Macromolecules, Vol.27, No.14, 3859-3863, 1994
Anomalous Relaxation in Polychlorinated Biphenyl Polybutadiene Mixtures
The phenomenon of faster relaxation of small-molecule glass-forming liquids upon addition of a higher T(g) polymer is examined for mixtures of Aroclor 1248 (PCB) with poly(vinylethylene) (PVE). In this system the anomaly can be ascribed to the positive changes in volume on mixing. Contributions to the observed behavior from changes in local friction coefficient, as deduced from the coupling model of relaxation, exert a less obvious influence. This can be contrasted with prior results on mixtures of poly(methyl-phenylsiloxane) (PMPS) with the small-molecule glass former 1,1-bis(p-methoxyphenyl)cyclohexane (BMC).1,2 Despite a similarly anomalous solvent modification, the volume change upon mixing is negative therein. This suggests that changes in local friction, as inferred from comparison of the components’ noncooperative relaxation times, are a general mechanism contributing to the local dynamics in mixtures.
Keywords:FREE-VOLUME INTERPRETATION;SOLVENT DYNAMICS;SEGMENTAL RELAXATION;POLYMER-SOLUTIONS;AROCLOR SOLUTIONS;FRICTION;GLASS;ANTIPLASTICIZATION;POLYBUTADIENES;POLYISOPRENE