Joint Institute for Nuclear Research, Frank Laboratory of Neutron Physics, 141980 Dubna, Russia.
J Chem Phys. 2012 Mar 28;136(12):124502. doi: 10.1063/1.3694531.
In a recent analysis [J. W. P. Schmelzer and I. Gutzow, J. Chem. Phys. 125, 184511 (2006)] it was shown for the first time that--in contrast to earlier belief arising from the works of Prigogine and Defay [Chemical Thermodynamics (Longman, London, 1954), Chap. 19; The first French edition of this book was published in 1950] and Davies and Jones [Adv. Phys. 2, 370 (1953); and Proc. R. Soc. London, Ser. A 217, 26 (1953)]--a satisfactory theoretical interpretation of the experimentally observed values of the so-called Prigogine-Defay ratio Π, being a combination of jumps of thermodynamic coefficients at glass transition, can be given employing only one structural order parameter. According to this analysis, this ratio has to be, in full agreement with experimental findings, larger than one (Π > 1). Its particular value depends both on the thermodynamic properties of the system under consideration and on cooling and heating rates. Based on above-mentioned analysis, latter dependence on cooling rates has been studied in detail in another own preceding paper [T. V. Tropin, J. W. P. Schmelzer, and C. Schick, J. Non-Cryst. Solids 357, 1303 (2011)]. In the present analysis, an alternative general method of determination of the Prigogine-Defay ratio is outlined, allowing one to determine this ratio having at ones disposal the generalized equation of state of the glass-forming melts under consideration and, in particular, the knowledge of the equilibrium properties of the melts in the glass transformation range. Employing, as an illustration of the method, a particular model for the description of glass-forming melts, theoretical estimates are given for this ratio being, again, in good agreement with experimental data.
在最近的一项分析中 [J. W. P. Schmelzer 和 I. Gutzow, J. Chem. Phys. 125, 184511 (2006)]，首次表明——与 Prigogine 和 Defay [Chemical Thermodynamics (Longman, London, 1954), Chap. 19; 该书的第一版法译本出版于 1950 年] 和 Davies 和 Jones [Adv. Phys. 2, 370 (1953); 和 Proc. R. Soc. London, Ser. A 217, 26 (1953)] 的早期工作所产生的观点相反——仅使用一个结构序参量，就可以对实验观测到的所谓 Prigogine-Defay 比 Π 的值给出令人满意的理论解释，Π 是热力学系数在玻璃转变时跳跃的组合。根据这项分析，这个比值必须与实验结果完全一致，即大于一（Π > 1）。它的特定值不仅取决于所考虑的系统的热力学性质，还取决于冷却和加热速率。基于上述分析，我们在之前的一篇论文中详细研究了后者对冷却速率的依赖性 [T. V. Tropin, J. W. P. Schmelzer, and C. Schick, J. Non-Cryst. Solids 357, 1303 (2011)]。在本分析中，提出了一种确定 Prigogine-Defay 比的替代方法，该方法允许在掌握所考虑的玻璃形成熔体的广义状态方程的情况下确定该比值，特别是熔体在玻璃转变范围内的平衡性质的知识。使用描述玻璃形成熔体的特定模型来说明该方法，再次给出了该比值的理论估计，这些估计与实验数据非常吻合。
