Using recurrence plots for the analysis of the nonlinear dynamical response of iron passivation-corrosion processes

Recurrence plots (RPs) and recurrence quantification analysis (RQA) are used in this work to study different nonlinear dynamical regimes emerging in an electrochemical system, namely, the electrodissolution-passivation of iron in chloride-containing sulfuric acid solutions. Current oscillations at different applied potentials and chloride concentrations exhibit bifurcations from periodic to complex (bursting) periodic and aperiodic or chaotic behaviors, associated with different dissolution states of iron. The clarification of these transitions is essential to understand the type of corrosion (uniform or localized) taking place as well as the underlying mechanisms governing the stability of the metal. The RQA reveals that the predictability of the chloride-perturbed Fe|0.75M H₂SO₄ system strongly depends on the chloride concentration and the applied potential. At relatively low chloride concentrations, RQA measures, based on vertical and diagonal structures in RPs, display a decrease upon the breakdown of the passivity on iron and the initiation of localized corrosion (pitting). Phases of pitting corrosion (propagation/growth and unstable pitting) that followed pit initiation are discerned by keen changes of complexity measures upon varying the applied potential. At higher chloride concentrations, the evolution of RQA measures with the potential signifies a transition from the passive-active state dissolution to the polishing state dissolution of iron inside pits. The increase of the applied potential at late stages of pitting corrosion increases the nonlinear correlations and thus the complexity of the system decreases, which corroborates the RQA.