Effect of pH on the Grain Size Dependence of Magnesium Corrosion

Prior works show that grain size can play a role in the corrosion of a metal; however, such works are nominally executed in a single electrolyte/environment at a single pH. In this work, the anodic and cathodic reaction kinetics of pure Mg specimens with grain sizes ranging from approximately 8 μm to 590 μm were compared as a function of pH in 0.1 mol dm⁻³ sodium chloride (NaCl) electrolytes using anodic polarization experiments and an in situ scanning vibrating electrode technique (SVET). Anodic polarization experiments showed that grain size is important in determining overall electrochemical response, but the environment dictates the form of the grain size vs. corrosion rate relationship (i.e., pH is the overall controlling factor). Consequently, the role of grain size upon corrosion cannot be fully assessed unless a variation in environment is simultaneously studied. For example, the anodic reaction, which dictates active corrosion, also dictates passivation, so the corrosion rate vs. grain size relationship has been shown to “flip” depending on pH. Further, SVET analysis of unpolarized Mg immersed in 0.1 mol dm⁻³ NaCl electrolyte at neutral pH showed that breakdown of passivity of cast Mg occurred after ~1 h immersion, giving filiform-like corrosion tracks. The front edges of these corrosion features were revealed as intense local anodes, while the remainder of the dark-corroded Mg surface, left behind as the anodes traversed the surface, became cathodically activated. In contrast, grain-refined Mg samples were significantly less susceptible to localized corrosion, and breakdown was not observed for immersion periods of up to 24 h.