Douglass Ian M, Dyre Jeppe C
Glass and Time, IMFUFA, Department of Science and Environment, Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark.
Phys Rev E. 2022 Nov;106(5-1):054615. doi: 10.1103/PhysRevE.106.054615.
Although it has been known for half a century that the physical aging of glasses in experiments is described well by a linear thermal-history convolution integral over the so-called material time, the microscopic definition and interpretation of the material time remains a mystery. We propose that the material-time increase over a given time interval reflects the distance traveled by the system's particles. Different possible distance measures are discussed, starting from the standard mean-square displacement and its inherent-state version that excludes the vibrational contribution. The viewpoint adopted, which is inspired by and closely related to pioneering works of Cugliandolo and Kurchan from the 1990s, implies a "geometric reversibility" and a "unique-triangle property" characterizing the system's path in configuration space during aging. Both of these properties are inherited from equilibrium, and they are here confirmed by computer simulations of an aging binary Lennard-Jones system. Our simulations moreover show that the slow particles control the material time. This motivates a "dynamic-rigidity-percolation" picture of physical aging. The numerical data show that the material time is dominated by the slowest particles' inherent mean-square displacement, which is conveniently quantified by the inherent harmonic mean-square displacement. This distance measure collapses data for potential-energy aging well in the sense that the normalized relaxation functions following different temperature jumps are almost the same function of the material time. Finally, the standard Tool-Narayanaswamy linear material-time convolution-integral description of physical aging is derived from the assumption that when time is replaced by distance in the above sense, an aging system is described by the same expression as that of linear-response theory.
尽管半个世纪以来人们就知道,在实验中玻璃的物理老化可以通过对所谓的材料时间进行线性热历史卷积积分很好地描述,但材料时间的微观定义和解释仍然是个谜。我们提出,在给定时间间隔内材料时间的增加反映了系统粒子所走过的距离。从标准均方位移及其排除振动贡献的固有态版本开始,讨论了不同的可能距离度量。所采用的观点受到20世纪90年代库利亚多洛和库尔昌开创性工作的启发并与之密切相关,这意味着在老化过程中系统在构型空间中的路径具有“几何可逆性”和“唯一三角形性质”。这两个性质都继承自平衡态,并且在这里通过对老化的二元 Lennard-Jones 系统的计算机模拟得到了证实。我们的模拟还表明,慢速粒子控制着材料时间。这激发了物理老化的“动态刚性渗流”图景。数值数据表明,材料时间由最慢粒子的固有均方位移主导,这可以方便地通过固有调和均方位移来量化。这种距离度量在不同温度跃变后的归一化弛豫函数几乎是材料时间的相同函数的意义上,很好地压缩了势能老化的数据。最后,物理老化的标准 Tool-Narayanaswamy 线性材料时间卷积积分描述是基于这样的假设推导出来的:当按照上述意义将时间替换为距离时,老化系统可以用与线性响应理论相同的表达式来描述。