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Mobilities of polymer liquids at constant temperature and at constant volume

Authors
Journal
Polymer
0032-3861
Publisher
Elsevier
Publication Date
Volume
19
Issue
8
Identifiers
DOI: 10.1016/0032-3861(78)90195-7
Disciplines
  • Chemistry
  • Physics

Abstract

Abstract Previously developed relationships between isomobility states and equilibrium p- v- T properties of vinyl polymers are extended to predict mobilities, μ, at constant temperature and at constant volume, with poly(vinyl acetate) as an example. At constant volume, μ changes by several orders of magnitude while the ‘internal pressure’ remains constant, suggesting that kinetic energy (temperature) dominates in governing μ. From μ at constant temperature the Vogel parameters, B and T 0, are found to increase with pressure, the former increasing linearly. A new Vogel type equation is developed in which one of the parameters, B v , depends only on the chemical composition of the polymer. Both μ and its ‘activation energy’ at constant pressure, E p , are shown to be constant at the glass transition.

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