Dissipation in a Crystallization Process

TL;DR

This paper investigates the irreversibility and heat dissipation during crystallization from a supersaturated melt, identifying regimes of slow and rapid crystallization and their effects on system resistance.

Contribution

It introduces an intrinsic compression rate that distinguishes quasi-static from rapid crystallization regimes and analyzes heat dissipation in non-equilibrium crystallization processes.

Findings

Dissipated heat grows linearly with compression rate in quasi-static regime.

Rapid crystallization opens relaxation channels, reducing resistance.

Higher non-equilibrium crystal structures form at faster rates.

Abstract

We discuss the crystallization process from the supersaturated melt in terms of its non-equilibrium properties. In particular, we quantify the amount of heat that is produced irreversibly when a suspension of hard spheres crystallizes. This amount of heat can be interpreted as arising from the resistance of the system against undergoing phase transition. We identify an intrinsic compression rate that separates a quasi-static regime from a regime of rapid crystallization. In the former the disspated heat grows linearly in the compression rate. In the latter the system crystallizes more easily, because new relaxation channels are opened, at the cost of forming a higher fraction of non-equilibrium crystal structures. In analogy to a shear-thinning fluid, the system shows a decreased resistance when it is driven rapidly.