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Thermodynamics of vitreous transition

Published online by Cambridge University Press:  13 March 2012

R.F. Tournier
R.F. Tournier*
Affiliation:
Centre National de la Recherche Scientifique, Université Joseph Fourier, Consortium de Recherches pour l’Émergence de Technologies Avancées, B.P. 166, 38042 Grenoble Cedex 09, France. e-mail: Robert.Tournier@grenoble.cnrs.fr
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Abstract

The maximum value at equilibrium of the relaxed enthalpy of some glasses is viewed as alinear function of the annealing temperature from the Kauzmann temperatureTK up to a vitreous transition temperature T*g which is not time dependent. The frozen enthalpy and entropy at T*gare determined from the specific heat difference between glass andundercooled melt which is constant between TKandT*g. The Gibbs free energy change at T*g is equal to zero. The vitreous transition is a thermodynamic transitionwithout latent heat. A model is used to describe this phenomenon. A volume energy saving εv equivalent to a complementary Laplace pressure has beenadded to the classical Gibbs free energy change for a crystal formation in a melt. Thereis a change of the Vogel–Fulcher–Tammann (VFT) temperature at T*g corresponding to a decrease of the free volume disappearancetemperature. Scaling laws linking the crystal homogeneous nucleation temperatures to T*g are used to predict the two VFT temperatures, the thermodynamic vitreoustransition induced by vitreous (super)-clusters and the frozen enthalpy and entropy at T*g only knowing T*g, the melting temperature Tmand the fusion heat ΔHm of any fragileglass-forming melt.

Keywords

glassesglass transitionsmetallic glassesnon metallic glassespolymersnucleation
Type
Research Article
Information
Metallurgical Research & Technology , Volume 109 , Issue 1 , 2012 , pp. 27 - 33
Copyright
© EDP Sciences 2012

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