The glass-forming ability of binary Lennard-Jones systems

TL;DR

This study uses molecular dynamics simulations to analyze how particle size and cohesive energy differences influence the glass-forming ability of binary Lennard-Jones systems, revealing geometric and local order factors that determine glass formation.

Contribution

It introduces a quantitative framework linking cohesive energy differences and local structural order to glass-forming ability in binary Lennard-Jones mixtures.

Findings

Logarithmic critical cooling rate contours are ellipsoidal in parameter space.

Larger particles with higher cohesive energy improve glass-forming ability.

Mahalanobis distance and local chemical order predict glass-forming tendencies.

Abstract

The glass-forming ability (GFA) of alloys, colloidal dispersions, and other particulate materials, as measured by the critical cooling rate $R_c$, can span more than ten orders of magnitude. Even after numerous previous studies, the physical features that control the GFA are still not well understood. For example, it is well-known that mixtures are better glass-formers than monodisperse systems and that particle size and cohesive energy differences among constituents improve the GFA, but it is not currently known how particle size differences couple to cohesive energy differences to determine the GFA. We perform molecular dynamics simulations to determine the GFA of equimolar, binary Lennard-Jones (LJ) mixtures versus the normalized cohesive energy difference $\epsilon_\_$ and mixing energy $\bar \epsilon_{AB}$ between particles A and B. We find several important results. First, the $\log_{10} R_c$ contours in the $\bar \epsilon_{AB}$-$\epsilon_\_$ plane are ellipsoidal for all diameter ratios, and thus $R_c$ is determined by the Mahalanobis distance $d_M$ from a given point in the $\bar \epsilon_{AB}$-$\epsilon_\_$ plane to the center of the ellipsoidal contours. Second, LJ systems for which the larger particles have larger cohesive energy are generally better glass formers than those for which the larger particles have smaller cohesive energy. Third, $d_M(\epsilon_\_,\bar \epsilon_{AB})$ is determined by the relative Voronoi volume difference between particles and local chemical order $S_{AB}$, which gives the average fraction of nearest-neighbor B particles surrounding an A particle and vice-versa. In particular, the shifted Mahalanobis distance $d_M - d^0_M$ versus the shifted chemical order $S_{AB}-S_{AB}^0$ collapses onto a hyperbolic master curve for all diameter ratios.