Abstract
The process of the electrolytic deposition of metals is considered as a particular case of heterogeneous phase formation. The basic set of kinetic equations describing the initial stage of formation of a thin metal film on an inert cathode is formulated in a general form. With the aid of these equations the mean crystallite radius, the overvoltage and the electric current flowing through the system can be found as functions of time if the total “ohmic” resistance of the electrolytic cell is known. Taking into account the Gibbs-Thomson effect of crystallite curvature, expressions are derived for this resistance in the particular cases when the crystallite growth is limited solely (i) by the specific electrical conductivity of the electrolyte, (ii) by volume diffusion of the metal ions from the bulk of the electrolyte towards the surface of the growing crystallites, and (iii) by impediments accompanying the transition of the metal ions through the crystallite/electrolyte interphase boundary. Finally, it is shown that electrodeposition processes characterized by other types of crystallite growth control can also be analysed by means of the basic set of kinetic equations if the total cell resistance is properly defined.
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