Examination of Copper Electrowinning Smoothing Agents. Part III. Chloride interaction with HydroStar and Cyquest N-900

"Chloride ions and their interactions with two organic smoothing additives – Cyquest® N-900 and HydroStar® 4208 – during copper electrodeposition were explored using cyclic voltammetry and electrochemical impedance spectroscopy. The results revealed that chloride ions, up to a concentration of 40 mg/L, depolarized the copper deposition reaction. A combination of chloride ions and Cyquest N-900 inhibited the depolarization reaction during copper electrodeposition. It is proposed that the chloride ions acted as bridging ligands between copper and Cyquest N-900. Addition of HydroStar at a concentration of 2.5 mg/L depolarized the copper deposition reaction when no chloride ions were present. This behavior did not change with the addition of chloride ions at the concentrations tested, indicating that chloride ions and the polysaccharide do not interact.IntroductionElectrowinning is a major production method used to obtain high-purity copper. In modern tankhouses, copper is electrodeposited onto stainless steel blanks and then stripped, washed and bundled for delivery. Significant improvements in the quality of electrowon copper have been made over the last few decades. Additives, temperature, current density, electrolyte concentrations and agitation are known to influence the quality of copper electrodeposits (Jenkins and Eamon, 1990).The influence of chloride and organic additives on copper electrodeposition has been the subject of considerable research. The addition of small quantities of chloride and organic additives has been recognized to significantly improve the properties of copper electrodeposits. These additives are critical in the prevention of dendrite growth and the production of smooth, dense cathode deposits.Chloride ions have been reported to catalyze the copper reduction reaction and assist in the production of uniform deposits (Lakshmanan et al., 1977; Sun and O’Keefe, 1992). Moreover, it is generally agreed that chloride ions depolarize the copper deposition process at low (several millimolar) chloride concentrations. This is because chloride ions catalyze the reduction of copper (II) ions to copper (I) ions (Cu2+ ? Cu+ + e-) in the rate-limiting step of this process (O’Keefe and Hurst, 1978; Ilgar and O’Keefe, 1997; Hebert, 2005; Shao, Pattanaik and Zangari, 2007)."