Deterministic chaos in the pitting phenomena of passivable alloys

It was shown that electrochemical noise recorded in stable pitting conditions exhibits deterministic (even chaotic) features. The occurrence of deterministic behaviors depend on the material/solution severity. Thus, electrolyte composition ([Cl-]/[NO3-] ratio, pH), passive film thickness or alloy composition can change the deterministic features. Only one pit is sufficient to observe deterministic behaviors. The electrochemical noise signals are non-stationary, which is a hint of a change with time in the pit behavior (propagation speed or mean). Modifications of electrolyte composition reveals transitions between random and deterministic behaviors. Spontaneous transitions between deterministic behaviors of different features (bifurcation) are also evidenced. Such bifurcations enlighten various routes to chaos. The routes to chaos and the features of chaotic signals allow to suggest the modeling (continuous and discontinuous models are proposed) of the electrochemical mechanisms inside a pit, that describe quite well the experimental behaviors and the effect of the various parameters. The analysis of the chaotic behaviors of a pit leads to a better understanding of propagation mechanisms and give tools for pit monitoring. (author)