Abstract
Molecular mobility is studied in poly(butyl methacrylate) and poly(methyl methacrylate) (PMMA) with molecular dynamics simulations in order to understand the effect of the α–β crossover on the β relaxation activation energy and co-operativity. In the high frequency range investigated, the estimated β process activation energy is decreased as compared to the low frequency value. This deviation is stronger in poly(n butyl methacrylate) (PnBMA) than in PMMA. The intra-molecular co-operativity related to the β process is also higher in PnBMA than in PMMA. These results could be related to the relative position of the simulation temperature range and of the extrapolated α–β crossover temperature.
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