Investigation of Nucleation and Plating Overpotentials during Copper Electrowinning Using the Galvanostatic Staircase Method

"The Winand Diagram was developed and has been used for decades to illustrate the interaction between polarization, mass transport and inhibition on the resulting structure of a metal electrodeposit. Recently, Adcock et al. criticized the Winand Diagram and developed their own structural diagram based on nucleation and plating overpotentials. Their work was based on zinc electrodeposition using a galvanostatic staircase method. This work explores the nucleation and plating overpotentials for copper electrodeposition using conditions typical for primary electrowinning and the galvanostatic staircase experimental technique. Additionally, the effects of organic additives and plating substrate on these overpotentials are reported.IntroductionThe control of electrodeposited structures is critically important to modem electrometallurgy operations to insure proper quality and efficient energy use. Electrodeposition of base metals for primary recovery (e.g. electrowinning or electrorefining), while similar to plating for decorative or device manufacturing, differs in the need to produce deposits that cover large areas and grow to significant thickness. Thus, controlling nucleation and particularly growth of electrodeposits is critically important for base metal electrometallurgical operations.The control of nucleation and growth on an industrial scale is most influenced by five parameters - current density, temperature, metal concentration, electrolyte agitation and additives. The effects of these parameters on electrodeposition are interrelated. To describe their effects on the type ofelectrodeposits generated and provide practitioners with a useful tool, Winand developed what is known as the Winand Diagram [1-2]. An adapted version of the Winand Diagram is shown in Figure 1.Winand characterized electrodeposits using Fischer's classification [3] and plotted the various deposit types versus inhibition on a vertical axis and the ratio of current density to bulk metal concentration on the horizontal axis. Inhibition intensity is a complex parameter and is still not well understood even though Fischer introduced the term in 1960 [4]. Often, inhibition intensity is simplified to equal the concentration of organic additive at the deposit surface and is related to the inverse of the exchange current density of the metal being deposited. The ratio of current density to bulk metal concentration is used to represent the ratio of crystallization overvoltage to mass transport of the depositing ion. As such i/iL could also be along the horizontal axis, where iL is the limiting current density of the electrodeposition reaction."