Pure and Applied Chemistry

Abstract: A rational understanding of what occurs during electrocrystallization, defined at a nanolevel, is developed to control electrodeposition processes. The electrokinetic behavior of the elements in solutions and the electrodeposits structure resulting from the electron exchange reaction at the cathodic surface are taken into consideration and compared. Transient electrokinetic parameters are measured with the secondary current pulse (SCP) technique, where a square galvanostatic pulse of a few ms duration is superimposed on the cathode while electrodeposition is running. Two parameters are obtained, the transient Tafel slope and the adsorption pseudo-capacitance; whilst a third parameter, the diffusive time constant, must be introduced if the overvoltage does not arrive to a steady state during the short pulse period. These parameters are related to the growth of different structures and permit a good control of the process. Control of the growth with nanodefinition is key to the development of innovative processes to keep pace with more and more demanding applications and environmental challenges. Examples are given to stress the relevance of the theoretical framework and to show possible implications for electrodeposition technology and its applications.