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It is shown that combined use of positron annihilation lifetime spectroscopy-an experimental tool to investigate the intermolecular sub-nanometric spaces (free volume) in amorphous polymer-and of specific-volume measurements supplies unique information on the occupied volume, allowing one to study its behavior under variation of thermodynamic quantities. In the present case thermal expansion is considered. The methodology has been applied to two members of a homologous series of polypropyleneglycol oligomers; however, it can be used in principle to any disordered macromolecular structure and liquids.
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Consolati et al. (2001) studied this question.
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