Ag⁺ Interference from Ag/AgCl Wire Quasi-Reference Counter Electrode Inducing Corrosion Potential Shift in an...

Quantitative scanning micropipette contact method measurements are subject to the deleterious effects of reference electrode interference. The commonly used Ag/AgCl wire quasi-reference counter electrode in the miniaturized electrochemical cell of the scanning micropipette contact method was found to leak Ag⁺ into the electrolyte solution. The reduction of these Ag⁺ species at the working electrode surface generates a faradaic current, which significantly affects the low magnitude currents inherently measured in the scanning micropipette contact method. We demonstrate that, during the microscopic corrosion investigation of the AA7075-T73 alloy using the oil-immersed scanning micropipette contact method, the cathodic current was increased by the Ag⁺ reduction, resulting in positive shifts of corrosion potentials. The use of a leak-free Ag/AgCl electrode or an extended distance between the Ag/AgCl wire and micropipette tip droplet eliminated the Ag⁺ contamination, making it possible to measure accurate corrosion potentials during the oil-immersed scanning micropipette contact method measurements.