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Thermodynamic consequences of the kinetic nature of the glass transition

In this paper, we consider the glass transition as a kinetic process and establish one universal equation for the pressure coefficient of the glass transition temperature, dT(g)/dp, which is a thermodynamic characteristic of this process. Our findings challenge the common previous expectations conce...

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Detalles Bibliográficos
Autores principales: Koperwas, Kajetan, Grzybowski, Andrzej, Tripathy, Satya N., Masiewicz, Elzbieta, Paluch, Marian
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4674716/
https://www.ncbi.nlm.nih.gov/pubmed/26657017
http://dx.doi.org/10.1038/srep17782
Descripción
Sumario:In this paper, we consider the glass transition as a kinetic process and establish one universal equation for the pressure coefficient of the glass transition temperature, dT(g)/dp, which is a thermodynamic characteristic of this process. Our findings challenge the common previous expectations concerning key characteristics of the transformation from the liquid to the glassy state, because it suggests that without employing an additional condition, met in the glass transition, derivation of the two independent equations for dT(g)/dp is not possible. Hence, the relation among the thermodynamic coefficients, which could be equivalent to the well-known Prigogine-Defay ratio for the process under consideration, cannot be obtained. Besides, by comparing the predictions of our universal equation for dT(g)/dp and Ehrenfest equations, we find the aforementioned supplementary restriction, which must be met to use the Prigogine-Defay ratio for the glass transition.