Understanding the pH effect on the magnesium corrosion by means of electrochemical impedance spectroscopy
Résumé
The corrosion mechanism of magnesium has been the subject of several papers, aiming to explain all the reported phenomena occurring at the Mg/electrolyte interface in general, and the negative difference effect (NDE) particularly [1]. In fact, this phenomenon consists on an increase of the hydrogen evolution rate with anodic polarization [2]. On this aspect, many mechanisms have been proposed including the uni-positive Mg+ ion mechanism [3], the magnesium hydride (MgH2) model [4], the partially protective surface film model [5], the incomplete film univalent Mg+ ion mechanism [6], the adsorptive univalent Mg+ ion dissolution model [7], and the Mg*H/Mg*OH catalysts model [8].
In this work, the pH effect on the corrosion of magnesium, at the early stages, was investigated using electrochemical impedance spectroscopy (EIS). A special attention has been paid to the low frequency (LF) inductive loops. Indeed, it is shown that depending on the pH value in acidic solution, one or two inductive time-constant can be observed (Fig. 1). On the basis of the obtained results, a model was established in view of understanding the elementary steps involved in the Mg corrosion mechanism and the impact of the pH on the kinetics of the different reactions. Interestingly, it is shown that a single mechanism can describe the corrosion behavior in the acidic to slightly alkaline pH domain (1.8 – 7.7) and that the presence of multiple LF time-constants is also to be linked to the thin oxide film present on the Mg surface.
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