Non-Arrhenius Behavior of the Viscosity and Glass Transition of 1,2-Propanediol Solutions Containing LiBF4.

A familiar polyalcohol, 1,2-propanediol (12PDO), is among the simple alcoholic solvents with high solubility for lithium tetrafluoroborate (LiBF4), as well as a wide temperature range for liquids. The viscosity of 12PDO solutions containing LiBF4 was measured in the temperature range of 280‒340 K using a vibrational viscometer, and it exhibited non-Arrhenius behavior fitted with the Vogel–Fulcher–Tamman (VFT) equation, which is an empirical model for describing liquid dynamics. The viscosity (η) increased with the increasing mole fraction of LiBF4 (x), and the variation in η was found to be mainly controlled by the pre-exponential factor η0 in the VFT expression. The VFT-fitting parameters, the strength parameter (D), and ideal glass transition temperature (T0), which indicate the Arrhenius behavior and an ideal glass transition temperature, respectively, correlated with the thermal analysis results that were obtained via differential scanning calorimetry. With the increasing x, the value of D decreased rapidly for x < 0.20, whereas it remained approximately unchanged for x > 0.20. The concentration dependence of T0 also differed at approximately x = 0.20. The changes in D and T0 with x indicated that the intrinsic hydrogen-bonding networks between the solvent molecules were rapidly destroyed by the added ions at reduced salt concentrations, while such a structural breaking effect of the added ions weakened owing to ion associations at increased salt concentrations. Thus, it was observed that the solvation structure and dynamics of the solutions strongly depended on the salt concentration. [ABSTRACT FROM AUTHOR]