From positron annihilation lifetime spectroscopy analyzed with the new routine LT9.0 and pressure-volume-temperature experiments analyzed employing the equation of state (EOS) Simha-Somcynsky lattice-hole theory (SS EOS) the microstructure of the free volume and its temperature dependence of an oligomeric epoxy resin (ER6, M(n) approximately 1750 g/mol , T(g)=332 K ) of diglycidyl ether of bisphenol-A (DGEBA) have been examined and characterized by the hole free-volume fraction h, the specific free and occupied volumes V(f)=hV and V(occ)=(1-h)V, and the size distribution (mean,
The microstructure of the free volume and its temperature dependence in polymethylphenylsiloxane (PMPS) have been examined using positron annihilation lifetime spectroscopy (PALS) and pressure-volume-temperature experiments. The hole-free volume fraction h and the specific hole-free and occupied volumes, Vf=hV and Vocc=(1-h)V, were estimated employing the Simha-Somcynsky (SS) lattice-hole theory. From the PALS spectra analyzed with the new routine LT9.0 the hole size distribution, its mean,
Changes in the microstructure of the free volume and its temperature dependence in ethylene-norbornene copolymer and bisphenol-A polycarbonate due to densification under pressure and swelling with CO2 gas have been examined using positron annihilation lifetime spectroscopy (PALS) and pressurevolume- temperature (PVT) experiments. Employing the Simha-Somcynsky equation of state the specific hole free and occupied volumes were estimated. From the PALS spectra analyzed with the new routine LT9.0 the size distribution of subnanometre holes and its mean and mean dispersion were calculated. Above Tg, the dispersion mirrors the thermal fluctuations in the free volume. From comparison of PALS and PVT data the specific number of holes was estimated. It was found that the occupied volume has a constant and identical compressibility in the glassy and rubbery state. It shows no memory for the history of the glass and mirrors only the pressure and temperature during the measurement. The change in the total volume due to the pre-treatments of the polymers occurs exclusively in the hole free volume Vf and the relative change in Vf is one order of magnitude larger than in the total volume. PALS data show that the mean hole size and its dispersion in the glassy state is decreased due to densification and increased due to swelling. PVT data show that the volume changes are frozen in the polymer glasses and that, when heating the samples, the volume begins to recover at temperatures ca. 50 K in gas swollen and 20 K in densified polymers below Tg. The PALS data show a corresponding behaviour.
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