Reorientational dynamics of highly asymmetric binary non-polymeric mixtures - a dielectric spectroscopy study

Phys Chem Chem Phys. 2021 Mar 28;23(12):7200-7212. doi: 10.1039/d0cp06652d. Epub 2021 Mar 18.

Abstract

We present an analysis of dielectric spectra measured for a specially designed non-polymeric asymmetric binary glass former characterized by a large difference of the component's Tg (ΔTg = 216 K). We cover the whole additive concentration range from 4% up to 90% (by mass). Two main relaxations α1 and α2 are identified, which are characterized by well separated time scales and are attributed to the dynamics associated with the high-Tg component (α1) and the low-Tg component (α2). Frequency-temperature superposition does not apply. To cope with the extraordinary spectral broadening, we introduce a model consisting of a generalized Cole-Davidson (α1) and a Havriliak-Negami function with a low frequency truncation (α2). Whereas the α1-relaxation reflects essentially homogeneous dynamics and its spectra mainly broaden on the high-frequency flank of the relaxation peak, the α2-relaxation becomes broader on the low-frequency side reflecting pronounced dynamic heterogeneity in a more or less arrested matrix of high-Tg molecules. From the extracted time constants, two glass transition temperatures Tg1 and Tg2 can be derived, showing a non-trivial concentration dependence for Tg2. Supplementary, we find a β-relaxation. The total relaxation strength Δε strongly deviates from ideal mixing, and therefore care has to be taken interpreting the corresponding Δεαi as representation of molecular populations.