Crossover region and entanglement in nearly monodisperse poly(ethyl acrylates) studied with electron spin resonance spectroscopy

Abstract

The topic of dynamic changes undergone by glass-forming materials in the supercooled region is addressed in this study. Crossover regions and temperatures are generally considered as key features in order for the glass transition phenomenon to be understood. The attention is here focused on the crossover region of polymers and its dependence on the polymeric entangled dynamics. To avoid the superposition of possible dependence on the polymeric polydispersity, nearly monodisperse syntheses of poly(ethyl acrylates) have been used. Rotational dynamics have been investigated with electron spin resonance spectroscopy, dissolving the cholestane molecular tracer in a poly(ethyl acrylate) (M_n  = 7500 amu). Comparison is carried out with the findings obtained in the case of an almost monodisperse poly(ethyl acrylate) with M _n = 58 200 amu. Different dynamic regimes and crossover regions were recognized in the temperature dependence of the molecular rotation. The crossover temperatures T _c were found to be dependent on the molecular weight. Moreover, the dynamics in non-Arrhenius regions were satisfactorily described as a fractionary law of structural relaxation.

Acknowledgements

We gratefully acknowledge Sezione C of Istituto Nazionale per la Fisica della Materia for financial support of the project CRORE within Paiss2000.