Thermodynamics of vitreous transition

The maximum value at equilibrium of the relaxed enthalpy of some glasses is viewed as a linear function of the annealing temperature from the Kauzmann temperature T K up to a vitreous transition temperature T * g which is not time dependent. The frozen enthalpy and entropy at T * g are determined from the specific heat difference between glass and undercooled melt which is constant between T K and T * g . The Gibbs free energy change at T * g is equal to zero. The vitreous transition is a thermodynamic transition without latent heat. A model is used to describe this phenomenon. A volume energy saving e v equivalent to a complementary Laplace pressure has been added to the classical Gibbs free energy change for a crystal formation in a melt. There is a change of the Vogel–Fulcher–Tammann (VFT) temperature at T * g corresponding to a decrease of the free volume disappearance temperature. Scaling laws linking the crystal homogeneous nucleation temperatures to T * g are used to predict the two VFT temperatures, the thermodynamic vitreous transition induced by vitreous (super)-clusters and the frozen enthalpy and entropy at T * g only knowing T * g , the melting temperature T m and the fusion heat Δ H m of any fragile glass-forming melt.

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