Electrochemical Behavior of High-Speed Low-Cyanide Silver Plating Baths

In a study of the electrochemical behavior of low-cyanide silver plating baths and of the properties of the deposits obtained, it was found that the current-potential curve obtained with a solid electrode showed a two-step reduction wave, the height of the first being 1/5 that of the second. Analysis of the results of polarographic and rotating disk electrode measurmenents sugests that the rate-controlling steps were AgCN+e-_??_Ag+CN-……(1) Ag(CN)2-+e-_??_Ag+2CN-……(2) for the first and second waves respectively. The Tafel plots of the two waves showed linear relationships at their rising portions, and the reactions are accordingly concluded to be slow chargetransfer controlled. In baths to which selenocyanate ion was added, the increase in current was markedly greater for the second wave than for the first, and the wave was shifted to the positive side. Potential decay curves for the baths containing selenocyanate ion obtained by the current interrupter method showed lower differential capacities than those for baths that were free of selenocyanate ion. This indicates that the selenocyanate ions were adsorbed preferentially at the electrode, suppress the adsorption of cyanide ions and enhancing the silver deposition reaction. Deposits obtained by jet plating were matt at current densities lower than 50A/dm2, and their appearance was not affected by the addition of selenocyanate ion. At above 50A/dm2, deposits obtained from selenocyanate-free baths were burnt, but deposits obtained from baths with selenocyanate ion added were mirror-bright with a strong (200) orientation up to around 150A/dm2.