Incorporating Physics-Based Models into Equivalent Circuit Analysis of EIS Data from Organic Coatings

Electrochemical impedance spectroscopy (EIS) is a widely used method for monitoring coatings because it can be done in situ and causes little damage to the coating. However, interpreting the impedance data from coatings in order to determine the state of the coating and its protective abilities is challenging. A modified version of the rapid electrochemical assessment of paint (REAP) equivalent circuit is developed here, along with a method to calculate the impedance of a circuit using matrix algebra. This new equivalent circuit and the calculation method are used to analyze EIS data obtained from a two-layer commercial organic coating system immersed in NaCl solutions with different concentrations and at different temperatures. The matrix calculation method is validated by comparing results obtained from commercial analysis software to this method for two different equivalent circuits, and the parameter values are nearly equal. Physics-based models of the equivalent circuit elements are derived and used to obtain both initial estimates for the regressions and physics-based constraints on the model parameters. These models are integrated into the regression procedure, and the corrected Akaike information criterion (AICc) is used to compare fits between the new circuit and classic equivalent circuits. The AICc values indicate the new circuit results in better fits than classic equivalent circuits used for coatings analysis.