Exploring the kinetics of switchable polymer surfaces with dynamic tensiometry

Abstract

Switchable polymer multilayer coatings consisting of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) were prepared via Layer-by-Layer (LbL) assembly and post-functionalized with poly(ethylene glycol methyl ether) (PEG). This resulted in a soft polar coating that reversibly and repeatedly rearranges from hydrophobic to hydrophilic (or vice versa) when contacted with water (or air). Goniometry is used to quantify the forward surface rearrangement in the form of transient measurements of the water contact angle. By examining the time evolution of the water contact angle at various temperatures, the apparent activation energy for the forward surface rearrangement (E_a,f) can be determined. Further insight can be gained into the kinetics of this surface reconstruction process by utilizing dynamic tensiometry to measure the evolution in the contact angle of a liquid meniscus at several rates and temperatures as it advances or recedes over the multilayer films. A simple first-order thermally-activated rate process is shown to describe the forward and reverse surface reconstruction and enables the shape of the measured tensiometric force curves during repeated immersion and emersion to be predicted quantitatively. Using this model we show that the character of this switchable surface coating can appear to be hydrophobic or hydrophilic depending on a single dimensionless parameter which incorporates the characteristic time-scale for temperature-dependent surface rearrangement, the speed of immersion and the capillary length of the liquid meniscus.