Electrodeposition of Silver under Direct and Pulsed Current

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Abstract
Electrodeposition of Ag+ ions on a vertical plane cathode immersed in stagnant and solutions was carried out under direct and pulsed current. The morphological variations with electrolytic conditions were examined by measuring the average diameters of the electrodeposits using the intercept method. The ratio of the particle diameter obtained in a solution under pulsed electrolysis to that under direct current at the same average current density was minimum near 50–60 mA/cm2. It was further enhanced with a decrease in the duty cycle when the pulse‐on time and the charge density were maintained at 1 ms and 9 C/cm2, respectively. The concentration profiles of Ag+ ions in solution were also measured by holographic interferometry. In these experiments, the duplex diffusion layer model proposed by Ibl (18) was found to adequately describe the phenomena provided that the pulse‐on time was sufficiently long. Based on the concentration profile measurements, it was deduced that the appearance of the minimum ratio of particle diameter was closely related to the depletion of the surface concentration of Ag+ ions during the pulse‐on time, that is, to the concept of limiting current pulse.

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