Additonal authors: Fiset, E.. Book title: Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019. Chapter: . Chapter title:
Arsenic (As), bismuth (Bi) and antimony (Sb) are known to affect the quality of copper deposits in copper electrowinning operations. The codeposition of As was previously believed to occur only at current densities far exceeding the range of typical current densities for copper electrowinning. In this study, we investigate the copper electrodeposition on different pretreated stainless steel (SS) substrates from bleed electrolyte in galvanostatic mode at –45 mA/cm². Scanning electron microscopy (SEM) micrographs illustrate that during the initial phases of copper nucleation and growth, the current density was locally increased due to the pretreatments. It was reasoned that the codepostion of As could possibly occur in normal electrowinning conditions, but the risk can be substantially reduced by good SS substrate handling and maintenance practices.
The presence of As, Bi and Sb is known to have a deleterious effect on the copper cathode quality in copper electrowinnings (Hiskey & Maeda, 2003; Hoffmann, 2004; Xiao, Cao, Shen, & Volinsky, 2012; Xiao, Cao, Mao, Shen, & Ren, 2014; Jafari et al., 2017). They are known to influence both the chemical and physical quality of the copper as they can contaminate the copper (Jafari et al., 2017) and affect the copper deposit structure (Hiskey & Maeda, 2003; Kim, Kim, & Chung, 2009), which contributes to a degraded market value of the copper (Tuddenham, 1984). The incorporation mechanisms of these impurities are believed to occur mainly through slime inclusion (F. Xiao et al, 2012) and electrolyte inclusion (Hiskey & Maeda, 2003). Other studies suggested that codeposition of these impurities is possible by their standard reduction potential being close to the one of copper (Xiao et al, 2014). Hiskey and Maeda (2003) investigated the copper electrodeposition on a copper electrode substrate in Cu electrolytes with a Cu, H2SO4, As, Bi, Sb composition representative for commercial copper tankhouses. The combination of voltammographic techniques and Auger electron spectroscopy showed that As was the first impurity to be electrodeposited from this electrolyte, yet at potentials where the limiting current density of the copper electrodeposition reaction is exceeded. The copper tankhouses usually operate at a current density ratio of 0.3 to the limiting current density in order to achieve tolerable copper quality deposits. The codeposition of As could be considered impossible in this current density condition. However, it is known that during the initial phases of electrodeposition on foreign substrates, a substantial part of the reaction proceeds by growth of individual nuclei where the current density is locally high and diffusion limited (Radisic, Ross, & Searson, 2006). Furthermore, it was observed that copper nucleation on TiO substrates occurred preferentially in the scratched oxide free areas which could serve as parts with high localized current densities (Chang, Choe, & Lee, 2005).