EP0059452B1 - Procédé de dépôt électrolytique de palladium et d'alliages de palladium - Google Patents

Procédé de dépôt électrolytique de palladium et d'alliages de palladium Download PDF

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Publication number
EP0059452B1
EP0059452B1 EP82101494A EP82101494A EP0059452B1 EP 0059452 B1 EP0059452 B1 EP 0059452B1 EP 82101494 A EP82101494 A EP 82101494A EP 82101494 A EP82101494 A EP 82101494A EP 0059452 B1 EP0059452 B1 EP 0059452B1
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EP
European Patent Office
Prior art keywords
palladium
plating
molar
process according
electroplating
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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
EP82101494A
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German (de)
English (en)
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EP0059452A2 (fr
EP0059452A3 (en
Inventor
Joseph Anthony Abys
Harvey Stewart Trop
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Trasformazione Societaria at & T Technologies Inc
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Western Electric Co Inc
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Publication of EP0059452A3 publication Critical patent/EP0059452A3/en
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    • 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
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used

Definitions

  • the invention is a process for electroplating palladium and palladium alloys of the type described in the preamble clause of claim 1.
  • Precious metals are used as protective films on surfaces for a variety of reasons. In the jewelry trade, it is used to improve the appearance of an article as in gold plated jewelry. In other applications, it is used to protect against corrosion of metals and other surface materials.
  • protective films made of precious metals are used as conduction paths in electrical circuits and as contact surfaces in devices with electrical contacts. Gold is used extensively in these applications with great success. However, the increased price of gold makes it attractive to look at other precious metals as protective films on various surfaces.
  • Palladium and palladium alloys are used extensively in a variety of industrial applications. Typical examples are the jewelry trade where such films are used to protect surfaces against corrosion and to improve appearance, in the electrical arts in various electrical devices and electronic circuits and in the optical field for various types of optical devices.
  • palladium is especially attractive as an electrical contact material in electrical connectors, relay contacts, switches, etc.
  • Palladium alloys with at least 10 mole percent palladium, remainder of at least one of the metals silver nickel and copper are also useful for the same applications. Indeed, because of the increasing cost of gold, palladium and palladium alloys become more and more attractive economically as a contact material, surface material, and in other applications. In many applications where gold is used, it is often economically attractive to use palladium, provided, an inexpensive and efficient method of plating ductile and adherent palladium is available.
  • Ethylenediamine has been used in a palladium alloy plating procedure (U.S.S.R. Patent No. 519,497 issued 30 June 1976); (C. A. 85: 113802m) and it was known to the inventors that ethylenediamine is useful in palladium electroplating in the following composition bath: 28 gm/I PdCI 2 , 140 gm/I Na 2 S0 4 and sufficient ethylenediamine to dissolve the PdCl 2 .
  • the bath is used at room temperature, the current density is 20 mA/cm 2 and the pH between 11 and 12.
  • DE-A-2244437 discloses electroplating of gold and gold alloys including gold alloyed with palladium. It describes a large number of complexing agents for the metallic ions in the bath, including various aliphatic polyamines with diethylenetriamine being mentioned as an example, and it is essentially directed to the production of ductile and bright decorative platings.
  • the invention is based on a critical selection of a few complexing agents from myriads of compounds; and it has been found that palladium and its mentioned alloys may be electroplated without simultaneous hydrogen evolution, if the used complexing agent is one or more organic aliphatic polyamines selected from diaminopropane (particularly 1,3-diaminopropane), diethylenetriamine, 1,4-diaminobutane, 1,6-diaminohexane N,N,N',N'-tetramethylethylenediamine and 2-hydroxy-1,3-diaminopropane.
  • the aqueous electroplating bath is alkaline, i.e.
  • pH between 7.5 and 13.5 to avoid corrosion of the surface being plated and sufficiently conductive to allow plating i.e. greater than 10- 3 ohm-' cm- 1 .
  • Additional substances may be added to the palladium plating bath to control and adjust pH (such as a buffer), to increase conductivity and to improve the properties of the plated metal.
  • Typical substances used to improve the plated metal are lactones (i.e., phenolphthalein, phenolsulfone- phthalein, etc.), lactams, cyclic sulfate esters, cyclic imides and cyclic oxazolinones.
  • Certain poly-alkoxylated alkylphenols may also be useful. The process is also useful for plating certain palladium alloys including at least 10 mole percent palladium, remainder copper, nickel and/or silver.
  • the Figure shows a typical apparatus useful in electroplating palladium and palladium alloys in accordance with the invention.
  • the invention is a process for electroplating palladium metal or palladium alloy in which the indicated group of organic aliphatic polyamines is used as complexing agent in the palladium plating bath.
  • the conditions (pH, temperature, etc.) under which optimum plating occurs with these preferred complexing agents permits rapid plating without incorporation or evolution of hydrogen.
  • undesirable chemical attack on the surface being plated is minimal or insignificant under optimum conditions of plating with these complexing agents.
  • Alloy plating may also be carried out using the indicated complexing agents.
  • Concerned palladium alloys consists of at least 10 mole percent palladium, remainder copper, silver and/ or nickel. Other useful alloys are 60 mole percent palladium, remainder silver, copper and/or nickel, or 40 mole percent palladium, remainder silver, copper and/or nickel, etc.
  • the palladium-silver alloys are particularly useful, especially for electrical contact surfaces.
  • a large variety of counter ions may be used in the electroplating bath provided the anions are stable (chemically and electrochemically) and in particular are not subject to oxidation or reduction under conditions of the electroplating process.
  • the anion should not interfere with the plating process by either chemical attack on the surface being plated or on the metal complex system.
  • Typical anions are halides, nitrate, sulfate and phosphates. Chloride ion is preferred because of the low cost of palladium chloride and the stability of the chloride ion under conditions of the electroplating process.
  • certain ions including those set forth above, may be used as supporting electrolyte to increase conductivity of the electroplating bath.
  • the cation used for the supporting electrolyte may be any soluble ion which does not interfere with the electroplating process.
  • Alkali-metal ions Na, K, Li
  • Palladium chloride is preferred because of availability and stability.
  • useful are compounds yielding tetrachloropalladate ion in aqueous solution such as alkali-metal tetrachloropalladate (i.e., K 2 PdCI 4 ). These compounds may be used initially to make the bath and to replenish the bath.
  • the pH of the bath may vary from 7.5 to 13.5, with the range from 11.0 to 12.5 preferred.
  • the preference particularly applies when the preferred polyamines are used, namely 1,3-diaminopropane and diethylenetriamine.
  • very rapid plating can be carried out with excellent plating results.
  • a bath composition which permits rapid plating with more alkaline solution is preferred because of decreased attack on the surface being plated and decreased chances of hydrogen evolution.
  • the plating process may be carried out with or without a buffer system.
  • a buffer system is often preferred because it maintains constant pH and adds to the conductivity of the bath.
  • Typical buffer systems are the phosphate system, borax, bicarbonate, etc.
  • Preferred is the HPO-VPO-14 system often made by adding an alkali-metal hydroxide (KOH, NaOH, etc.) to an aqueous solution of the hydrogen phosphate ion.
  • concentration of buffer varies from about 0.1 Molar to 2 Molar (about 1.0+0.2 Molar preferred) and the mole ratio of hydrogen phosphate to phosphate varies from 5/1 to 1/5 (with equal mole amounts within ⁇ 50 percent preferred). These mole ratios often depend on the particular pH desired for the plating bath.
  • the bath temperature often depends on bath composition and concentration, plating cell design, pH and plating rate. Contemplated temperatures for typical conditions are from room temperature to about 80 degrees C with 40 to 60 degrees C most preferred.
  • Various surfaces may be plated using the disclosed process. Usually, the plating would be carried out on a metal surface or alloy surface but any conducting surface would appear sufficient. Also, electrolessly plated surfaces may be useful. Typical metal and alloy surfaces are copper, nickel, gold, platinum, palladium (as, for example, a surface electrolessly plated with palladium and then electroplated with palladium in accordance with the invention). Various alloy surfaces may also be used such as copper-nickel-tin alloys.
  • composition of the bath may vary within the claimed limits. In general, sufficient polyamine should be present to complex with the palladium. Usually, it is advantageous if excess polyamine is present in the bath solution.
  • the palladium concentration in the bath varies from 0.01 Molar to saturation. Preferred concentrations often depend on plating rate, cell geometry, agitation, etc. Typical preferred palladium concentration ranges for high-speed plating (54 to 1076 mA/cm 2 ) [50 to 1000 ASF] are higher than for low-speed plating (up to 54 mA/cm 2 ) [up to 50 ASF]. Preferred palladium concentration ranges for high-speed plating vary also from 0.1 1 0 1.0 Molar. For low-speed plating, the preferred range is from 0.05 to 0.2 Molar. Where palladium alloy plating is included, the alloy metal (i.e. copper, silver or nickel) replaces part of the palladium in the composition of the plating bath. Up to 90 mole percent of palladium may be replaced by alloy metal.
  • the alloy metal i.e. copper, silver or nickel
  • the amount of complexing agent may vary from 0.5 times (on the basis of moles) the concentration of the palladium species to saturation of the complexing agent. Generally, it is preferred to have excess complexing agent, typically from two times to 12 times the mole concentration of the palladium species. Most preferred is about six times the mole concentration of palladium.
  • the preferred ranges of complexing agent in terms of palladium species are the same for high-speed and low-speed baths.
  • the concentration of buffer may vary over large limits. Such concentrations often depend on cell design, plating rates, etc. Typically, the buffer concentration varies from 0.1 Molar to saturation with from 0.2 to 2.0 Molar preferred.
  • the bath may be prepared in a variety of ways well known in the art.
  • a typical preparation procedure which yields excellent result is set forth below: Equal volumes (142 ml) of 1,3-diaminopropane and water are mixed in a beaker. Heat of solution is sufficient to heat the resulting solution to about 60 degrees C. To this solution with vigorous stirring are added 50 gms of PdCI 2 in portions of 0.5 g every two minutes. Since the resulting reaction is exothermic, the solution can be maintained at 60 degrees C by adjusting the rate of addition of PdCl 2 . The solution is filtered to remove solid matter (generally undissolved PdC1 2 or PdO) and diluted to one liter.
  • Electroplating experiments are carried out in an electroplating cell provided with means for high agitation. Temperature is maintained between 50 and 65 degrees C, 55 degrees preferred. Current is passed through anode, electroplating bath and cathode. The electrical energy is supplied by a conventional power supply. The current density is 188 mA/cm 2 (175 ASF). Typical thicknesses in these experiments are 102 to 381 ⁇ m (40 to 150 microinches). The deposit is crack free as determined by a scanning electron micrograph at 10,000 magnification. Both adherence and ductility are excellent. Similar results are obtained using 0.1 Molar palladium and 0.5 Molar palladium. Plating rate is often determined by the thickness desired after a predetermined period of plating.
  • a strip line plating apparatus see, for example, US-A-4,153,523 and US-A-4,230,538 the strip line being plated is exposed to the plating solution for a set period of time (depending on the speed the strip is moving down the line and the length of the plating cell) and the plating rate is adjusted to give the desired thickness in this period of time. Similar results are obtained with diethylenetriamine. Experiments carried out with 2 hydroxy-1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane yield similar results.
  • a typical bath contains 16.66 g PdCl 2 , 42 g polyamine complexing agent, 42 g K 3 PO 4 , 139 g K 2 HP0 4 and sufficient water to make one liter.
  • the preparation procedure is exactly the same as above.
  • the pH is about 10.8 at 55 degrees C and plating is carried out in the temperature range from 50 to 65 degrees C. Typical slow plating rates are about 11 mA/cm 2 (10 ASF).
  • Electroplating was carried out at 55 degrees C.
  • Electroplating was carried out at 55 degrees C.
  • Electroplating was carried out at 55 degrees C.
  • Electroplating was carried out at 55 degrees C.
  • Palladium alloys may also be electroplated in accordance with the invention.
  • a typical bath composition for palladium alloy plating is as follows: 69.6 g Ag 2 0, 53.2 g PdCl 2 , 222 g 1,3-diaminopropane, 106.2 g K 3 PO 4 , 86.5 g K 2 HP0 4 and water to one liter.
  • the pH of the bath is adjusted to 11.3 by the addition of KOH or H 3 P0 4 .
  • the bath temperature is maintained between 40 and 65 degrees C and current density between 1.1 and 538 mA/cm 2 (1 and 500 ASF).
  • the other polyamine complexing agents mentioned above are also useful, including diethylenetriamine.
  • a useful bath for palladium-nickel plating is as follows: 38.9 g NiCl 2 , 53.2 g PdCl 2 , 222 g 1,3-diaminopropane, 106 g K 3 P0 4 , 86.5 g K 2 HP0 4 and water to one liter.
  • Preferred operating temperature is from 40 to 65 degrees C
  • pH is about 12
  • current density from 1.1 to 538 mA/cm 2 (1 to 500 ASF).
  • cobalt salt added to the bath.
  • the stripline plating apparatus described in the above-cited patents are particularly advantageous for carrying out the process. They permit good control of the bath conditions, the rate of plating and permit rapid palladium plating.
  • the palladium plating process is highly advantageous for plating electrical contact pins for electrical connectors such as described in the above references.
  • Fig. 1 shows apparatus 10 useful in the practice of the invention.
  • the surface to be plated 11 is made the cathode in the electrolytic process.
  • the anode 12 is conveniently made of platinized titanium or may be made of various other materials such as oxides of platinum group metals, binder metal oxides, etc.
  • Both anode and cathode are at least partially immersed in the electroplating bath 13 containing source of palladium complex with an organic aliphatic polyamine.
  • a container 14 is used to hold the palladium plating solution and the anode 12 and cathode 11 are electrically connected to an adjustable source of electrical energy 15.
  • An ammeter 16 and voltmeter 17 are used to monitor current and voltage.

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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 (9)

1. Procède d'electrodéposition du palladium et d'alliages de palladium contenant au moins 10% en mole de palladium, le reste étant l'un au moins des métaux que sont l'argent, le cuivre et le nickel, qui consiste à faire passer du courant électrique dans une cathode, dans un bain d'électrodéposition et dans une anode, sous potentiel cathodique suffisamment grand pour l'électrodeposition du palladium, ce bain comprenant une solution aqueuse d'un complexe de palladium et d'une polyamine aliphatique et ayant une conductivité supérieure à 10-3 ohm-1 cm-1, et à effectuer le processus d'électrodéposition à une température allant de la température ambiante à 80°C, caractérisé en ce que le pH est de 7,5 à 13,5 et la polyamine aliphatique est choisie parmiun diaminopropane, la diéthylène- triamine, le 1,4-diaminobutane, le 1,6-diaminohexane, la N,N,N',N'-tétraméthyléthylène- diamine et le 2-hydroxy-1,3-diaminopropane, la solution aqueuse du complexe de palladium et de polyamine aliphatique provenant de la réaction d'une source de palladium sur au moins l'une desdites polyamines aliphatiques, la concentration molaire de palladium allant de 0,01 mole à la saturation, et la concentration molaire de polyamine aliphatique allant de 0,5 fois la concentration molare de palladium à la saturation en la polyamine aliphatique.
2. Procédé suivant la revendication 1, caractérisé en ce que le diaminopropane comprend du 1,3-diaminopropane.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que la concentration molaire de polyamine aliphatique représente de 2 à 12 fois la concentration molaire de palladium.
4. Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce que le procédé de dépôt électrolytique est effectué à une température comprise entre 40 et 60°C.
5. Procédé suivant la revendication 1 ou 2 ou 3 ou 4, caractérisé en ce que la concentration molaire de palladium est de 0,1 à 1,0 mole et la densité de courant de dépôt est comprise entre 0,054 et 1,076 A/cm2 (50 et 1000 ASF).
6. Procédé suivant la revendication 1 ou 2 ou 3 ou 4, caractérisé en ce que la concentration molaire de palladium et de 0,05 à 0,2 mole et la densité de courant de dépot va jusqu'à 0,054 A/cm2 (50 ASF).
7. Procédé suivant l'une quelconque des revendications précédentes 1 à 6, caractérisé en ce que le bain d'électrodéposition inclut un tampon comprenant un ion phosphate acide et un ion phosphate.
8. Procédé suivant la revendication 7, caractérisé en ce que la concentration du tampon va de 0,1 à 2 moles et le rapport de l'ion phosphate acide à l'ion phosphate va de 5/1 à 1/5.
9. Procédé suivant l'une quelconque des revendications 1 à 8, caractérisé en ce que le pH va de 11,0 à 12,5.
EP82101494A 1981-02-27 1982-02-26 Procédé de dépôt électrolytique de palladium et d'alliages de palladium Expired EP0059452B1 (fr)

Applications Claiming Priority (2)

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US23915181A 1981-02-27 1981-02-27
US239151 1994-05-05

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EP0059452A2 EP0059452A2 (fr) 1982-09-08
EP0059452A3 EP0059452A3 (en) 1982-11-10
EP0059452B1 true EP0059452B1 (fr) 1985-10-09

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EP82901061A Expired EP0073236B1 (fr) 1981-02-27 1982-02-18 Procede de revetement par electrodeposition de palladium et des alliages de palladium
EP82101494A Expired EP0059452B1 (fr) 1981-02-27 1982-02-26 Procédé de dépôt électrolytique de palladium et d'alliages de palladium

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EP (2) EP0073236B1 (fr)
JP (1) JPS58500289A (fr)
CA (1) CA1189016A (fr)
DE (1) DE3266736D1 (fr)
GB (1) GB2112018B (fr)
HK (1) HK48088A (fr)
WO (1) WO1982002908A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4444232C1 (de) * 1994-07-21 1996-05-09 Heraeus Gmbh W C Bad zum galvanischen Abscheiden von Palladium-Silber-Legierungen

Families Citing this family (9)

* 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
US4741818A (en) * 1985-12-12 1988-05-03 Learonal, Inc. Alkaline baths and methods for electrodeposition of palladium and palladium alloys
EP0693579B1 (fr) * 1994-07-21 1997-08-27 W.C. Heraeus GmbH Bain pour le dépÔt électrolytique d'alliages Palladium-Argent
DE4431847C5 (de) * 1994-09-07 2011-01-27 Atotech Deutschland Gmbh Substrat mit bondfähiger Beschichtung
FR2807450B1 (fr) * 2000-04-06 2002-07-05 Engelhard Clal Sas Bain electrolytique destine au depot electrochimique du palladium ou de ses alliages
TWI354716B (en) * 2007-04-13 2011-12-21 Green Hydrotec Inc Palladium-containing plating solution and its uses
US8900436B2 (en) * 2008-05-07 2014-12-02 Umicore Galvanotechnik Gmbh Pd and Pd-Ni electrolyte baths
JP2012241260A (ja) * 2011-05-23 2012-12-10 Kanto Gakuin 電解パラジウム−リン合金めっき液、めっき被膜及びめっき製品
DE102018126174B3 (de) * 2018-10-22 2019-08-29 Umicore Galvanotechnik Gmbh Thermisch stabile Silberlegierungsschichten, Verfahren zur Abscheidung und Verwendung

Citations (1)

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Publication number Priority date Publication date Assignee Title
DE2244437A1 (de) * 1971-09-06 1973-03-15 Omf California Inc Elektrolytisches bad zur elektrochemischen abscheidung von goldlegierungen und dessen anwendung

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
US2452308A (en) * 1946-02-28 1948-10-26 George C Lambros Process of plating palladium and plating bath therefor
DE2360834C3 (de) * 1973-12-06 1978-05-18 Inovan-Stroebe Kg, 7534 Birkenfeld Bad und Verfahren zum galvanischen Abscheiden von Palladiumschichten
DE2506467C2 (de) * 1975-02-07 1986-07-17 Schering AG, 1000 Berlin und 4709 Bergkamen Bad und Verfahren zur galvanischen Abscheidung von Palladium-Nickel-Legierungen
US4066517A (en) * 1976-03-11 1978-01-03 Oxy Metal Industries Corporation Electrodeposition of palladium
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
US4278514A (en) * 1980-02-12 1981-07-14 Technic, Inc. Bright palladium electrodeposition solution

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2244437A1 (de) * 1971-09-06 1973-03-15 Omf California Inc Elektrolytisches bad zur elektrochemischen abscheidung von goldlegierungen und dessen anwendung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4444232C1 (de) * 1994-07-21 1996-05-09 Heraeus Gmbh W C Bad zum galvanischen Abscheiden von Palladium-Silber-Legierungen

Also Published As

Publication number Publication date
HK48088A (en) 1988-07-08
DE3266736D1 (en) 1985-11-14
GB2112018B (en) 1984-08-15
WO1982002908A1 (fr) 1982-09-02
EP0073236A4 (fr) 1983-01-14
GB2112018A (en) 1983-07-13
CA1189016A (fr) 1985-06-18
JPH0219197B2 (fr) 1990-04-27
JPS58500289A (ja) 1983-02-24
EP0073236B1 (fr) 1985-10-09
EP0059452A2 (fr) 1982-09-08
EP0059452A3 (en) 1982-11-10
EP0073236A1 (fr) 1983-03-09

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