Free volume from positron lifetime and pressure-volume-temperature experiments in relation to structural relaxation of van der Waals molecular glass-forming liquids.

Positron annihilation lifetime spectroscopy (PALS) is employed to characterize the temperature dependence of the free volume in two van der Waals liquids: 1, 1'-bis(p-methoxyphenyl)cyclohexane (BMPC) and 1, 1'-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC). From the PALS spectra analysed with the routine LifeTime9.0, the size (volume) distribution of local free volumes (subnanometer size holes), its mean, [v(h)], and mean dispersion, σ(h), were calculated. A comparison with the macroscopic volume from pressure-volume-temperature (PV T) experiments delivered the hole density and the specific hole free volume and a complete characterization of the free volume microstructure in that sense. These data are used in correlation with structural (α) relaxation data from broad-band dielectric spectroscopy (BDS) in terms of the Cohen-Grest and Cohen-Turnbull free volume models. An extension of the latter model allows us to quantify deviations between experiments and theory and an attempt to systematize these in terms of T(g) or of the fragility. The experimental data for several fragile and less fragile glass formers are involved in the final discussion. It was concluded that, for large differences in the fragility of different glass formers, the positron lifetime mirrors clearly the different character of these materials. For small differences in the fragility, additional properties like the character of bonds and chemical structure of the material may affect size, distribution and thermal behaviour of the free volume.