The Evidence of Cathodic Micro-discharges during Plasma Electrolytic Oxidation Process

TL;DR

This study investigates cathodic micro-discharges during plasma electrolytic oxidation of magnesium alloy, revealing their behavior, optical properties, and the influence of fluoride ions, advancing understanding of PEO coating mechanisms.

Contribution

It provides the first detailed analysis of cathodic micro-discharges in PEO, including optical emission spectroscopy and the role of fluoride ions, which was previously not well understood.

Findings

Cathodic micro-discharges exhibit collective intermittent behavior.

Electron density is approximately 10^15 cm^-3, and temperature around 7500 K.

F-anions influence the appearance of cathodic micro-discharges.

Abstract

Plasma electrolytic oxidation (PEO) processing of EV 31 magnesium alloy has been carried out in fluoride containing electrolyte under bipolar pulse current regime. Unusual PEO cathodic micro-discharges have been observed and investigated. It is shown that the cathodic micro-discharges exhibit a collective intermittent behavior which is discussed in terms of charge accumulations at the layer/electrolyte and layer/metal interfaces. Optical emission spectroscopy is used to determine the electron density (typ. 10 15 cm-3) and the electron temperature (typ. 7500 K) while the role of F-anions on the appearance of cathodic micro-discharges is pointed out. Plasma Electrolytic Oxidation (PEO) is a promising plasma-assisted surface treatment of light metallic alloys (e.g. Al, Mg, Ti). Although the PEO process makes it possible to grow oxide coatings with interesting corrosion and wear resistant properties, the physical mechanisms of coating growth are not yet completely understood. Typically, the process consists in applying a high voltage difference between a metallic piece and a counter-electrode which are both immersed in an electrolyte bath. Compare to anodizing, the main differences concern the electrolyte composition and the current and voltage ranges which are at least one order of magnitude higher in PEO 1. These significant differences in current and voltage imply the dielectric breakdown and consequently the appearance of micro-discharges on the surface of the sample under processing. Those micro-discharges are recognized as being the main contributors to the formation of a dielectric porous crystalline oxide coating. 2 Nevertheless, the breakdown mechanism that governs the appearance of those micro-discharges is still under investigation. Hussein et al. 3 proposed a mechanism with three different plasma formation processes based on differences in plasma chemical composition. The results of Jovovi{\'c} et al. 4,5 concerning physical properties of the plasma seem to corroborate this mechanism, and also point out the importance of the substrate material in the plasma composition. 6 Compared with DC conducted PEO process, using a bipolar pulsed DC or AC current supply gives supplementary control latitude through the current waveform parameters. The effect of these parameter on the micro-discharges behavior has been investigated in several previous works. 2,3,7,8 One of the main results of these studies is the absence of micro-discharge during the cathodic current half-period. 9-11 Even if the cathodic half-period has an obvious effect on the efficiency of PEO as well as on the coating growth and composition, the micro-plasmas appear only in anodic half-period. Sah et al. 8 have observed the cathodic breakdown of an oxide layer but at very high current density (10 kA.dm-${}^2$), and after several steps of sample preparation. Several models of micro-discharges appearance in AC current have already been proposed. 1,2,8,12,13 Though cathodic micro-discharges have never been observed within usual process conditions, the present study aims at defining suitable conditions to promote cathodic micro-discharges and at studying the main characteristics of these micro-plasmas.