Electrostatic properties of PE and PTFE subjected to atmospheric pressure plasma treatment; correlation of experimental results with atomistic modeling

The use of an atmospheric pressure glow discharge (APGD) plasma was used at Kennedy Space Center (KSC) to increase the hydrophilicity of spaceport materials to enhance their surface charge dissipation and prevent possible electrostatic discharge (ESD) in spaceport operations. Significant decreases in charge decay times were observed after tribocharging the materials using the standard KSC tribocharging test. The polarity and amount of charge transferred was dependant upon the effective work function differences between the respective materials. In this study, PE and PTFE were exposed to a He+O2 APGD. The pre and post-treatment surface chemistries were analyzed by X-ray photoelectron spectroscopy and contact angle measurements. Semi-empirical and ab initio calculations were performed to correlate the experimental results with some plausible molecular and electronic structure features of the oxidation process. For the PE, significant surface oxidation was observed, as indicated by XPS showing C–O, C O, and O–C O bonding, and a decrease in the surface contact angle from 98.9° to 61.2°. For the PTFE, no C–O bonding appeared and the surface contact angle increased indicating the APGD only succeeded in cleaning the PTFE surface without affecting the surface structure. The calculations using the Parametric Method 3 (PM3) and Density Function Theory (DFT) methods were performed on single and multiple oligomers to simulate a wide variety of oxidation scenarios. Calculated work function results suggest that regardless of oxidation mechanism, e.g. –OH, O or a combination thereof, the experimentally observed levels of surface oxidation are unlikely to lead to a significant change in the electronic structure of PE and that its increased hydrophilic properties are the primary reason for the observed changes in its electrostatic behavior. The calculations for PTFE argue strongly against significant oxidation of that material, as confirmed by the XPS results.