Yu Yingtian, Wang Mengyi, Smedskjaer Morten M, Mauro John C, Sant Gaurav, Bauchy Mathieu
Physics of AmoRphous and Inorganic Solids Laboratory (PARISlab), Department of Civil and Environmental Engineering, University of California, Los Angeles, California 90095, USA.
Department of Chemistry and Bioscience, Aalborg University, 9220 Aalborg, Denmark.
Phys Rev Lett. 2017 Sep 1;119(9):095501. doi: 10.1103/PhysRevLett.119.095501. Epub 2017 Aug 31.
Despite the dramatic increase of viscosity as temperature decreases, some glasses are known to feature room-temperature relaxation. However, the structural origin of this phenomenon-known as the "thermometer effect"-remains unclear. Here, based on accelerated molecular dynamics simulations of alkali silicate glasses, we show that both enthalpy and volume follow stretched exponential decay functions upon relaxation. However, we observe a bifurcation of their stretching exponents, with β=3/5 and 3/7 for enthalpy and volume relaxation, respectively, in agreement with Phillips's topological diffusion-trap model. Based on these results, we demonstrate that the thermometer effect is a manifestation of the mixed alkali effect. We show that relaxation is driven by the existence of stressed local structural instabilities in mixed alkali glasses. This driving force is found to be at a maximum when the concentrations of each alkali atom equal each other, which arises from a balance between the concentration of each alkali atom and the magnitude of the local stress that they experience.
尽管随着温度降低粘度急剧增加,但已知一些玻璃具有室温弛豫特性。然而,这种被称为“温度计效应”的现象的结构起源仍不清楚。在此,基于碱金属硅酸盐玻璃的加速分子动力学模拟,我们表明,在弛豫过程中,焓和体积均遵循拉伸指数衰减函数。然而,我们观察到它们的拉伸指数出现了分叉,焓弛豫和体积弛豫的拉伸指数分别为β = 3/5和3/7,这与菲利普斯的拓扑扩散陷阱模型一致。基于这些结果,我们证明温度计效应是混合碱效应的一种表现。我们表明,弛豫是由混合碱玻璃中存在的应力局部结构不稳定性驱动的。当每个碱原子的浓度相等时,这种驱动力最大,这是由每个碱原子的浓度与其所经历的局部应力大小之间的平衡所导致的。