Solidification fronts in supercooled liquids: how rapid fronts can lead to disordered glassy solids

TL;DR

This paper investigates the speed of solidification fronts in supercooled liquids using density functional theory, revealing how rapid fronts can produce disordered glassy solids instead of well-ordered crystals.

Contribution

It introduces a method to calculate solidification front speeds and shows how deep quenches lead to disorder, advancing understanding of glass formation in supercooled liquids.

Findings

Fast fronts can produce disordered glasses instead of crystals

Wavelength selection depends on quench depth, affecting order

Disorder increases with random initial conditions

Abstract

We determine the speed of a crystallisation (or more generally, a solidification) front as it advances into the uniform liquid phase after the system has been quenched into the crystalline region of the phase diagram. We calculate the front speed by assuming a dynamical density functional theory model for the system and applying a marginal stability criterion. Our results also apply to phase field crystal (PFC) models of solidification. As the solidification front advances into the unstable liquid phase, the density profile behind the advancing front develops density modulations and the wavelength of these modulations is a dynamically chosen quantity. For shallow quenches, the selected wavelength is precisely that of the crystalline phase and so well-ordered crystalline states are formed. However, when the system is deeply quenched, we find that this wavelength can be quite different from that of the crystal, so that the solidification front naturally generates disorder in the system. Significant rearrangement and ageing must subsequently occur for the system to form the regular well-ordered crystal that corresponds to the free energy minimum. Additional disorder is introduced whenever a front develops from random initial conditions. We illustrate these findings with results obtained from the PFC.