Understanding Flow Behaviors of Supercooled Liquids by Embodying Solid-Liquid Duality at Particle Level
Abstract
Supercooled liquids exhibit intricate flow behaviors, which progressively become nonlinear as flow rate increases. Conceptually, this complexity can be understood by the solid-liquid duality in Maxwell's understanding of materials' response to external load. Nevertheless, the microscopic foundation of this duality in supercooled liquids remains elusive, thereby impeding the modeling of flow behaviors from a microscopic viewpoint. The existence of dynamic heterogeneity adds to this difficulty. To tackle these problems, we propose the concept of local configurational relaxation time $\tau_\rm{LC}$, which is defined at the particle level. The spatial distribution of $\tau_\rm{LC}$ in flow is heterogeneous. Depending on the comparison between the local mobility measured by $\tau_\rm{LC}$ and the external shear rate, the response of local regions is either solid-like or liquid-like. In this way, $\tau_\rm{LC}$ plays a role similar to the Maxwell time. By applying this microscopic solid-liquid duality to different conditions of shear flow, we describe the emergence of shear thinning in steady shear, and predict the major characteristics of the transient response to start-up shear. Furthermore, we reveal a clear structural foundation for $\tau_\rm{LC}$ and the solid-liquid duality associated with it by introducing an order parameter extracted from local configuration. Thus, we establish a framework that connects microscopic structure, dynamics, local mechanical response, and flow behaviors for supercooled liquids. Finally, we rationalize our framework by leveraging the connection among structure, dynamics, and potential energy landscape (PEL). The PEL model illustrates how local structure, convection and thermal activation collectively determine $\tau_\rm{LC}$. Notably, it predicts two distinct response groups, which well correspond to the microscopic solid-liquid duality.