Real-time observation of the isothermal crystallization kinetics in a deeply supercooled liquid

TL;DR

This study uses time-resolved neutron diffraction to observe and model the isothermal crystallization process of supercooled GeO₂ at 1100 K, revealing a predator-prey-like mechanism between crystalline and amorphous phases.

Contribution

First direct real-time observation and quantitative modeling of deep supercooled GeO₂ crystallization kinetics using neutron diffraction.

Findings

Crystallization involves continuous reorganization towards alpha-quartz phase.

Crystalline domains form within a residual amorphous matrix.

A predator-prey-like mechanism governs the crystallization process.

Abstract

Below the melting temperature $T_m$ crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below $T_m$, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature $T_g$. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototypical strong glassformer GeO$_2$ in the deep supercooled liquid at 1100 K, about half-way between $T_m$ and $T_g$. The crystallization process has been observed through time-resolved neutron diffraction for about three days. Data show a continuous reorganization of the amorphous structure towards the alpha-quartz phase with the final material composed by crystalline domains plunged into a low-density, residual amorphous matrix. A quantitative analysis of the diffraction patterns allows determining the time evolution of the relative fractions of crystal and amorphous, that was interpreted through an empirical model for the crystallization kinetics. This approach provides a very good description of the experimental data and identifies a predator-prey-like mechanism between crystal and amorphous, where the density variation acts as blocking barrier.