On the nature of the liquid-to-glass transition equation

Аннотация

Within the model of delocalized atoms, it is shown that the parameter δT_g, which enters the glasstransition equation qτ_g = δT_g and characterizes the temperature interval in which the structure of a liquid is frozen, is determined by the fluctuation volume fraction \({f_g} = {\left( {{{\Delta {V_e}} \mathord{\left/ {\vphantom {{\Delta {V_e}} V}} \right. \kern-\nulldelimiterspace} V}} \right)_{T = {T_g}}}\) frozen at the glass-transition temperature T_g and the temperature T_g itself. The parameter δT_g is estimated by data on f_g and T_g. The results obtained are in agreement with the values of δT_g calculated by the Williams–Landel–Ferry (WLF) equation, as well as with the product qτ_g—the left-hand side of the glass-transition equation (q is the cooling rate of the melt, and τ_g is the structural relaxation time at the glass-transition temperature). Glasses of the same class with f_g ≈ const exhibit a linear correlation between δT_g and T_g. It is established that the currently used methods of Bartenev and Nemilov for calculating δT_g yield overestimated values, which is associated with the assumption, made during deriving the calculation formulas, that the activation energy of the glass-transition process is constant. A generalized Bartenev equation is derived for the dependence of the glass-transition temperature on the cooling rate of the melt with regard to the temperature dependence of the activation energy of the glasstransition process. A modified version of the kinetic glass-transition criterion is proposed. A conception is developed that the fluctuation volume fraction f = ΔV_e/V can be interpreted as an internal structural parameter analogous to the parameter ξ in the Mandelstam–Leontovich theory, and a conjecture is put forward that the delocalization of an active atom—its critical displacement from the equilibrium position—can be considered as one of possible variants of excitation of a particle in the Vol’kenshtein–Ptitsyn theory. The experimental data used in the study refer to a constant cooling rate of q = 0.05 K/s (3 K/min).