Revisiting the glass transition and dynamics of supercooled benzene by calorimetric studies

The glass transition and dynamics of benzene are studied in binary mixtures of benzene with five glass forming liquids, which can be divided into three groups: (a) o-terphenyl and m-xylene, (b) N-butyl methacrylate, and (c) N,N-dimethylpropionamide and N,N-diethylformamide to represent the weak, moderate, and strong interactions with benzene. The enthalpies of mixing, ΔH(mix), for the benzene mixtures are measured to show positive or negative signs, with which the validity of the extrapolations of the glass transition temperature T(g) to the benzene-rich regions is examined. The extrapolations for the T(g) data in the mixtures are found to converge around the point of 142 K, producing T(g) of pure benzene. The fragility m of benzene is also evaluated by extrapolating the results of the mixtures, and a fragility m ∼ 80 is yielded. The obtained T(g) and m values for benzene allow for the construction of the activation plot in the deeply supercooled region. The poor glass formability of benzene is found to result from the high melting point, which in turn leads to low viscosity in the supercooled liquid.