Effect of chain length on fragility and thermodynamic scaling of the local segmental dynamics in poly(methylmethacrylate)
Abstract
Local segmental relaxation properties of poly(methylmethacrylate) (PMMA) of varying molecular weight are measured by dielectric spectroscopy, and analyzed in combination the equation of state obtained from PVT measurements. The usual variation of glass transition temperature and fragility with molecular weight are observed. We also find, in accord with the general properties of glass-forming materials, that a single molecular weight dependent scaling exponent, g, is sufficient to define the mean segmental relaxation time, taualpha, and its distribution. This exponent can be connected to the Gruneisen parameter and related thermodynamic quantities, thus demonstrating the interrelationship between dynamics and thermodynamics in PMMA. Changes in the relaxation properties ("dynamic crossover") are observed as a function of both temperature and pressure, with taualpha serving as the control parameter for the crossover. At longer taualpha another change in the dynamics is apparent, associated with a decoupling of the local segmental process from ionic conductivity.
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