Drozd-Rzoska Aleksandra
Institute of High Pressure Physics Polish Academy of Sciences, ul. Sokołowska 29/37, 01-142, Warsaw, Poland.
Sci Rep. 2019 May 2;9(1):6816. doi: 10.1038/s41598-019-42927-y.
Despite decades of studies on the grand problem of the glass transition the question of well-defined universal patterns, including the key problem of the previtreous behavior of the primary (structural) relaxation time, remains elusive. This report shows the universal previtreous behavior of the apparent fragility, i.e. the steepness index m (T > T) = d logτ(T)/d( T/T). It is evidenced that m(T) = 1(T - T*), for T → T and T*= T - Δ T*. Basing on this finding, the new 3-parameter dependence for portraying the previtreous behavior of the primary relaxation time has been derived: τ(T) = C((T - T*)/T) × [exp((T - T*)/T)]. The universality of obtained relations is evidenced for glass formers belonging to low molecular weight liquids, polymers (melt and solid), plastic crystals, liquid crystals, resins and relaxors. They exhibit clear preferences either for the VFT or for the critical-like descriptions, if recalled already used modeling. The novel relation can obey even above the dynamic crossover temperature, with the power exponent Ω ranging between ~17 (liquid crystals) to ~57 (glycerol), what may indicate the impact of symmetry on the previtreous effect. Finally, the emerging similarity to the behavior in the isotropic phase of nematic liquid crystals is recalled.
尽管对玻璃化转变这一重大问题进行了数十年的研究,但包括初级(结构)弛豫时间的玻璃前行为这一关键问题在内的明确通用模式问题仍然难以捉摸。本报告展示了表观脆性的通用玻璃前行为,即陡度指数m(T > T)= d logτ(T)/d(T/T)。结果表明,对于T → T且T* = T - ΔT*,m(T)= 1(T - T*)。基于这一发现,推导出了用于描述初级弛豫时间玻璃前行为的新的三参数依赖关系:τ(T)= C((T - T*)/T)× [exp((T - T*)/T)]。对于属于低分子量液体、聚合物(熔体和固体)、塑性晶体、液晶、树脂和弛豫体的玻璃形成体,所得到关系的通用性得到了证明。如果回顾已经使用过的建模方法,它们对于VFT或类临界描述表现出明显的偏好。即使在动态交叉温度以上,新关系也能成立,幂指数Ω在17(液晶)到57(甘油)之间,这可能表明对称性对玻璃前效应的影响。最后,回顾了与向列型液晶各向同性相行为的新出现的相似性。