"Glass and Time," IMFUFA, Department of Science and Environment, Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark.
J Chem Phys. 2017 Apr 21;146(15):154504. doi: 10.1063/1.4979658.
This paper presents data for supercooled squalane's frequency-dependent shear modulus covering frequencies from 10 mHz to 30 kHz and temperatures from 168 K to 190 K; measurements are also reported for the glass phase down to 146 K. The data reveal a strong mechanical beta process. A model is proposed for the shear response of the metastable equilibrium liquid phase of supercooled liquids. The model is an electrical equivalent-circuit characterized by additivity of the dynamic shear compliances of the alpha and beta processes. The nontrivial parts of the alpha and beta processes are each represented by a "Cole-Cole retardation element" defined as a series connection of a capacitor and a constant-phase element, resulting in the Cole-Cole compliance function well-known from dielectrics. The model, which assumes that the high-frequency decay of the alpha shear compliance loss varies with the angular frequency as ω, has seven parameters. Assuming time-temperature superposition for the alpha and beta processes separately, the number of parameters varying with temperature is reduced to four. The model provides a better fit to the data than an equally parametrized Havriliak-Negami type model. From the temperature dependence of the best-fit model parameters, the following conclusions are drawn: (1) the alpha relaxation time conforms to the shoving model; (2) the beta relaxation loss-peak frequency is almost temperature independent; (3) the alpha compliance magnitude, which in the model equals the inverse of the instantaneous shear modulus, is only weakly temperature dependent; (4) the beta compliance magnitude decreases by a factor of three upon cooling in the temperature range studied. The final part of the paper briefly presents measurements of the dynamic adiabatic bulk modulus covering frequencies from 10 mHz to 10 kHz in the temperature range from 172 K to 200 K. The data are qualitatively similar to the shear modulus data by having a significant beta process. A single-order-parameter framework is suggested to rationalize these similarities.
本文提供了超冷 squalane 频依赖剪切模量的数据,涵盖了从 10 mHz 到 30 kHz 的频率和从 168 K 到 190 K 的温度;还报告了玻璃相下至 146 K 的测量结果。数据显示出强烈的机械β过程。提出了一个超冷液体亚稳平衡液相剪切响应模型。该模型是一个电等效电路,其特征是α和β过程的动态剪切柔量可加。α和β过程的复杂部分分别由一个“Cole-Cole 延迟元件”表示,该元件定义为一个电容器和一个恒相元件的串联连接,导致熟知的介电常数的 Cole-Cole 柔量函数。该模型假设α剪切柔量损耗的高频衰减随角频率ω变化,具有七个参数。假设α和β过程分别进行时间-温度叠加,随温度变化的参数数量减少到四个。该模型比具有相同参数的 Havriliak-Negami 型模型更能拟合数据。从最佳拟合模型参数的温度依赖性得出以下结论:(1)α松弛时间符合推斥模型;(2)β松弛损耗峰频率几乎与温度无关;(3)α柔量大小,在模型中等于瞬时剪切模量的倒数,仅随温度略有变化;(4)在研究的温度范围内冷却时,β柔量大小减小了三倍。本文的最后一部分简要介绍了在 172 K 至 200 K 的温度范围内从 10 mHz 到 10 kHz 的动态绝热体膨胀系数的测量结果。数据与剪切模量数据相似,具有显著的β过程。建议采用单序参量框架来合理化这些相似性。