Conformational Entropy Contributions to the Glass Temperature of Blends of Miscible Polymers

Because of negligible contributions of combinatorial entropy, miscibility of polymers is attributed predominantly to favorable (exothermic) enthalpic effects of mixing, i.e., to strong interactions between the blend components, which have to overcome the cohesive forces acting within the components. Miscibility of amorphous polymers usually is associated with the presence of a single glass temperature of the blend. Although stronger hetero-contact interactions are thermodynamically required for polymer miscibility, the majority of miscible binary polymer blends exhibit negative deviations of the glass temperature from values predicted by the free volume or flexible bond additivity rules, suggesting a looser packing within those blends. A reasonable explanation assumes that binary hetero-contact formation within the blend may be accompanied by local interchain orientation contributing consequently to conformational entropy changes. The smaller the induced interchain orientation by hetero-contact formation, the larger the mobility in the neighborhood of the contacts and the probability of related conformational entropy changes, causing an equivalent increase of the "free volume" within the blend, i.e., a corresponding decrease of the blend Tg, which finally can be situated below the values predicted by the additivity rules. Vice versa, the corresponding argument will hold for blends with higher interchain orientation induced by intensive exothermic hetero-contact forces.