Summary:The microstructure of the free volume and its temperature dependence in two poly(dimethyl siloxane)s (PDMS), one in the pure state and the other filled with 35 wt.‐% of an in situ hydrophobized fumed silica with a specific surface area of 200–300 m2 · g−1, were studied by pressure‐volume‐temperature experiments (PVT, T = 22–156 °C, P = 10–200 MPa) and positron annihilation lifetime spectroscopy (PALS, T = −173–100 °C, P = 10−5 MPa). The Simha‐Somcynsky equation of state was used to estimate the hole free volume fraction, h, and free and occupied volumes, Vf = hV and Vocc = (1 − h)V, from the specific total volume, V. The PALS spectra were analyzed with the routine LT9.0, which allowed for a dispersion, σi, in all three of the lifetimes: the para‐positronium (p‐Ps, τ1), positron (e+, τ2), and ortho‐positronium (o‐Ps) lifetime (τ3). This kind of analysis delivered correct p‐Ps lifetime parameters, τ1, σ1, and I1. It was speculated that e+, like o‐Ps, undergoes Anderson localization at empty sites of the, static or dynamic, disordered structure. The hole size distribution, its mean value, 〈vh〉, and dispersion, σh, were calculated from the o‐Ps lifetimes. A comparison of 〈vh〉 with Vf was used to estimate the specific hole number, $N'_{\rm h}$. During melting of the semicrystalline samples at−38 °C (Tm), 〈vh〉 increased abruptly, and σh suddenly decreased. Both effects are explained by the disappearance of the rigid‐amorphous fraction (RAF) and, thus, a reduction in the dynamic heterogeneity. The following leveling‐off in 〈vh〉 and the low value of σh are attributed to the fast segmental relaxation in the PDMS melts which leads to a smearing of the molecule density distribution around a hole during the o‐Ps lifetime.
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