Composition dependence of the glass forming ability in binary mixtures: The role of demixing entropy

TL;DR

This study investigates how the composition of binary mixtures influences their ability to form glasses, highlighting the roles of demixing entropy, structural frustration, and energetics in preventing crystallization.

Contribution

It reveals the non-monotonic dependence of glass forming ability on composition and distinguishes the effects of demixing entropy and local structural frustration.

Findings

Lower free energy for CsCl nucleus formation correlates with increased demixing.

Maximum entropic penalty occurs near the Kob-Anderson model composition.

Crystallization tendencies differ between systems due to energetics and dynamics.

Abstract

We present a comparative study of the glass forming ability of binary systems with varying composition, where the systems have similar global crystalline structure (CsCl+fcc). Biased Monte Carlo simulations using umbrella sampling technique shows that the free energy cost to create a CsCl nucleus increases as the composition of the smaller particles are decreased. We find that the systems with comparatively lower free energy cost to form CsCl nucleus exhibit more pronounced pre-crystalline demixing near the liquid/crystal interface. The structural frustration between the CsCl and fcc crystal demands this demixing. We show that closer to the equimolar mixture the entropic penalty for demixing is lower and a glass forming system may crystallize spontaneously when seeded with a nucleus. This entropic penalty as a function of composition shows a non-monotonic behavior with a maximum at a composition similar to the well known Kob-Anderson (KA) model. Although the KA model shows the maximum entropic penalty and thus maximum frustration against CsCl formation, it also shows a strong tendency towards crystallization into fcc lattice of the larger "A" particles which can be explained from the study of the energetics. Thus for systems closer to the equimolar mixture although it is the requirement of demixing which provides their stability against crystallization, for KA model it is not demixing but slow dynamics and structural frustration caused by the locally favored structure around the smaller "B" particles which make it a good glass former. Although the glass forming binary systems studied here are quite similar, differing only in composition, we find that their glass forming ability cannot be attributed to a single phenomena.