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Savin, Daniel A.
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article
Effect of Composition on the Width of the Calorimetric Glass Transition in Polymer-Solvent and Solvent-Solvent Mixtures
Abstract
<p>The calorimetric glass-transition temperature (T<sub>g</sub>) and transition width were measured over the full composition range for solvent-solvent mixtures of o-terphenyl with tricresyl phosphate and with dibutyl phthalate and for polymer-solvent mixtures of polystyrene with three dialkyl phthalates. T<sub>g</sub> shifted smoothly to higher temperatures with the addition of the component with the higher T<sub>g</sub> for both sets of solvent-solvent mixtures. The superposition of the differential scanning calorimetry traces showed almost no composition dependence for the width of the transition region. In contrast, the composition dependence of T<sub>g</sub> in polymer-solvent mixtures was different at high and low polymer concentrations, and two distinct T<sub>g</sub>'s were observed at intermediate compositions. These results were interpreted in terms of the local length scale and associated local composition variations affecting T<sub>g</sub>. The possible implications of these results for the dynamics of miscible polymer blends were examined.</p>