Koperwas Kajetan, Grzybowski Andrzej, Tripathy Satya N, Masiewicz Elzbieta, Paluch Marian
Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
Silesian Center for Education and Interdisciplinary Research, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland.
Sci Rep. 2015 Dec 10;5:17782. doi: 10.1038/srep17782.
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, dTg/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 dTg/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 dTg/dp and Ehrenfest equations, we find the aforementioned supplementary restriction, which must be met to use the Prigogine-Defay ratio for the glass transition.
在本文中，我们将玻璃化转变视为一个动力学过程，并建立了一个关于玻璃化转变温度压力系数dTg/dp的通用方程，该系数是此过程的一个热力学特征。我们的研究结果挑战了此前关于从液态到玻璃态转变关键特性的普遍预期，因为这表明在没有采用玻璃化转变中所满足的附加条件时，不可能推导出两个关于dTg/dp的独立方程。因此，无法得到与所考虑过程中著名的普里高津 - 德法依比相当的热力学系数之间的关系。此外，通过比较我们关于dTg/dp的通用方程和埃伦费斯特方程的预测结果，我们发现了上述补充限制条件，要使用玻璃化转变的普里高津 - 德法依比就必须满足该条件。
