This study demonstrates a significant improvement of the corrosion resistance of an AZ31B magnesium alloy achieved by the application of 1 μm-thin coatings generated by an environmentally friendly flash plasma electrolytic oxidation (FPEO) process in Ca-containing electrolytes. Two compounds with different solubility, calcium oxide (CaO) or calcium glycerophosphate (CaGlyP), were used as sources of Ca in the electrolyte. Very short durations (20–45 s) of the FPEO process were employed with the aim of limiting the energy consumption. The corrosion performance of the developed coatings was compared with that of a commercial conversion coating (CC) of similar thickness. The viability of the coatings in a full system protection approach, consisting of FPEO combined with an inhibitor-free epoxy primer, was verified in neutral salt spray and paint adhesion tests. The superior corrosion performance of the FPEO_CaGlyP coating, both as a stand-alone coating and as a full system, was attributed to the formation of a greater complexity of Ca²⁺ bonds with SiO₂ and PO₄³⁻ species within the MgO ceramic network during the in situ incorporation of Ca into the coating from a double chelated electrolyte and the resultant difficulties with the hydrolysis of such a network. The deterioration of the FPEO_CaGlyP coating during immersion was found over ten times slower compared with Ca-free flash-PEO coating.

Layered double hydroxide (LDHs) coatings were developed for the corrosion protection of AZ31 Mg alloy. AZ31 is widely used in the transport industry due to its low mass density and good mechanical properties. LDH coatings were fabricated under co-precipitation conditions and applied under hydrothermal conditions. Two different systems Zn-Al LDH and Li-Al LDH were studied. Specimens were post-treated via immersion for 2 h at 45 °C in inhibitor aqueous baths. Na₂WO₄·H₂O and LiNO₃ inorganic inhibitors were used, respectively, to produce inhibitor-loaded systems: Zn-Al LDH(W) and Li-Al LDH(Li). The characterization of the coatings was carried out by field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The corrosion process was studied by electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET). The surface was also evaluated via the determination of water drop contact angle and the performance of a paint adhesion test using an epoxy primer. The characterization of the coating revealed two-layered coatings with a denser inner layer and a flaky outer layer. Both coatings improved the corrosion resistance of the AZ31 alloy. Loading with inhibitor further increased the corrosion resistance by one order of magnitude (bare substrate, Z_10mHz~10² Ω cm²; LDH, Z_10mHz~10^3–4 Ω cm²; LDH-inhibitor, Z_10mHz~10⁵ Ω cm²).