Department of Intelligent Systems Engineering, Indiana University, Bloomington, IN 47408.
Department of Physics and Astronomy, Johns Hopkins University, Baltimore, MD 21218.
Proc Natl Acad Sci U S A. 2017 Jul 25;114(30):7952-7957. doi: 10.1073/pnas.1705978114. Epub 2017 Jul 10.
For decades, scientists have debated whether supercooled liquids stop flowing below a glass transition temperature [Formula: see text] or whether motion continues to slow gradually down to zero temperature. Answering this question is challenging because human time scales set a limit on the largest measurable viscosity, and available data are equally well fit to models with opposite conclusions. Here, we use short simulations to determine the nonequilibrium shear response of a typical glass-former, squalane. Fits of the data to an Eyring model allow us to extrapolate predictions for the equilibrium Newtonian viscosity [Formula: see text] over a range of pressures and temperatures that change [Formula: see text] by 25 orders of magnitude. The results agree with the unusually large set of equilibrium and nonequilibrium experiments on squalane and extend them to higher [Formula: see text] Studies at different pressures and temperatures are inconsistent with a diverging viscosity at finite temperature. At all pressures, the predicted viscosity becomes Arrhenius with a single temperature-independent activation barrier at low temperatures and high viscosities ([Formula: see text] Pa[Formula: see text]s). Possible experimental tests of our results are outlined.
几十年来,科学家们一直在争论超冷液体在玻璃化转变温度 [Formula: see text]以下是否停止流动,还是运动继续逐渐减慢至零温度。回答这个问题具有挑战性,因为人类的时间尺度限制了可测量的最大粘度,而且可用数据同样适用于具有相反结论的模型。在这里,我们使用短时间模拟来确定典型玻璃形成体 squalane 的非平衡剪切响应。对数据的 Eyring 模型拟合允许我们推断在一系列压力和温度下的平衡牛顿粘度 [Formula: see text],这些压力和温度的变化范围为 [Formula: see text],跨越 25 个数量级。结果与对 squalane 的大量非平衡和平衡实验一致,并将它们扩展到更高的 [Formula: see text]。在不同压力和温度下的研究与有限温度下粘度发散不一致。在所有压力下,预测的粘度在低温和高粘度下([Formula: see text] Pa[Formula: see text]s)表现为阿累尼乌斯关系,具有单个与温度无关的激活能垒。概述了对我们结果进行可能的实验测试的方案。