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AuthorDlubek, Gunter
AuthorBondarenko, Vladimir
AuthorAl-Qaradawi, Ilham Y.
AuthorKilburn, Duncan
AuthorKrause-Rehberg, Reinhard
Available date2015-11-05T06:57:46Z
Publication Date2004
Publication NameMacromolecular Chemistry and Physics
ResourceWiley Online Library
CitationDlubek, G., Bondarenko, V., Al-Qaradawi, I. Y., Kilburn, D. and Krause-Rehberg, R. (2004), The Structure of the Free Volume in Poly(styrene-co-acrylonitrile) from Positron Lifetime and Pressure Volume Temperature (PVT) Experiments. Macromolecular Chemistry and Physics, 205(4):512-522
ISSN1521-3935
URIhttp://dx.doi.org/10.1002/macp.200300104
URIhttp://hdl.handle.net/10576/3636
AbstractSummary: The structure of the free volume and its temperature dependence between 25 and 190 °C of copolymers of styrene with acrylonitrile, SAN (0 to 50 mol-% AN), is studied by pressure volume temperature (PVT) experiments and positron annihilation lifetime spectroscopy (PALS). In this second part of the work, PALS data are reported from which the temperature dependence of the mean size and size distribution of local free volumes (subnanometer size holes) is analysed. The mean hole volume, vh, varies in PS between 105 Å3 (27 °C) and 220 Å3 (190 °C), and shows a systematic decrease with increasing AN content, at Tg from 121 Å3 for PS to 102 (±2) Å3 for SAN50. The specific number of holes, equation image, estimated from a comparison of PVT and PALS results, is independent on the temperature and the composition of SAN, equation image = (0.56 ± 0.02) × 1021 g−1 which corresponds to Nh(Tg) = equation image/V(Tg) = 0.59 nm−3 and 1/Nh(Tg) = 1.7 nm3 for the volume which contains one hole. The analysed size distributions of the holes above Tg follow the compressibility of the free volume as it is predicted by the theory of thermal volume fluctuation. Moreover, we showed that the bulk elasticity modulus follows mastercurves as a function of vh above and below Tg.
Languageen
PublisherWILEY-VCH Verlag
Subjectfree volume
glass transition
microstructure
positron lifetime
styrene copolymers
TitleThe Structure of the Free Volume in Poly(styrene-co-acrylonitrile) from Positron Lifetime and Pressure Volume Temperature (PVT) Experiments
TypeArticle
Issue Number4
Volume Number205


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