The Use of the Fractal Dimension with an Aggregation Model to Characterize Copper Electrodeposition in the Presence of Thiourea

"This work is an extension of a previous investigation on the development of surface roughness during electrodeposition of copper. A comprehensive model based on diffusion and migration in a force field together with surface diffusion and sticking probabilities is used to generate profiles which are compared to those produced experimentally. The roughness is characterized by using the technique of fractal geometry which is shown to describe both qualitatively and 9uantitatively the development of surface morphology during electrodeposition.The work is extended to the deposition of copper in the presence of various concentrations of thiourea. The development of roughness is observed experimentally on the edge of a thin copper disc mounted between two glass plates. This enables photographs to be taken at various stages during growth. The surface outline is digitized using an image analyzer which enables the fractal dimension to be determined as growth proceeds. As expected, the presence of thiourea at low concentrations produces a fractal dimension which is closer to unity (i.e. the surface becomes smoother).IntroductionThe development of surface morphology during electrodeposition has far-reaching implications for copper plating in the electrowinning and electrorefining processes. Short circuits as the cathode surface grows unevenly require operator intervention in a dangerous environment and imply processing delays, and the inclusion of electrolyte in small gaps in the plated cathode have implications in downstream processing of the cathode. Higher current densities are obviously desirable, as they result in greater production rates, but as shown by Ettel et. al.(l), Harvey et. al.(2), Cook (3), and Harvey et. al.(4), it is not possible to operate near the projected economically optimum conditions because the electrodeposition of copper from sulphate and acid solutions is a mass transfer controlled process. It has been shown (Ettel et. al.(l), Harvey et. al.(2)) that the closer a system operates to mass transfer limiting conditions, the poorer the resulting cathode quality. One solution is to use agitation techniques to increase the limiting current density. Another is to add surface active additives to the electrolyte which has been shown by Ettel et. al.(l), Harveyet. al.(2) and Afifi et. a1.(5) to allow higher rates of production without decreasing cathode quality. The second proposed solution is of interest in this work, since there is very little knowledge of the conditions under which these additives operate effectively, and little fundamental understanding of the mechanism by which they operate. The current work seeks to contribute to this field by correlating a simulation model with experimental results to describe the development of surface morphology in the electrodeposition process."