range 5 to 30 g/l and a nickel content in the same range 5 to 30 g/l, together with an addition of sulphonic acid salts, the ration of palladium to nickel being adjusted to that the electrolytically deposited alloy has a palladium content of 30 to 90% by weight, to which is added one or more of the following substances: sodium vinylsulphonate, sodium allylsulphonate, sodium propinesulphonate, sodium methylalylsulphonate, N-pyridinium propylsulpho-betaine, N-pyridinum ethylsulphobetaine, sodium N- benzylpyridinium-2-ethylsulphonate.

Description

SPECIFICATION A bath for the electrolytic deposition of a palladium-nickel alloy This invention relates to a bath for the electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes, consisting of an aqueous solution of palladium- and nickelamines having a palladium content in the range 5 to 30 g/l, a nickel content in the same range 5 to 30 g/l and an addition of sulphonic acid salts, in which aqueous solution the ratio of palladium to nickel is so adjusted that the electrolytically deposited alloy 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 (G.B.-P.S. 1 143178), the sulphonic acids and/or their salts are added as brighteners. The substances specifically named are the salts of naphthalene-sulphonic acid and aromatic sulphonamides such as the sodium salt of naphthalene-1 ,5-disulphonic acid, the sodium salts of naphthalene- 1 ,3,6-trisulphonic acid, saccharin (o-sulpho-benzoic acid imide) and ptoluenesulphonamide. However, it has been found by experience that electroplatings produced in this type of bath fail to meet requirements in respect of mechanical properties -- and even their lustre is inadequate for many decorative purposes. According to the discoveries on which the present invention is based, these deficiencies arise from defective mixed crystal formation.
The object of the invention is to provide a bath of the type defined in which satisfactory mixed crystal formation is ensured.
According to the present invention, this object is achieved by the addition to a bath of the type defined, of one or more of the following substances: sodium vinylsulphonate sodium allylsulphonate sodium propinesulphonate sodium methallylsulphonate N-pyridinium propylsulpho-beta-ine N-pyridinium ethylsulpho-beta-ine sodium N-benzylpyridinium-2-ethylsulphonate With an additive from the above selection electrolytic deposition from the bath produces palladium-nickel finishes with an outstandingly fine and uniform grain structure and satisfactory mixed crystal formation. This enhances their brightness, ductility and resistance to the widest variety of corrosive media. Moreover, the smoothing action may be improved.
The invention and the effects it achieves will now be described with reference to some typical embodiments thereof: EXAMPLE 1 (Addition of an aliphatic sulphonic acid salt): An electrolyte was prepared from: 20 g palladium as (Pd(NH3)4Cl2 10 9 nickel as (Ni(NH3)6)SO4 50 g conductivity as (NH4)2SO4 or Nh4CI to salt give the electrolyte adequate conductivity NH4OH to adjust the pH to 8.5 water to bring the volume to 1 litre 2.5 9 sodium allylsulphonate The electrolyte temperature was 300 C; the articles were kept moving gently: 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 inhibitive action.
To check the corrosion resistance, the test sheet made as above was immersed for 60 s in dilute nitric acid at room temperature; the medium contained equal parts of concentrated nitric acid and water. there was no visible evidence of corrosive attack.
Following G.B.-P.S. 1143178 previously referred to and adding 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 a deficient mixed crystal formation. X-ray examinations have detected the presence of free nickel, which constitutes the cause of corrosion.
EXAMPLE2 (Addition of an aliphatic sulphonic acid salt combination): An electrolyte was prepared from: 20 g palladium as (Pd(NH3)4)CI2 10 9 nickel as (Ni(NH3)6) SO4 50 g conductivity as (NH4)2SO4 or Nh4CI to salt give the electrolyte adequate conductivity NH4OH to adjust the pH to 8.5 water to bring the volume to 1 litre 2.5 g sodium allylsulphonate 0.25 g sodium propinesulphonate The electroplating temperature was 300C; the articles were kept moving gently; 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, compared with Example 1 , with no significant smoothing and no inhibitive action. The nitric acid test as in Example 1 was again easily withstood.
EXAMPLE3 (Addition of a combination of an aliphatic and a heterocyclic sulphonic acid salt): An electrolyte was prepared from: 20 g palladium as (Pd(NH3)4)SO4 10 9 nickel as (Ni(NH3)6)Cl2 50 g conductivity as (NH4)2S04 or NH4CI to salt give the electrolyte adequate conductivity NH40H to adjust the pH to 8.5 water to bring the volume to 1 litre 2.5 g sodium allylsulphonate 0.1 g N-pyridinium propylsulpho-beta-ine The electroplating temperature was 300C; the articles were kept moving gently; 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, with no detectable smoothing and no inhibitive action. The nitric acid test was easily withstood.

Claims (2)

1. A bath for electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes, consisting of an aqueous solution of palladium- and nickel-amines having a palladium content in the range 5 to 30 g/l, a nickel content in the same range 5 to 30 g/l and an addition of sulphonic acid salts, in which aqueous solution the ratio of palladium to nickel is so adjusted that the electrolytically deposited alloy has a palladium content of 30 to 90% by weight, to which is added one or more of the following substances: sodium vinylsulphonate sodium allylsulphonate sodium propinesulphonate sodium methallylsulphonate N-pyridinium propylsulpho-beta-ine N-pyridinium ethylsulpho-beta-ine sodium N-benzylpyridinium-2-ethylsulphonate.
2. A bath for the electrolytic deposition of a palladium-nickel alloy for decorative and/or technical finishes substantially as hereinbefore described with reference to any one of the Examples.
GB8204857A 1981-03-06 1982-02-18 A bath for the electrolytic deposition of a palladium-nickel alloy Expired GB2094836B (en)

Applications Claiming Priority (1)

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

Publications (2)

Publication Number Publication Date
GB2094836A true GB2094836A (en) 1982-09-22
GB2094836B GB2094836B (en) 1984-12-05

Family

ID=6126504

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8204857A Expired GB2094836B (en) 1981-03-06 1982-02-18 A 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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2242200A (en) * 1990-02-20 1991-09-25 Omi International Plating compositions and processes
EP0916747A1 (en) * 1997-11-15 1999-05-19 AMI Doduco GmbH Electrolytic bath for the deposition of palladium and palladium alloys
CN113699565A (en) * 2021-09-28 2021-11-26 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 solution

Families Citing this family (4)

* Cited by examiner, † Cited by third party
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
US5415685A (en) * 1993-08-16 1995-05-16 Enthone-Omi Inc. Electroplating bath and process for white palladium

Family Cites Families (8)

* Cited by examiner, † Cited by third party
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2242200A (en) * 1990-02-20 1991-09-25 Omi International Plating compositions and processes
GB2242200B (en) * 1990-02-20 1993-11-17 Omi International Plating compositions and processes
EP0916747A1 (en) * 1997-11-15 1999-05-19 AMI Doduco GmbH Electrolytic bath for the deposition of palladium and palladium alloys
CN113699565A (en) * 2021-09-28 2021-11-26 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 solution

Also Published As

Publication number Publication date
FR2501243A1 (en) 1982-09-10
ATA82182A (en) 1984-06-15
IT8219992A0 (en) 1982-03-05
JPS5816089A (en) 1983-01-29
DE3108508C2 (en) 1983-06-30
AT377013B (en) 1985-01-25
CH649318A5 (en) 1985-05-15
FR2501243B1 (en) 1988-05-27
BE892344A (en) 1982-07-01
JPS6112038B2 (en) 1986-04-05
SE8201299L (en) 1982-09-07
IT1150627B (en) 1986-12-17
GB2094836B (en) 1984-12-05
ZA821367B (en) 1983-01-26
BR8201157A (en) 1982-11-23
DE3108508A1 (en) 1982-09-16
AU8104982A (en) 1982-09-09
AU535531B2 (en) 1984-03-29
CA1176204A (en) 1984-10-16
NL8200908A (en) 1982-10-01

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PCNP Patent ceased through non-payment of renewal fee