Drozd-Rzoska Aleksandra, Rzoska Sylwester J, Starzonek Szymon
Institute of High Pressure Physics of the Polish Academy of Sciences, Warsaw, Poland.
Sci Rep. 2022 Feb 23;12(1):3058. doi: 10.1038/s41598-022-05897-2.
We show that on cooling towards glass transition configurational entropy exhibits more significant changes than predicted by classic relation. A universal formula according to Kauzmann temperature [Formula: see text] is given: [Formula: see text], where [Formula: see text]. The exponent [Formula: see text] is hypothetically linked to dominated local symmetry. Such a behaviour is coupled to previtreous evolution of heat capacity [Formula: see text] associated with finite temperature singularity. These lead to generalised VFT relation, for which the basic equation is retrieved. For many glass-formers, basic VFT equation may have only an effective meaning. A universal-like reliability of the Stickel operator analysis for detecting dynamic crossover phenomenon is also questioned. Notably, distortions-sensitive and derivative-based analysis focused on previtreous changes of configurational entropy and heat capacity for glycerol, ethanol and liquid crystal is applied.
我们表明，在冷却至玻璃化转变时，构型熵呈现出比经典关系所预测的更为显著的变化。给出了一个根据考兹曼温度[公式：见原文]的通用公式：[公式：见原文]，其中[公式：见原文]。指数[公式：见原文]假设与主导的局部对称性相关联。这种行为与与有限温度奇点相关的热容的玻璃化前演化[公式：见原文]相耦合。这些导致了广义的VFT关系，从中可以得到基本方程。对于许多玻璃形成体，基本的VFT方程可能仅具有有效意义。用于检测动态交叉现象的施蒂克尔算子分析的类似通用的可靠性也受到质疑。值得注意的是，应用了对甘油、乙醇和液晶的构型熵和热容的玻璃化前变化进行的畸变敏感和基于导数的分析。
