Changes in the free volume in CYTOP due to pressure densification and swelling with CO2 have been examined using PALS and PVT experiments. Employing the Simha‐Somcynsky equation of state the specific hole free, Vf, and occupied, Vocc, volumes were estimated. The change in the total volume due to the pre‐treatments occurs exclusively in the hole free volume and the relative change in Vf is one order of magnitude larger than in the total volume. Vocc shows no memory for the history of the polymer glass. The mean and width of the size distribution of subnanometre holes in the glassy state decrease upon densification and increase upon swelling. The volume changes which are frozen in the polymer glass begin to recover at temperatures distinctly below Tg. magnified image
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Dlubek et al. (2008) studied this question.
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