Correlated heterogeneous dynamics in glass-forming polymers

Abstract

We report x-ray photon correlation spectroscopy experiments on the dynamics of the glass-former polypropylene glycol covering a temperature range from room temperature to the glass transition at Tg=205 K using silica tracer particles. Three temperature regimes are identified: At high temperatures, Brownian motion of the tracer particles is observed. Near Tg, the dynamics is hyperdiffusive and ballistic. Around 1.12Tg, we observe an intermediate regime. Here the stretching exponent of the Kohlrausch-Williams-Watts function becomes q dependent. By analyzing higher-order correlations in the scattering data, we find that dynamical heterogeneities dramatically increase in this intermediate-temperature regime. This leads to two effects: increasing heterogeneous dynamics and correlated motion at temperatures close to and below 1.12Tg.