Abstract
Atactic polystyrenes of narrow molar mass distribution with average molar masses larger than the critical molar massM c were mixed with similar polystyrenes of molecular masses lower thanM c . Linear viscoelastic melt properties of these binary blends were measured with a dynamic viscometer of the concentric cylinder type. One of the experimental findings is that the time-temperature shift factorsa T are dependent on the composition of the samples. This can be understood, if free volume due to chain-ends is taken into account. A computer-fitted WLF-equation being modified in a proper way leads to the following results: At the glass-transition-temperature the fraction of free volume in polystyrene of infinite molar mass is only 0.015. At a temperature of 180 °C the mean value of the free volume at a chain end is 0.029 nm3 for the polystyrene investigated.
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Knoglinger, H., Schausberger, A. & Janeschitz-Kriegl, H. The role of short chain molecules for the rheology of polystyrene melts.. Rheol Acta 26, 460–467 (1987). https://doi.org/10.1007/BF01333847
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DOI: https://doi.org/10.1007/BF01333847