EP0081788B1 - Zusatzfreies, schnellabscheidendes galvanisches Palladiumbad - Google Patents

Zusatzfreies, schnellabscheidendes galvanisches Palladiumbad Download PDF

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Publication number
EP0081788B1
EP0081788B1 EP82111270A EP82111270A EP0081788B1 EP 0081788 B1 EP0081788 B1 EP 0081788B1 EP 82111270 A EP82111270 A EP 82111270A EP 82111270 A EP82111270 A EP 82111270A EP 0081788 B1 EP0081788 B1 EP 0081788B1
Authority
EP
European Patent Office
Prior art keywords
bath
palladium
electrolyte
phosphoric acid
ammonia
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
Application number
EP82111270A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0081788A1 (de
Inventor
Frank Dr. Vangaever
Jacky Dr. Vanhumbeeck
Laurent Danneels
Luc Boone
Luc Demaegd
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP0081788A1 publication Critical patent/EP0081788A1/de
Application granted granted Critical
Publication of EP0081788B1 publication Critical patent/EP0081788B1/de
Expired 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals

Definitions

  • the invention relates to a method for producing an additive-free, fast-depositing electroplating bath for depositing shiny and crack-free palladium layers and a method for the electroplating of shiny and crack-free palladium layers using such a bath.
  • the palladium baths working in the acidic range are usually characterized by low stability of the palladium complex, a low deposition rate (1 to 8 ⁇ m per min) and high packaging costs. However, they have the advantage that they allow a 100% current yield and the coatings are therefore usually crack-free.
  • the known alkaline palladium baths are based on ammonia complexes or amine compounds. With these baths it is usually very difficult to keep the pH constant. Another disadvantage of these baths is that only a low deposition rate between 0.25 and 1 ⁇ m can be achieved.
  • the coatings tend to crack, either through the use of glossy images, which lead to residual stresses, or through a non-100% current efficiency, since the hydrogen produced during the deposition is built into the layer; As is well known, hydrogen is very strongly absorbed by palladium.
  • the constantly evaporating ammonia in the case of ammoniacal baths requires extensive suction devices because of the odor load.
  • palladium compounds such as PdC1 2 , Pd (OH) 2 , K 2 Pd (N0 2 ) 4 , Pd (NH 2 S0 3 ) 2 , Pd (NH 3 ) 2 C1 2 and Pd (NH 3 ) 2 (N0 2 ) 2 are used.
  • EP-A-0 076 523 discloses a quick-depositing galvanic palladium bath for depositing shiny, crack-free palladium layers, which contains an ammoniacal solution of a palladium tetraamino complex and a phosphate anion or carbonate anion.
  • This bath should be free of quaternized pyridinium additives.
  • the addition of palladium in the form of palladium tetraamine chloride is preferred.
  • the invention has for its object to provide a palladium bath for the deposition of shiny, crack-free palladium layers, which only requires low manufacturing costs and high deposition rates of at least 10 to 25 microns / min with a 100% current yield. Furthermore, it should be possible to dispense with any addition of gloss and a high bath stability should be guaranteed. In order to achieve permanent corrosion resistance, the deposited layer should not contain any sulfur.
  • This object is achieved in a process for producing a generic bath by adding phosphoric acid, ammonia to the neutralization of the phosphoric acid and palladium in the form of palladium chloride in succession in distilled water heated to 90 ° C., then the use pH adjusted with ammonia or phosphoric acid and the bath is replenished to the final volume with distilled water.
  • the palladium bath according to the invention is also particularly advantageous because it is based on palladium chloride, one of the cheapest palladium salts.
  • the process for the galvanic deposition of shiny, crack-free palladium layers using such a bath is characterized in that the bath temperatures in the range from 20 to 80 ° C., with current densities in the range from 40 to 180 A / dm 2 and with an electrolyte movement, which is defined by a rotating disk electrode with an outer diameter of 10 mm and a disk diameter of 2 mm at a rotational speed of 3600 to 10,000 rpm.
  • the layers are of excellent quality. Even with an enlargement up to 15000, no cracks could be detected.
  • the free ammonia content is so low that there is no fear of odor and no corrosion of the treated material and the system.
  • the pH stability is better than with the other known alkaline baths. In the bath according to the invention the palladium does not tend to self-reduction, so that the bath is highly stable.
  • the palladium bath according to the invention is advantageously used in continuously operating electroplating systems, possibly also for the partial coating of components, such as Connectors or the like., Which are connected together to form a band.
  • the increased electrolyte movement is preferably achieved by spraying the electrolyte onto the workpiece with the aid of nozzles.
  • the nozzles form the anode, while the strip is contacted cathodically.
  • the free ends of the parts sprayed with electrolyte are preferably continuously wetted with electrolyte by an arrangement of a channel or the like.
  • the bath produces glossy and crack-free layers at a temperature of 60 ° C and a current density of 75 A / dm 2 when the rotating disk electrode is operated at 5000 rpm.
  • the bath produces glossy and crack-free layers at a temperature of 65 ° C and an electrolyte movement over spray nozzles at a current density of 140 A / dm 2 and with an electrolyte quantity of 2.8 ml / sec per nozzle.
  • the bath gives a shiny and crack-free palladium layer at a temperature of 60 ° C and a current density of 60 A / dm 2 and an electrolyte movement over spray nozzles with an amount of electrolyte of 1.7 ml / sec and per nozzle.

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)
  • Electroplating Methods And Accessories (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP82111270A 1981-12-09 1982-12-06 Zusatzfreies, schnellabscheidendes galvanisches Palladiumbad Expired EP0081788B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3148788A DE3148788C2 (de) 1981-12-09 1981-12-09 Wäßriges Bad und Verfahren zum galvanischen Abscheiden von glänzenden und rißfreien Palladiumschichten sowie Verfahren zur Herstellung des Bades
DE3148788 1981-12-09

Publications (2)

Publication Number Publication Date
EP0081788A1 EP0081788A1 (de) 1983-06-22
EP0081788B1 true EP0081788B1 (de) 1987-09-16

Family

ID=6148299

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82111270A Expired EP0081788B1 (de) 1981-12-09 1982-12-06 Zusatzfreies, schnellabscheidendes galvanisches Palladiumbad

Country Status (4)

Country Link
US (1) US4451336A (enExample)
EP (1) EP0081788B1 (enExample)
JP (1) JPS58107492A (enExample)
DE (2) DE3148788C2 (enExample)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4545868A (en) * 1981-10-06 1985-10-08 Learonal, Inc. Palladium plating
US4622110A (en) * 1981-10-06 1986-11-11 Learonal, Inc. Palladium plating
DE3443420A1 (de) * 1984-11-26 1986-05-28 Siemens AG, 1000 Berlin und 8000 München Galvanisches bad zur schnellabscheidung von palladium-legierungen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076523A1 (en) * 1981-10-06 1983-04-13 LeaRonal, Inc. A method of high speed electroplating palladium and palladium electroplating solution therefor

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US330149A (en) * 1885-11-10 Gaston pilbt and clement cabby
SU454280A1 (ru) * 1972-10-17 1974-12-25 Киевский Ордена Ленина Политехнический Институт Им.50-Летия Великой Октябрьской Социалистической Революции Электролит дл осаждени сплава платина-палладий
US3925170A (en) * 1974-01-23 1975-12-09 American Chem & Refining Co Method and composition for producing bright palladium electrodepositions
US3972787A (en) * 1974-06-14 1976-08-03 Lea-Ronal, Inc. Palladium electrolyte baths utilizing quaternized pyridine compounds as brighteners
DE2551988A1 (de) * 1975-11-17 1977-05-26 Schering Ag Verfahren zur selektiven galvanischen abscheidung von metallen sowie vorrichtung zur durchfuehrung des verfahrens
DE2657925A1 (de) * 1976-12-21 1978-06-22 Siemens Ag Ammoniakfreies, waessriges bad zur galvanischen abscheidung von palladium bzw. palladiumlegierungen
FR2403399A1 (fr) * 1977-09-19 1979-04-13 Oxy Metal Industries Corp Bains de revetement electrolytique de palladium brillant
GB2028870B (en) * 1978-07-26 1982-11-03 Effluent Treatment Ltd Electrolysis method and apparatus for treating solutions
NL7812196A (nl) * 1978-12-15 1980-06-17 Galentan Ag Inrichting voor het electrolytisch aanbrengen van metalen deklagen.
DE2939920C2 (de) * 1979-10-02 1982-09-23 W.C. Heraeus Gmbh, 6450 Hanau Verwendung eines Amins in einem Bad zum galvanischen Abscheiden von Palladium
US4392921A (en) * 1980-12-17 1983-07-12 Occidental Chemical Corporation Composition and process for electroplating white palladium
DE3108358C2 (de) * 1981-03-05 1985-08-29 Siemens AG, 1000 Berlin und 8000 München Vorrichtung zum partiellen Galvanisieren von zu elektrisch leitenden Bändern, Streifen oder dgl. zusammengefaßten Teilen im Durchlaufverfahren

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076523A1 (en) * 1981-10-06 1983-04-13 LeaRonal, Inc. A method of high speed electroplating palladium and palladium electroplating solution therefor

Also Published As

Publication number Publication date
JPS58107492A (ja) 1983-06-27
EP0081788A1 (de) 1983-06-22
US4451336A (en) 1984-05-29
JPH0341556B2 (enExample) 1991-06-24
DE3277311D1 (en) 1987-10-22
DE3148788A1 (de) 1983-07-21
DE3148788C2 (de) 1986-08-21

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