X-RAY PHOTOELECTRON-SPECTROSCOPY STUDY OF ARGON-PLASMA-TREATED FLUOROPOLYMERS

Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether(approximate to 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to approximate to 0.10, and from 0.012 to approximate to 0.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C-1s, spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximate to 285 - 290 eV) representing various CH, CC, CO, CN, and CF functionalities.