Understanding Flow Behaviors of Supercooled Liquids by Embodying Solid-Liquid Duality at Particle Level

TL;DR

This paper introduces a local configurational relaxation time to embody the solid-liquid duality at the particle level, providing a microscopic framework to understand flow behaviors, shear thinning, and transient responses in supercooled liquids.

Contribution

It proposes a novel microscopic relaxation time $ au_{LC}$ embodying solid-liquid duality, linking structure, dynamics, and flow behaviors in supercooled liquids.

Findings

Heterogeneous spatial distribution of $ au_{LC}$ in flow.

Prediction of shear thinning and transient response characteristics.

Identification of structural basis for $ au_{LC}$ and duality.

Abstract

Understanding the flow behaviors of supercooled liquids presents a major challenge in liquid-state physics due to the strong nonlinearity and rich phenomena. To unravel this complexity, we introduce the concept of local configurational relaxation time $\tau_\rm{LC}$, which allows us to embody the solid-liquid duality, proposed by Maxwell for phenomenologically describing materials' response to external load, 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 shear 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 with a wide range of shear rates, 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 in terms of activations from energy basins that are facilitated by shear. This 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.