Plasma electrolytic oxidation coatings were prepared in aluminate, phosphate, and silicate-based electrolytic solutions using a soft-sparking regime in a multi-frequency stepped process to compare the structure, corrosion, and wear characteristics of the obtained coatings on AZ31 magnesium alloy. The XRD results indicated that all coatings consist of MgO and MgF₂, while specific products such as Mg₂SiO₄, MgSiO₃, Mg₂P₂O₇, and MgAl₂O₄ were also present in specimens based on the selected solution. Surface morphology of the obtained coatings was strongly affected by the electrolyte composition. Aluminate-containing coating showed volcano-like, nodular particles and craters distributed over the surface. Phosphate-containing coating presented a sintering-crater structure, with non-uniform distributions of micro-pores and micro-cracks. Silicate-containing coating exhibited a scaffold surface involving a network of numerous micro-pores and oxide granules. The aluminate-treated sample offered the highest corrosion resistance and the minimum wear rate (5 × 10⁻⁵ mm³ N⁻¹ m⁻¹), owing to its compact structure containing solely 1.75% relative porosity, which is the lowest value in comparison with other samples. The silicate-treated sample was degraded faster in long-term corrosion and wear tests due to its porous structure, and with more delay in the phosphate-containing coating due to its larger thickness (30 µm).

Plasma electrolytic oxidation (PEO) coatings were grown on AZ31 Mg alloy in a silicate-based electrolyte containing KF using unipolar and bipolar (usual and soft-sparking) waveforms. The coatings were dual-layered consisting of MgO, MgF₂ and Mg₂SiO₄ phases. Surface morphology of the coatings was a net-like (scaffold) containing a micro-pores network, micro-cracks and granules of oxide compounds. Deep pores were observed in the coating produced by unipolar and usual bipolar waveforms. The soft-sparking eliminated the deep pores and produced the lowest porosity in the coatings. It was found that the corrosion performance of the coatings evaluated using EIS in 3.5 wt. % NaCl solution is mostly determined by the inner layer resistance, because of its higher compactness. After 4 days of immersion, the inner layer resistances were almost the same for all coatings. However, the coatings produced by unipolar and usual bipolar waveforms showed sharp decays in inner layer resistances after 1 week and even the barrier effect of outer layer was lost for the unipolar-produced coating after 3 weeks. The low-frequency inductive loops appeared after a 3-week immersion for all coatings indicated that the substrate was under local corrosion attack. However, both coatings produced by soft-sparking waveforms provided the highest corrosion performance.

In this research, plasma electrolytic oxidation (PEO) coatings were prepared on 7075 Al alloy in a silicate-based solution with Na₂MoO₄ additive using a unipolar waveform at constant current density. The coatings displayed micro-pores, micro-cracks, pancake-like and crater-like features, and also solidified molten oxide particles on the surface. The coatings were majorly composed of Al₂O₃ (γ, δ, and α), SiO₂ (amorphous), and MoO₃ phases, which confirms the incorporation of molybdenum in the case of additive-containing coatings. Molybdenum species were transported through cracks, channels, and micropores, as the ready access pathways into the coating and partly sealed the coating pores. The EIS technique was used to evaluate the long-term corrosion performance of the coatings up to 168 h of immersion in 3.5 wt.% NaCl solution. The results showed that the barrier action of the PEO coatings was highly enhanced by adding Na₂MoO₄ due to the higher resistance that alumina achieved to chlorine absorption and also its higher stability by the incorporation of MoO₃. The coating formed in the presence of 5 g L⁻¹ Na₂MoO₄ showed the highest thickness and the lowest porosity percent (15.15%), which provided the highest corrosion performance at long immersion times.