In this study, scanning electron microscopy and electrochemical techniques were used to investigate the effect of the Cu content on the microstructure and corrosion resistance of plasma electrolytic oxidation (PEO) coatings on Al–xCu alloys. The results showed that Cu in the substrate alloy was used to promote the intensity and the transformation process of the microdischarges, which led to the undulating-ribbon feature of cross-sectional morphologies. The formation of pores and cracks in the coatings was facilitated by the oxygen release due to the oxidation of O²⁻ and the dissolution of copper oxide. Meanwhile, the average porosity of PEO coatings distinctly increased with the increase in the Cu content, which is the key factor causing the decreased corrosion resistance of PEO coatings.

Reducing the loose-layer-to-dense-layer ratio in PEO coatings on aluminum and its alloys is the key to improving their corrosion resistance and expanding their applications in the aerospace industry and other fields. In this paper, we describe the discharge evolution during the PEO process in exhaustive detail and report the appearance of a novel “chain-like” discharge for the first time. We investigated the microstructure and composition of PEO coatings using a scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS) and an X-ray diffractometer (XRD). The results reflected that the coating composition changed from amorphous Al₂O₃ to crystalline γ-Al₂O₃ and α-Al₂O₃ phases with the evolution of the plasma spark discharge state. We evaluated the electrochemical behavior of the coatings using a potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. Under “chain-like” discharge, the icorr of the coating on Al was 8.564 × 10^–9 A∙cm⁻², which was five orders of magnitude lower than that of the sample without the PEO coating. Moreover, we evaluated the adhesion strength of the coatings at different stages using a pull-off test. The adhesion strength of the PEO coatings at stage V reached 70 MPa. Furthermore, the high content of α-Al₂O₃ increased the hardness of the coating to 2000 HV. Therefore, the “chain-like” discharge promoted the formation of a single dense layer with 2.8% porosity and that demonstrated excellent properties. We also propose a mechanism to explain the influence of the plasma spark discharge state on the microstructure and composition of the PEO coatings.