EP0239876A1 - Bain de dépôt électrolytique des alliages en argent-palladium - Google Patents

Bain de dépôt électrolytique des alliages en argent-palladium Download PDF

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Publication number
EP0239876A1
EP0239876A1 EP87103932A EP87103932A EP0239876A1 EP 0239876 A1 EP0239876 A1 EP 0239876A1 EP 87103932 A EP87103932 A EP 87103932A EP 87103932 A EP87103932 A EP 87103932A EP 0239876 A1 EP0239876 A1 EP 0239876A1
Authority
EP
European Patent Office
Prior art keywords
palladium
bath
silver
bath according
polyphosphate
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.)
Granted
Application number
EP87103932A
Other languages
German (de)
English (en)
Other versions
EP0239876B1 (fr
Inventor
Hermann Dr. Dipl.-Chem. Grossmann
Alfons Dipl.-Ing. Holländer (FH)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Doduco Solutions GmbH
Original Assignee
Doduco GmbH and Co KG Dr Eugen Duerrwaechter
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Doduco GmbH and Co KG Dr Eugen Duerrwaechter filed Critical Doduco GmbH and Co KG Dr Eugen Duerrwaechter
Publication of EP0239876A1 publication Critical patent/EP0239876A1/fr
Application granted granted Critical
Publication of EP0239876B1 publication Critical patent/EP0239876B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver

Definitions

  • the present invention relates to an aqueous bath for the electrolytic deposition of silver-palladium alloys with the features specified in the preamble of claim 1.
  • a bath with these features which is used to deposit silver-palladium alloys with up to 5 percent by weight of palladium, is known from DE-OS 27 04 691.
  • it contains silver as silver nitrate, palladium as palladiumethylene diamine sulfate and succinimide and sodium hydroxide solution , with which a pH value of 8 is set.
  • the known bath composition is unsuitable for the deposition of silver-palladium alloys with a higher palladium content.
  • the invention has for its object to provide an aqueous, cyanide-free, alkaline bath for the deposition of silver-palladium alloys with a higher proportion of palladium and with the largest possible composition range.
  • potassium hydroxide or sodium hydroxide can additionally be added in a manner known per se. Usable separation conditions are achieved with a pH between 7 and 12; a pH value between 8 and 10 is optimal.
  • a buffer substance can be added in a manner known per se; Standard buffers are suitable, for example borates, phosphates and dicarboxylic acids;
  • the pH value can be stabilized to values between 8 and 10 using a boric acid / sodium hydroxide solution.
  • the bath according to the invention contains the silver in the form of a complex compound with succinimide or its derivatives (e.g. 2-methylsuccinimide, 2-ethylsuccinimide or maleimide) insofar as they are easily soluble in weakly alkaline, aqueous solution.
  • succinimide or its derivatives e.g. 2-methylsuccinimide, 2-ethylsuccinimide or maleimide
  • the bath according to the invention can contain between 0.5 and 15 g / l silver and between 1 and 25 g / l palladium. It can be used to deposit silver-palladium alloys in which the weight ratio of silver to palladium can be set between 20/80 and 80/20; the setting is made by appropriately setting the silver concentration and palladium concentration in the bath and by choosing the bath temperature.
  • the palladium is in the bath according to the invention in the form of palladium diphosphate and / or palladium polyphosphate contain. These compounds can be added directly to the bath; it is also possible to add a palladium nitrite complex compound to the bath and to react it in excess with diphosphoric acid or polyphosphoric acid or its salts, for example with potassium diphosphate. Instead of a palladium nitrite complex compound, it is also possible to start from other palladium compounds, in particular from palladium hydroxide, and to react this in excess with di- or polyphosphoric acid or its salts. The succinimide should expediently also be present in excess. The excess of complexing substances is intended to make it possible for the palladium and the silver, which have been in the bath from the beginning or have been added in the form of a supplemental salt over time, to be bound in a completely complex manner.
  • the bath according to the invention expediently contains an additive which acts as a wetting agent and favors the formation of a fine-grained and crack-free silver-palladium alloy.
  • Water-soluble, sulfonated, aromatic aldehydes of which anisaldehyde sulfonic acid and benzaldehyde disulfonic acid are particularly noteworthy, have proven to be particularly suitable fine grain additives and wetting agents for the bath according to the invention.
  • Other suitable representatives from the group of the sulfonated aromatic aldehydes are sulfonated vanillin, sulfonated salicylaldehyde and sulfonated cinnamaldehyde.
  • the sulfonated aldehydes are advantageously added to the bath in an amount of 0.1 to 5 g / l, preferably 1 to 3 g / l.
  • Ductile, crack-free coatings made of silver-palladium alloys with a satin-gloss surface can be deposited with baths of the composition according to the invention.
  • the bath contains 10 g / l palladium as potassium tetranitritopalladate (II), 2 g / l silver as a silver succinimide complex 30 g / l succinimide 40 g / l potassium diphosphate, 30 g / l boric acid 1 g / l salicylaldehyde sulfonic acid.
  • a pH of 9.5 is set in the bath by adding potassium hydroxide and the deposition is carried out at a temperature of 25 ° C. and a current density of 0.5 A / dm2. It is best to use platinum-coated titanium as anodes, which do not dissolve in the bath.
  • the deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
  • the bath contains: 7 g / l palladium as palladium polyphosphate, made from palladium oxide hydrate and polyphosphate, 1 g / l silver as silver succinimide complex, 25 g / l succinimide, 20 g / l sodium polyphosphate, 30 g / l boric acid 1 g / l benzaldehyde disulfonic acid.
  • a pH of 9.5 is set by adding potassium hydroxide and the deposition is carried out at a temperature of 40 ° C. and a current density of 0.5 A. / dm2.
  • Platinum-plated titanium is best chosen as the anode material.
  • the deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
  • the bath contains: 5 g / l palladium as palladium polyphosphate, 0.5 g / l silver as a silver succinimide complex, 20 g / l succinimide, 60 g / l sodium polyphosphate, 15 g / l of a soluble dicarboxylic acid, for example malonic acid or higher homologues, 0.5 g / l benzaldehyde disulfonic acid.
  • a pH of 9.5 is set by adding potassium hydroxide and the deposition is carried out at a temperature of 40 ° C. and a current density of 0.5 A. / dm2.
  • Platinum-plated titanium is best chosen as the anode material.
  • the deposited silver-palladium alloy is ductile and crack-free and has a satin surface.

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)
EP87103932A 1986-03-20 1987-03-18 Bain de dépôt électrolytique des alliages en argent-palladium Expired - Lifetime EP0239876B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3609309 1986-03-20
DE19863609309 DE3609309A1 (de) 1986-03-20 1986-03-20 Bad zum elektrolytischen abscheiden von silber-palladium-legierungen

Publications (2)

Publication Number Publication Date
EP0239876A1 true EP0239876A1 (fr) 1987-10-07
EP0239876B1 EP0239876B1 (fr) 1990-09-05

Family

ID=6296792

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87103932A Expired - Lifetime EP0239876B1 (fr) 1986-03-20 1987-03-18 Bain de dépôt électrolytique des alliages en argent-palladium

Country Status (2)

Country Link
EP (1) EP0239876B1 (fr)
DE (2) DE3609309A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4412253A1 (de) * 1993-04-07 1994-10-13 Atotech Deutschland Gmbh Elektrolytische Abscheidung von Palladium oder Palladiumlegierungen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02104699A (ja) * 1988-10-11 1990-04-17 C Uyemura & Co Ltd 銀の電解剥離剤及び電解剥離方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2343062A2 (fr) * 1976-03-01 1977-09-30 Technic Bain d'electrolyse ne contenant pas de cyanure pour le depot electrolytique de l'argent
GB2046794A (en) * 1979-04-04 1980-11-19 Engelhard Min & Chem Silver and gold/silver alloy plating bath and method
FR2496127A1 (fr) * 1980-12-17 1982-06-18 Hooker Chemicals Plastics Corp Bains et procede electrolytique pour le depot de palladium blanc

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478692A (en) * 1982-12-22 1984-10-23 Learonal, Inc. Electrodeposition of palladium-silver alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2343062A2 (fr) * 1976-03-01 1977-09-30 Technic Bain d'electrolyse ne contenant pas de cyanure pour le depot electrolytique de l'argent
GB2046794A (en) * 1979-04-04 1980-11-19 Engelhard Min & Chem Silver and gold/silver alloy plating bath and method
FR2496127A1 (fr) * 1980-12-17 1982-06-18 Hooker Chemicals Plastics Corp Bains et procede electrolytique pour le depot de palladium blanc

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 97, Nr. 12, September 1982, Seite 570, Zusammenfassung Nr. 100709j, Columbus, Ohio, US; & JP-A-82 76 196 (KUMAMOTO PREFECTURE) 13-05-1982 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4412253A1 (de) * 1993-04-07 1994-10-13 Atotech Deutschland Gmbh Elektrolytische Abscheidung von Palladium oder Palladiumlegierungen

Also Published As

Publication number Publication date
EP0239876B1 (fr) 1990-09-05
DE3609309C2 (fr) 1988-06-01
DE3609309A1 (de) 1987-09-24
DE3764685D1 (de) 1990-10-11

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