Penetrant-Induced Glass-like Transition in Thin Chitosan Films.

We present the water vapor-induced swelling and the emergence of a penetrant-induced glass-like transition in the substrate-supported glassy chitosan thin films. The time evolution of the film thickness under different levels of relative humidity conditions is measured in real-time using a spectroscopic ellipsometer equipped with a humidity cell. In a dry film, the network of chitosan chains is in a glassy state, and upon exposure to water vapor, initially, the film swells by Fickian diffusion of water molecules, which triggers the structural relaxations of the chains. Under higher humidity conditions, a relatively slower evolution of thickness succeeds the initial rapid swelling due to the non-Fickian sorption of water molecules. The swelling characteristics of the polymer films are accounted for by considering the diffusion-relaxation mechanism of chains in the presence of smaller penetrant molecules. The penetrant-induced glass-like transition (Pg), where the polymer film isothermally transits from a glassy to a rubbery state, is determined for pristine and cross-linked chitosan films. Pg is determined from the abrupt change in the rate of swelling observed upon increasing the relative humidity. Chemical crosslinking has an evident influence on the penetrant-induced glass-like transition of the chitosan films. Pg was found to rise sharply for stiffer films with higher cross-linking density.