Modification and functionalization of polymer surface properties is desired in numerous applications, and a standard technique is a treatment with non-equilibrium gaseous plasma. Fluorinated polymers exhibit specific properties and are regarded as difficult to functionalize with polar functional groups. Plasma methods for functionalization of polyvinylidene fluoride (PVDF) are reviewed and different mechanisms involved in the surface modification are presented and explained by the interaction of various reactive species and far ultraviolet radiation. Most authors used argon plasma but reported various results. The discrepancy between the reported results is explained by peculiarities of the experimental systems and illustrated by three mechanisms. More versatile reaction mechanisms were reported by authors who used oxygen plasma for surface modification of PVDF, while plasma sustained in other gases was rarely used. The results reported by various authors are analyzed, and correlations are drawn where feasible. The processing parameters reported by different authors were the gas pressure and purity, the discharge configuration and power, while the surface finish was predominantly determined by X-ray photoelectron spectroscopy (XPS) and static water contact angle (WCA). A reasonably good correlation was found between the surface wettability as probed by WCA and the oxygen concentration as probed by XPS, but there is hardly any correlation between the discharge parameters and the wettability.
Keywords: activation; functionalization; gaseous plasma; polyvinylidene fluoride; surface modification; wettability.