Study on initiation of localised corrosion on copper thin film electrode by combinational use of an EQCM with a liquid-phase ion gun

A new method allowing simultaneous measurements of anodic currents and small mass changes during initiation and early growth of a single localised corrosion site was discussed. An electrochemical quartz crystal microbalance (EQCM) was combined with a liquid-phase ion gun consisting of an Ag/AgCl microelectrode which produces chloride ions, causing local breakdown of passive film and pit growth. The method was applied to copper thin films polarised anodically at 0.6 or 0.8 V (SHE) in pH 8.4 borate buffer solution. It was found from comparison between coulometry and gravimetry that copper dissolves as Cu²⁺ during the pit growth. The shape of the pit was almost circular and the average pit current density, i_p=25 A cm⁻² was evaluated from the kinetics of 2D pit growth.