Water desorption from a confined biopolymer.

We study desorption of water from a confined biopolymer (chitosan thin films) by employing temperature dependent specular X-ray reflectivity and spectroscopic ellipsometry. The water desorption is found to occur via three distinct stages with significantly different desorption rates. The distinct rates of water desorption are attributed to the presence of different kinds of water with disparate mobilities inside the biopolymer film. We identify two characteristic temperatures (Tc1 and Tc2) at which the water desorption rate changes abruptly. Interestingly, the characteristic temperatures decrease with decreasing the film thickness. The thickness dependence of the characteristic temperature is interpreted in the context of a higher mobility of polymer chains at the free surface for polymers under one-dimensional confinement.

Stratification and two glass-like thermal transitions in aged polymer films.

Using X-ray reflectivity, spectroscopic ellipsometry and Raman spectroscopy, we have studied the stratified structure and the two glass-like thermal transitions in sufficiently aged glassy polystyrene films. We find that favorable interaction between the solid substrate and the polymer film induces stratification within the film resulting in different densities across the film thickness. Existence of two glass-like thermal transitions (one at 70 °C and the other at 95 °C) is independently confirmed by temperature dependent spectroscopic ellipsometry and Raman spectroscopy measurements. Interestingly, the thermal coefficient of expansion of the polymer film displays anomalous behavior with temperature and is found to have the lowest value over the temperature range 70-95 °C, i.e. between the two observed glass-like thermal transition temperatures.