Quantitative Interpretation of Potentiodynamic Polarization Curves Obtained at High Scan Rates in Scanning Electrochemical Cell Microscopy

Anal Chem. 2024 Sep 10. doi: 10.1021/acs.analchem.4c01476. Online ahead of print.

Abstract

Scanning electrochemical cell microscopy is becoming the tool of choice for the investigation of localized metal corrosion. Typically, potentiodynamic polarization measurements in scanning electrochemical cell microscopy are performed at high potential scan rates. However, Tafel extrapolation applied to high-scan-rate potentiodynamic polarization curves would yield inaccurate corrosion kinetics due to the interference of double-layer charging current or mass transport of species in the metal oxide. Instead, the high field model was used to simulate the potentiodynamic polarization curves of pure aluminum at 25, 50, 100, and 200 mV/s in neutral and acidic phosphate solutions, thus enabling quantitative analysis of local corrosion kinetics by fitting the potentiodynamic polarization curve.