Examination of Copper Electrowinning Smoothing Agents. Part IV: Nucleation and Growth of Copper on Stainless Steel

"Nucleation and growth of copper on 316L stainless steel from synthetic acidified copper sulfate was studied in the absence and presence of chloride ions and/or organic additives – HydroStar® 4208, DXG-F7® and Cyquest® N-900 – using a potentiostatic technique. The current–time data obtained at 0.16V versus the SHE were analyzed using nucleation and growth models. Scanning electron microscope (SEM) images of deposits produced at 300 A/m2 show that the addition of 20 mg/L chloride ions increased the size and reduced the number of copper nuclei. Potentiostatic current–time data from the electrolyte without organic additives, and confirmed by SEM images, indicate progressive nucleation with two-dimensional growth under diffusion control. None of the organic additives studied at a concentration of 2.5 mg/L with 20 mg/L chloride changed the nucleation and growth mechanism, but the additives increased the number and reduced the size of copper nuclei, leading to more uniform coverage of the stainless steel substrate.IntroductionElectrowinning of copper is an important process in the manufacture of high-purity copper metal. Approximately 20 percent of the world’s refined copper is produced from acidified copper sulfate solutions by electrowinning (Schlesinger, Sole and Davenport, 2011). In many plants, copper is electrodeposited on AISI 316L stainless steel substrates for a period of 6-7 days, after which the copper is stripped from the blanks. Even though the deposition time for a commercial copper electrowinning circuit is around one week, it is critically important to control the nucleation, growth and nature of the initial deposit (Sun and O’Keefe, 1992).Deposit morphology and structure are influenced by the real current density at the electrode surface. The real current density across the cathode surface is made uniform by proper design of the electrowinning cell and electrodes and careful operational practice. Even with good design and control, some current maldistribution occurs. The outcome of severe current maldistribution is poor deposits that affect product quality and/or increase energy consumption. To combat current maldistribution and create a larger operating window in terms of current density, temperature and copper concentration, small amounts of organic smoothing agents – traditionally, guar products – are added to copper electrowinning electrolytes. Moreover, these additives inhibit the growth of copper nodules and lead to improved deposit quality by producing bright, smooth and dense cathodes.Recently, the use of polysaccharides, such as HydroStar 4208 and DXG-F7, and polyacrylamides, such as Cyquest N-900, has been reported in commercial electrowinning tankhouses as replacements for guar (Ashford, Clayton and Sandoval, 2012; Robinson et al., 2013; Sandoval, Morales and Bernu, 2010). However, little information has been published on the effect of these new organic additives, especially regarding the nucleation and growth mechanisms of copper electrodeposits in their presence."