Influence of Experimental Parameters on the Determination of Copper Dissolution in Corrosion Processes Using Gold Microelectrodes ^†

In situ electrochemical imaging of corrosion reactions is performed directly by scanning electrochemical microscopy (SECM) in generation-collection mode. This method involves redox conversion of soluble metal ions at the amperometric tip for quantification. Unfortunately, many metals, such as copper, do not undergo redox conversion to a soluble state and are deposited on the SECM tip. They therefore modify the electrochemical behavior of the tip and require consideration of metal stripping processes. In addition, the miniaturization of the electrode to operate as a microelectrode tip can be accompanied by variations in the potential range and distribution of the redox processes related to copper deposition and redissolution, thus complicating the adequate choice of electrochemical conditions applied to the tip for the unambiguous operation of SECM in the generation-collection mode to study the corrosion of copper-based materials. Therefore, in this work, a study of different parameters for the amperometric determination of Cu²⁺ ions was conducted using gold disk electrodes of 500 and 10 μm diameter to represent the typical sizes employed in conventional and scanning microelectrochemical measurements. The investigation was performed to analyze the effect of underpotential deposition (UPD) and overpotential deposition (ODP) on the voltammetric characteristics of copper deposition and redissolution resulting from variations in the solution composition, i.e., the nature of anions and pH. The dependence and limits of the reduction and reoxidation waves were analyzed as functions of the Cu²⁺ ion concentration, the ionic strength of the electrolyte, and the pH of the solution. The results were interpreted as UPD and OPD. Under conditions close to the marine environment, the release of Cu²⁺ ions can be unambiguously detected and quantified from potentials above −0.1 V vs. Ag/AgCl.