Electrolyte for the electrolytic deposition of silver-palladium alloys and method for deposition thereof

Abstract

The present invention relates to an electrolyte and to a method for the electrolytic deposition of silver-rich silver-palladium alloys which to a minor degree also include selenium and/or tellurium. The electrolyte of the invention allows uniform deposition of such an alloy on conductive surfaces across a wide range of current densities.

Claims

1. A cyanide-free, acidic, and aqueous electrolyte for the electrolytic deposition of silver-palladium alloys comprising 70 to 99 percent by weight of silver, said electrolyte comprising in dissolved form: 1) a silver compound in a concentration of 0.01-2.5 mol/l silver; 2) a palladium compound in a concentration of 0.002-0.75 mol/l palladium; 3) a tellurium compound or selenium compound in a concentration of 0.075-80 mmol/l tellurium/selenium; 4) urea in a concentration of 0.2-2 mol/l, and/or one or more amino acids selected from the group consisting of: alanine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, lysine, leucine, methionine, phenylalanine, phenylglycine, proline, serine, tyrosine, and valine, in a concentration of 0.2-35 mmol/l; and 5) a sulfonic acid in a concentration of 0.25-4.75 mol/l, wherein the electrolyte has a pH of <2.

2. The electrolyte as claimed in claim 1, characterized in that one or more amino acids selected from the group consisting of glycine, alanine, and valine are used.

3. The electrolyte as claimed in claim 1, characterized in that the selenium and/or tellurium is used as a compound in which the selenium and/or tellurium has an oxidation state of +4 or +6.

4. The electrolyte of claim 1, wherein the silver compound is selected from the group consisting of silver carbonate, silver sulfate, silver phosphate, silver pyrophosphate, silver nitrate, silver oxide, and silver lactate.

5. The electrolyte of claim 4, wherein the silver compound is selected from the group consisting of silver carbonate, silver phosphate, silver pyrophosphate, silver oxide, and silver lactate.

6. The electrolyte of claim 1, wherein the silver-palladium alloys comprise 75 to 97 percent by weight of silver.

7. The electrolyte of claim 6, wherein the silver-palladium alloys comprise 85 to 95 percent by weight of silver.

8. A method for the electrolytic deposition of silver-palladium coats comprising 70 to 99 percent by weight of silver from the electrolyte of claim 1, comprising: immersing an electrically conductive substrate into the electrolyte and establishing a current flow between an anode in contact with the electrolyte, and the substrate as cathode.

9. The method as claimed in claim 8, characterized in that the temperature of the electrolyte is 45-60° C.

10. The method as claimed in claim 8, characterized in that the current flow during electrolysis is between 0.5-100 A/dm.sup.2.

11. The method as claimed in claim 8, characterized in that the electrolyte has a pH and the pH is adjusted continually to a value <1 during electrolysis.

12. A cyanide-free, acidic, and aqueous electrolyte for the electrolytic deposition of silver-palladium alloys comprising predominantly silver, said electrolyte comprising in dissolved form: 1) a silver compound in a concentration of 0.01-2.5 mol/l silver; 2) a palladium compound in a concentration of 0.002-0.75 mol/l palladium; 3) a tellurium compound or selenium compound in a concentration of 0.075-80 mmol/l tellurium/selenium; 4) urea in a concentration of 0.2-2 mol/l, and/or one or more amino acids selected from the group consisting of: alanine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, lysine, leucine, methionine, phenylalanine, phenylglycine, proline, serine, tyrosine, and valine, in a concentration of 0.2-35 mmol/l; and 5) a sulfonic acid in a concentration of 0.25-4.75 mol/l, wherein the electrolyte has a pH of <2.

13. The electrolyte of claim 12, wherein the one or more amino acids is selected from the group consisting of glycine, alanine, and valine are used.

14. The electrolyte of claim 12, wherein the selenium and/or tellurium are used as a compound in which the selenium and/or tellurium have an oxidation state of +4 or +6.

15. The electrolyte of claim 12, wherein the silver compound is selected from the group consisting of silver carbonate, silver sulfate, silver phosphate, silver pyrophosphate, silver nitrate, silver oxide, and silver lactate.

16. The electrolyte of claim 15, wherein the silver compound is selected from the group consisting of silver carbonate, silver phosphate, silver pyrophosphate, silver oxide, and silver lactate.

17. A method for the electrolytic deposition of silver-palladium coats comprising predominantly silver from the electrolyte of claim 12, comprising: immersing an electrically conductive substrate into the electrolyte and establishing a current flow between an anode in contact with the electrolyte, and the substrate as cathode.

18. The method of claim 17, wherein the temperature of the electrolyte is 45-60° C. and the current flow during electrolysis is between 0.5-100 A/dm.sup.2.

19. The method of claim 17, wherein the electrolyte has a pH and the pH is adjusted continually to a value <1 during electrolysis.

20. A cyanide-free, acidic, and aqueous electrolyte for the electrolytic deposition of silver-palladium alloys comprising less than 30 percent by weight of palladium, said electrolyte comprising in dissolved form: 1) a silver compound in a concentration of 0.01-2.5 mol/l silver; 2) a palladium compound in a concentration of 0.002-0.75 mol/l palladium; 3) a tellurium compound or selenium compound in a concentration of 0.075-80 mmol/l tellurium/selenium; 4) urea in a concentration of 0.2-2 mol/l, and/or one or more amino acids selected from the group consisting of: alanine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, lysine, leucine, methionine, phenylalanine, phenylglycine, proline, serine, tyrosine, and valine, in a concentration of 0.2-35 mmol/l; and 5) a sulfonic acid in a concentration of 0.25-4.75 mol/l, wherein the electrolyte has a pH of <2.

21. The electrolyte of claim 20, wherein the silver compound is selected from the group consisting of silver carbonate, silver sulfate, silver phosphate, silver pyrophosphate, silver nitrate, silver oxide, and silver lactate.

22. The electrolyte of claim 20, wherein the selenium and/or tellurium are used as a compound in which the selenium and/ or tellurium have an oxidation state of +4 or +6.

23. A method for the electrolytic deposition of silver-palladium coats comprising less than 30 percent by weight of palladium from the electrolyte of claim 20, comprising: immersing an electrically conductive substrate into the electrolyte and establishing a current flow between an anode in contact with the electrolyte, and the substrate as cathode.

Description

FIGURES

(1) FIG. 1: Coating cell after testing of the inventive electrolyte, with no precipitations on the container/cell walls.

(2) FIG. 2: Coating cell after testing of the AiF electrolyte (report of Forschungsinstitut Edelmetallchemie & Metallchemie aus Schwäbisch Gmünd; project number: AiF 14160 N), with dark precipitations on the container/cell walls.

(3) FIG. 3: FIG. 3 shows the change in the deposition rate with the current density selected. It is apparent that deposition occurs at virtually the same rate across a wide current density range.

(4) FIG. 4: FIG. 4 shows the evolution of the rate of deposition as a function of the current density. Evident here is a preferred linear dependence between the parameters.

(5) Embodiments of the electrolyte for high-speed applications:

EXAMPLE 1

(6) 50 ml/l 70% methanesulfonic acid 3 g/l glycine 10 g/l palladium (as palladium hydroxide) 10 g/l silver (as silver methanesulfonate) 0.5 g/l tellurium (as tellurous acid) Temperature: 50° C. Anodes: PtTi Current density: 1 to 14 A/dm.sup.2 Weight of deposit: see FIG. 3 Deposition rate: see FIG. 4

(7) Alloy composition obtained over the indicated current density range: 90% by weight silver, 7-8% by weight palladium, and 3-2% by weight tellurium.

EXAMPLE 2

(8) 80 ml/l 70% methanesulfonic acid 5 g/l alanine 10 g/l palladium (as palladium chloride) 6 g/l silver (as silver carbonate) 1.0 g/l tellurium (as potassium tellurite) Temperature: 60° C. Anodes: PtTi Current density: 0.5 to 12 A/dm.sup.2

(9) Alloy composition obtained over the indicated current density range: 88% by weight silver, 7-10% by weight palladium, and 5-2% by weight tellurium.

EXAMPLE 3

(10) 100 ml/l 70% methanesulfonic acid 5 g/l valine 8 g/l palladium (as palladium hydroxide) 15 g/l silver (as silver nitrate) 1.5 g/l tellurium (as tellurous acid) Temperature: 60° C. Anodes: graphite Current density: 1 to 20 A/dm.sup.2

(11) Alloy composition obtained over the indicated current density range: 92% by weight silver, 3-4% by weight palladium, and 5-4% by weight tellurium.

EXAMPLE 4

(12) 150 ml/l 70% methanesulfonic acid 2 g/l glycine 15 g/l palladium (as palladium sulfate) 8 g/l silver (as silver carbonate) 0.5 g/l tellurium (as tellurous acid) Temperature: 55° C. Anodes: PtTi Current density: 1 to 16 A/dm.sup.2

(13) Alloy composition obtained over the indicated current density range: 90% by weight silver, 8-9% by weight palladium, and 2-1% by weight tellurium.

EXAMPLE 5

(14) 100 ml/l 70% methanesulfonic acid 1 g/l glycine 3 g/l alanine 15 g/l palladium (as palladium methanesulfonate) 8 g/silver (as silver nitrate) 2.0 g/tellurium (as tellurous acid) Temperature: 60° C. Anodes: graphite Current density: 1 to 28 A/dm.sup.2

(15) Alloy composition obtained over the indicated current density range: 87% by weight silver, 9-10% by weight palladium, and 4-3% by weight tellurium.