Modulation of Copper Cathodes by Electrorefining Addition Aoents Thiourea, Glue and Chloride ION

Spontaneous nodulation leading to growth of well developed glossy spheroids (generally hemispheres) of up to 0.06 cm width in 120 min has been observed during copper electrodeposition with certain levels of glue, thiourea and C1-. Thiourea alone can produce spontaneous nodulation but addition of glue and/or Cl- is required for rapid and sustained growth. In most cases once the glossy nodules develop they consume the majority of the copper deposited; thus, the specific current densities (and hence copper electrodeposition rates) on the glossy nodules are about an order of magnitude or, more greater than on the adjacent planar surfaces. The texture of the adjaoent planar surfaces is not glossy in appearance but is well faceted showing the usual deposition grain structure for such additives. Cathode potentials when spontaneous nodulation occurs are about TOO my more negative than with usual copper electroplating. This fact associated with evidence of extremely high levels of cathode surface passivation based on cyclic voltammograms indicates that the conditions which lead to spontaneous nodulation result from a very tightly adsorbed additive surface film. This film breaks down in specific points initiating the glossy nodules which then grow at extremely rapid rates. Current density is also important in spontaneous nodulation. At equal deposition times a current density of 21.5 mA/cm produced much larger glossy nodules than at 48 mA/cm2. The surface concentration of the glossy nodules was much greater in the latter case, however. The role of current density is still not well understood. The role of it as well as the relative roles of the three additives, thiourea, glue and Cl- in spontaneous nodulation is presented. Preliminary results and some possible correlations of these to help explain spontaneous nodulation are presented. It is believed that tankhouse upsets where cathode nodulation occurs may be related to this phenomenon.