Convergence of Levenberg-Marquardt Estimates of Nonlinear Parameters in EIS Analysis of Coated Aluminum Panels

Abstract

Equivalent circuit models are frequently employed to analyze electrochemical impedance spectroscopy (EIS) data. However, aside from some simple cases in which the equivalent circuit element parameters can be estimated directly from a plot of the data, the parameters for each of the equivalent circuit elements must often be estimated through the implementation of a nonlinear least-squares regression method. One frequently-used approach is the powerful Levenberg-Marquardt algorithm. This algorithm functions as a damped least-squares method that performs an interpolation between the steepest-descent and the Gauss-Newton methods for estimating nonlinear parameters. However, there are several challenges to using a Levenberg-Marquardt algorithm to model EIS data. The nonlinear nature of the impedance equations along with the difference in the magnitude of the parameter values can result in the algorithm failing to converge to a local minimum in the parameter space. This convergence challenge can be seen in determining equivalent circuit values for undamaged coating systems that have a high pore resistance, a small capacitance, as well as contributions from the underlying metal substrate. A Levenberg-Marquardt algorithm, along with a heuristic approach to use the raw data to improve the initial parameter estimates, is implemented that provides an improved approach for nonlinear regression fits of equivalent circuit models. A comparison of three equivalent circuit models fits, with residuals, for a two-layer coating system on an aluminum substrate is shown in the attached figure.Figure caption: Plot of EIS data (+ symbols) from a cured coating system prior to any environmental exposures compared with 3 equivalent circuit model fits (solid lines). The model fits were obtained using an NRL-developed Levenberg-Marquardt nonlinear regression fitting routine.The Department of Defense Strategic Environmental Research and Development Program (SERDP) sponsored this project under work unit 5399. The views and conclusions contained herein are those of the authors and should not be interpreted as necessarily representing the official policies or endorsements, either expressed or implied, of the Office of Naval Research, the U.S. Navy, the Department of Defense, or the U.S. government. Figure 1