Frequency Response Evaluation as Diagnostic and Optimization Tool for Pulsed Unipolar Plasma Electrolytic Oxidation Process and Resultant Coatings on Zirconium.

This study aims to bridge various diagnostic tools for the development of smart plasma electrolytic oxidation (PEO) technologies. PEO treatments of commercially pure Zr were carried out using the pulsed unipolar polarisation (PUP) regime with frequency sweep in an alkaline phosphate-silicate electrolyte. Methods of in situ impedance spectroscopy and electrical transient analysis were used for the process diagnostics under the video imaging of the PEO. Two cutoff frequencies, 170-190 Hz and 620-650 Hz, were identified for the PEO-assisted charge transfer process. An equivalent circuit for the metal-oxide-electrolyte system under PUP PEO conditions was developed; from the capacitance values, two geometrical dielectric barriers were evaluated: a thinner 0.5-1 µm inner layer of the coating and a thicker 4-6 µm outer layer. These estimates were in agreement with the coating cross-sectional morphology. Based on comparing the results obtained using different techniques, the frequencies at which the uniform coatings with the best protective properties were formed were identified. For the selected electrolyte system and polarisation regime, these frequencies ranged from 2 to 5 kHz where the overall circuit reactance was minimal; therefore, the power factor was as close to one as possible. This opens the possibilities for the optimization of the pulsed PEO process and online control of unobservable surface characteristics, e.g., the thickness of the coating layers, thus contributing towards the development of smart PEO technologies.