Dynamic Crossover in Polymers, Role of Molecular Weight

One of the most characteristic features of glass-forming liquids is the sharp slowing down of relaxation times, τ, upon cooling. In these materials relaxation dynamics exhibit a non-Arrhenius temperature dependence usually described by Vogel-Fulcher-Tamman (VFT) relation [1]. However, for majority of glassforming liquids it is impossible to fit data in the entire temperature range with a single set of VFT parameters. Above some characteristic temperature it is necessary to use another set of VFT parameters. Existence of this dynamic crossover was predicted by the mode-coupling theory (MCT) [2]. The theory predicts a transition from a liquidlike to a solidlike dynamics on a molecular time and length scale at some specific temperature, TC, above the glass transition temperature Tg. The dynamic crossover becomes even more evident with the use of derivative analysis proposed by Stickel et al [3] 2 , where x is the relaxation time or frequency. If