The iso-structural viscosity, configurational entropy and fragility of oxide liquids

This paper describes how the fragility of a liquid is linked to the ratio between the energy barrier (E-eq) for the equilibrium Viscous behavior and that (E-iso) for the non-equilibrium iso-structural viscous behavior. Using the concept of iso-structural Viscosity, two functions describing the variation of the configurational entropy (S-c) with temperature (T) are obtained from the Avramov-Milchev (AM) and the Vogel-Fulcher-Tammann (VFT) viscosity equations, respectively. The two S-c(T) functions exhibit different relations to the liquid fragility. The AM S-c(T) function is a power function with the exponent of F - 1, where F is the AM fragility index. In this case, S-c vanishes at T = 0 K. For the VFT function, S-c vanishes as T is lowered to a finite temperature T-0, whereas it reaches the maximum Value S-c,S-max at infinitively high T. S-c.max is proportional to the VFT fragility index. Thus, the VFT equation is not only a dynamical, but also a thermodynamic model. It is proved that for oxide liquids, the VFT equation describes viscosity data better than the AM equation, provided the pre-exponential factor eta(0) is fixed to a generally accepted value, e.g., 10(-3.5) Pa s. (C) 2009 Elsevier B.V. All rights reserved.