EP0693579B1 - Bain pour le dépÔt électrolytique d'alliages Palladium-Argent - Google Patents

Bain pour le dépÔt électrolytique d'alliages Palladium-Argent Download PDF

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Publication number
EP0693579B1
EP0693579B1 EP95107534A EP95107534A EP0693579B1 EP 0693579 B1 EP0693579 B1 EP 0693579B1 EP 95107534 A EP95107534 A EP 95107534A EP 95107534 A EP95107534 A EP 95107534A EP 0693579 B1 EP0693579 B1 EP 0693579B1
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EP
European Patent Office
Prior art keywords
silver
palladium
bath according
acid
bath
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
Application number
EP95107534A
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German (de)
English (en)
Other versions
EP0693579A1 (fr
Inventor
Günter Dr. Herklotz
Thomas Frey
Otto Camus
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.)
WC Heraus GmbH and Co KG
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WC Heraus GmbH and Co KG
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Filing date
Publication date
Priority claimed from DE4444232A external-priority patent/DE4444232C1/de
Application filed by WC Heraus GmbH and Co KG filed Critical WC Heraus GmbH and Co KG
Publication of EP0693579A1 publication Critical patent/EP0693579A1/fr
Application granted granted Critical
Publication of EP0693579B1 publication Critical patent/EP0693579B1/fr
Anticipated expiration legal-status Critical
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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
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
    • 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 invention relates to an ammoniacal bath for the electrodeposition of palladium-silver alloys, which contains complex-bound palladium, a silver compound and a capto compound.
  • German patent 1 221 874 describes a method for the electrodeposition of pore-free palladium-silver alloy coatings (thickness approximately 5 to 100 micrometers) from ammoniacal palladium and silver nitrate solution with a pH of 7.5 to 11, a temperature of 35 to 90 ° C and a current density of 1 to 10 mA / cm 2 at a voltage of 0.5 to 7 volts. Good results are obtained when the solution contains about 0.5 to 10 g of the metal or metals per liter of solution. However, solutions with up to 150 g and more metal per liter can also be used.
  • the bath known from the Swiss patent specification 649 582 for the electroplating of substrates with palladium or palladium alloys at 20 to 75 ° C and a current density of 0.1 to 10 A / dm 2 is characterized in that it prevents unwanted precipitation of Palladium or the alloy metal (copper, cobalt, cadmium, gold, iron, indium, nickel, silver, tin, zinc) has a pH of 6.5 to 9.5 buffered by ammonium, amine or alkali metal borate during operation .
  • the bath contains 1 to 50 g / l palladium as a palladium-amine complex (palladium (II) di or tetrammine complex), 0 to 20 g / l of the alloy metal, 10 to 50 g / l borate and optionally to to 5 g / l of gloss agent aromatic sulfonated imide or amide, aromatic alkali metal sulfonate and / or aromatic sulfonic acid.
  • palladium (II) di or tetrammine complex palladium (II) di or tetrammine complex
  • 0 to 20 g / l of the alloy metal 10 to 50 g / l borate and optionally to to 5 g / l of gloss agent aromatic sulfonated imide or amide, aromatic alkali metal sulfonate and / or aromatic sulfonic acid.
  • a similar bath is known from Platinum Metals Review 1984, 28 (3), 117-124. It contains palladium and silver as amine complexes Pd (NH 3 ) 4 (NO 3 ) 2 and Ag (NH 3 ) 2 NO 3 and has a pH of 11.5.
  • EP 0 059 452 B1 and EP 0 073 236 B1 relate to processes for the electrodeposition of coatings made of palladium and its alloys with silver, copper and / or nickel from baths, which, as palladium source, use complexes of palladium with aliphatic polyamines (1,3-diaminopropane, N, N, N ', N'-tetramethylethylenediamine, 2-hydroxy-1,3-diaminopropane) and have a pH between 7.5 and 13.5.
  • a special aqueous bath for the galvanic deposition of the palladium-silver alloys consists of 69.6 g / l silver (I) oxide, 53.2 g / l palladium (II) chloride, 222 g / l 1.3 -Diaminopropane, 106.2 g / l K 3 PO 4 and 86.5 g / l K 2 HPO 4 together and has a pH of 11.3 adjusted with KOH or H 3 PO 4 .
  • the bath temperature is between 40 and 65 ° C, the current density between 1.1 and 538 mA / cm 2 .
  • the palladium-silver alloys are particularly suitable as surfaces for electrical contacts.
  • the bath contains 1 - 50 g / l of an aliphatic or aromatic mercapto compound (mercaptoacetic acid, mercaptopropionic acid, mercapto-succinic acid, thioglycerol, thiophenol, thiosalicylic acid) as a brightener and, if necessary, additionally that Amide of an aliphatic carboxylic acid, as a result of which black silver-containing precipitates that may occur in the bath can be largely avoided.
  • an aliphatic or aromatic mercapto compound mercaptoacetic acid, mercaptopropionic acid, mercapto-succinic acid, thioglycerol, thiophenol, thiosalicylic acid
  • Ammonium phosphate, acetate and / or nitrate can also be contained in the bath borate and as the conductive salt.
  • This bath can be used to deposit shiny, ductile, pore and crack-free coatings made of palladium-silver alloys with up to 40% by weight of silver, which are particularly suitable as contact layers for electrical contacts.
  • the object of the invention is to find a bath for depositing contact layers made of palladium-silver alloys suitable for electrical contacts, also with a higher silver content.
  • the bath should be able to be operated both at room temperature and at elevated temperature - then higher deposition rates are possible - and allow long operating times without the formation of black silver-containing precipitates. It should be able to be used in bell and drum systems as well as in continuous processes.
  • the bath of the type characterized at the outset, which is the solution to the problem, is characterized according to the invention by the preparation from water and 5 - 50 g / l Palladium as a palladium-amine complex, 2 - 40 g / l Silver as a silver compound, 30-150 g / l Leitsalz, 5 - 100 g / l Amine component from one or more aliphatic polyamines with 2 - 10 amino groups in the molecule and 2 - 50 g / l Mercaptoalkan carboxylic acid and / or mercaptoalkane sulfonic acid and / or their salts and a pH of 7.0-10.0 adjusted with ammonium hydroxide.
  • the bathroom has proven particularly useful when it consists of water and 5 - 20 g / l Palladium as a palladium-amine complex, 2 - 30 g / l Silver as a silver compound, 50-100 g / l Leitsalz, 5 - 100 g / l Amine component from one or more aliphatic polyamines with 2 - 10 amino groups in the molecule and 2 - 20 g / l Mercaptoalkan carboxylic acid and / or mercaptoalkane sulfonic acid and / or their salts prepared and its pH is adjusted to 7.0-10.0 with ammonium hydroxide.
  • Palladium diammine dichloride, palladium diammine dibromide or palladium diamine dinitrite as palladium amine complex and silver chloride, silver nitrate, silver sulfate or a silver diammine complex as silver compound are well suited for the preparation of the bath; palladium diammonitrite and silver nitrate are preferred.
  • the amine component can consist of one or more of the polyamines.
  • an increase in the silver content of the deposited palladium-silver alloys can be achieved by using a polyamine mixture (see examples).
  • the conductive salt are carboxylic acids, such as tartaric acid and citric acid, or their salts, boric acid and ammonium salts of inorganic acids, such as ammonium bromide, ammonium chloride, ammonium nitrate and ammonium sulfate, it being possible for the conductive salt to consist of one or more of these compounds.
  • carboxylic acids such as tartaric acid and citric acid
  • boric acid and ammonium salts of inorganic acids such as ammonium bromide, ammonium chloride, ammonium nitrate and ammonium sulfate
  • Preferred mercapto acids are 2- and 3-mercaptopropionic acid and 3-mercaptopropanesulfonic acid. They can be used individually or in a mixture with one another and as free acids and / or in the form of their salts, especially the alkali metal and ammonium salts, for the preparation of the bath.
  • the bath can be operated at temperatures of 20 - 80 ° C. Current densities up to about 20 A / dm 2 can be used; current densities of 0.5-10 A / dm 2 are preferably selected.
  • An increase in the pH value and / or the bath temperature enables - with a given palladium and silver concentration in the bath - the deposition of palladium-silver alloys with a higher silver content.
  • the bath can be supplemented by adding the palladium and silver compounds used for its preparation or - with regard to the silver concentration - also by using soluble silver anodes.
  • the bath according to the invention is very stable even if it is kept at a temperature higher than room temperature. If the components forming the bath are supplemented accordingly, it can be operated for several months without a black, silver-containing precipitate forming. These very good properties which are characteristic of the bath are based, as comparative experiments show, on the interaction (synergistic effect) of the amine component with the mercapto acid.
  • the bath can be used for electroplating small parts as well as tapes and wires and enables the deposition of alloys with a silver content of up to about 99% by weight.
  • the deposited palladium / silver coatings are shiny, ductile and free of pores and cracks and are therefore particularly suitable as contact layers for electrical contacts.
  • Table III shows the dependence of the silver content of the deposited palladium / silver layers on the pH and the temperature of the bath.
  • Table III PH value Bath temperature [° C] Pd / Ag [% by weight] Pd Ag 7.5 25th 85 15 8.5 25th 72 28 9.5 25th 59 41 7.5 50 75 25th 8.5 50 57 43 9.5 50 43 57
  • Table IV shows the dependency of the silver content of the deposited palladium / silver layers on the pH and the temperature of the bath.
  • Table IV PH value Bath temperature [° C] Pd / Ag [% by weight] Pd Ag 7.5 25th 80 20th 8.5 25th 60 40 9.5 25th 40 60 7.5 50 61 39 8.5 50 43 57 9.5 50 35 65
  • Example 12 (comparative example )

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  • 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)

Claims (13)

  1. Bain alcalin d'ammoniaque pour le dépôt galvanique d'alliages de palladium-argent, qui contient du palladium lié de manière complexe, un composé d'argent et un composé mercapto, caractérisé par la préparation aqueuse et 5 - 50 g/l de palladium sous forme de complexe palladium-ammine, 2 - 40 g/l d'argent sous forme de composé d'argent, 30 - 150 g/l de sel conducteur, 5 - 100 g/l d'un composé amine à partir d'une ou plusieurs polyamines aliphatiques avec 2-10 groupes amino dans la molécule et 2 - 50 g/l d'acide mercaptoalcanecarboxylique et/ou d'acide mercapto- alcanesulfonique et/ou leurs sels
    et a un pH réglé entre 7,0 et 10,0 par l'hydroxyde d'ammonium.
  2. Bain selon la revendication 1, caractérisé par une préparation aqueuse et 5 - 20 g/l de palladium sous forme de complexe palladium-ammine, 2 - 30 g/l d'argent sous forme de composé d'argent, 50 - 100 g/l de sel conducteur, 5 - 100 g/l d'un composé amine à partir d'une ou plusieurs polyamines aliphatiques avec 2-10 groupes amino dans la molécule et 2 - 20 g/l d'acide mercaptoalcanecarboxylique et/ou d'acide mercapto-alcanesulfonique et/ou leurs sels
    et a un pH réglé entre 7,0 et 10,0 par l'hydroxyde d'ammonium.
  3. Bain selon la revendication 1 ou 2, caractérisé en ce que le complexe palladium-ammine est du dichlorure de palladiumdiammine, du dibromure de palladiumdiammine ou du dinitrite de palladiumdiammine.
  4. Bain selon l'une des revendications 1 à 3, caractérisé en ce que le composé d'argent est du chlorure d'argent, du nitrate d'argent, du sulfate d'argent ou un complexe argent-diammine.
  5. Bain selon l'une des revendications 1 à 4, caractérisé en ce qu'il y existe comme polyamine une alkylènediamine avec 2-6 atomes de C dans le groupe alkylène.
  6. Bain selon la revendication 5, caractérisé en ce qu'il y existe comme alkylènediamine de l'éthylènediamine et/ou de l'hexaméthylènediamine.
  7. Bain selon l'une des revendications 1 à 6, caractérisé en ce que la polyamine est une polyéthylèneamine de formule générale NH2(CH2CH2NH)nH avec n = 2-5.
  8. Bain selon la revendication 7, caractérisé en ce qu'il y existe comme polyéthylèneamine de la diéthylènetriamine, de la triéthylènetétramine et/ou de la pentaéthylènehexamine.
  9. Bain selon les revendications 6 et 8, caractérisé en ce qu'il y existe comme polyamine un mélange d'éthylènediamine et de triéthylènetétramine.
  10. Bain selon l'une des revendications 1 à 9, caractérisé par des acides carboxyliques éventuellement par leurs sels comme sels conducteurs.
  11. Bain selon l'une des revendications 1 à 10, caractérisé par des sels d'ammonium d'acides minéraux comme sels conducteurs.
  12. Bain selon l'une des revendications 1 à 11, caractérisé par l'acide 2- ou 3-mercaptopropionique comme acide mercaptoalcanecarboxylique.
  13. Bain selon l'une des revendications 1 à 12, caractérisé par l'acide 3-mercaptopropancsulfonique comme acide mercaptoalcanesulfonique.
EP95107534A 1994-07-21 1995-05-18 Bain pour le dépÔt électrolytique d'alliages Palladium-Argent Expired - Lifetime EP0693579B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4425813 1994-07-21
DE4425813 1994-07-21
DE4444232A DE4444232C1 (de) 1994-07-21 1994-12-13 Bad zum galvanischen Abscheiden von Palladium-Silber-Legierungen
DE4444232 1994-12-13

Publications (2)

Publication Number Publication Date
EP0693579A1 EP0693579A1 (fr) 1996-01-24
EP0693579B1 true EP0693579B1 (fr) 1997-08-27

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EP95107534A Expired - Lifetime EP0693579B1 (fr) 1994-07-21 1995-05-18 Bain pour le dépÔt électrolytique d'alliages Palladium-Argent

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EP (1) EP0693579B1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5976344A (en) * 1996-05-10 1999-11-02 Lucent Technologies Inc. Composition for electroplating palladium alloys and electroplating process using that composition
DE19629658C2 (de) * 1996-07-23 1999-01-14 Degussa Cyanidfreies galvanisches Bad zur Abscheidung von Gold und Goldlegierungen
JP3301707B2 (ja) * 1997-01-20 2002-07-15 ディップソール株式会社 錫−銀合金酸性電気めっき浴
JP2000212763A (ja) * 1999-01-19 2000-08-02 Shipley Far East Ltd 銀合金メッキ浴及びそれを用いる銀合金被膜の形成方法
US7537799B2 (en) * 2003-07-11 2009-05-26 Hewlett-Packard Development Company, L.P. Methods of forming electrically conductive pathways using palladium aliphatic amine complexes
PL3159435T3 (pl) * 2015-10-21 2018-10-31 Umicore Galvanotechnik Gmbh Dodatek do elektrolitów do stopu srebro-palladowego

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL276877A (fr) * 1961-04-06
US4126524A (en) * 1975-03-12 1978-11-21 Technic, Inc. Silver complex, method of making said complex and method and electrolyte containing said complex for electroplating silver and silver alloys
US4066517A (en) * 1976-03-11 1978-01-03 Oxy Metal Industries Corporation Electrodeposition of palladium
DE3266736D1 (en) * 1981-02-27 1985-11-14 Western Electric Co Palladium and palladium alloys electroplating procedure
US4673472A (en) * 1986-02-28 1987-06-16 Technic Inc. Method and electroplating solution for deposition of palladium or alloys thereof
DE3935664C1 (en) * 1989-10-26 1991-03-28 W.C. Heraeus Gmbh, 6450 Hanau, De Palladium-silver alloys for electrical contacts - deposited from ammoniacal bath contg. palladium tetramine complex, silver di:amine complex and organic sulphur cpd.

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EP0693579A1 (fr) 1996-01-24
US5549810A (en) 1996-08-27

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