Abstract
A comparative study of five different experimental and computational methods is presented for the characterization of the overall free volume (FV) and the free volume element (FVE) size and shape distribution in amorphous glassy perfluoropolymers (PFPs). Experimental results from the photochromic probe (PCP) method, positron annihilation lifetime spectroscopy (PALS), and inverse gas chromatography (IGC) were confronted with literature data from 129Xe NMR spectroscopy, and the experimental data were further compared with molecular dynamics (MD) simulations and a combination of MD studies and the well-known Bondi method as well as a modified Bondi method. An evaluation of the advantages and the limits of each method is presented. This is the first reported study on a so vast number of complementary techniques applied on a single glassy polymer, in this case Hyflon AD perfluoropolymer, and is also the first successful application of the photochromic probe technique in such materials. In two different grades ...
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