Size effect on melting temperatures of alumina nanocrystals: Molecular dynamics simulations and thermodynamic modeling

N Joshi and N Mathur and T Mane and D Sundaram, COMPUTATIONAL MATERIALS SCIENCE, 145, 140-153 (2018).

DOI: 10.1016/j.commatsci.2017.12.064

Molecular dynamics (MD) simulations and thermodynamic analysis are conducted to investigate size effect on melting point of alumina nanocrystals. Different geometries including spherical and cubic particles, planar thin films, and spherical shells are considered. The atomic interactions in MD simulations are captured using Vashishta et al.'s potential function. Thermophysical properties of concern such as the bulk melting point, latent heat, density, and surface free energy are calculated using MD simulations and fed as inputs to the thermodynamic models. Predictions of MD simulations are compared with those of thermodynamic melting models. For all cases, heterogeneous melting is observed, where nucleation of the melt phase occurred at the free surface and the melting front propagated into the interior regions of the crystal. Results suggest that the melting point drops sharply below a threshold particle size, which is a function of the geometry. The threshold particle size of spherical particles is greater than that of planar films. Melting point predictions are quite sensitive to the choice of thermodynamic model and thermo-physical property values. To ascertain the effects of curvature and core size on shell melting point, melting points of planar semi-infinite films and spherical shells are calculated and compared. For particle sizes of concern to practical applications (similar to 100 nm or greater), shell melting point is nearly independent of core size and the semi-infinite planar film approximation is reasonable to estimate the melting point of alumina shells. In this size regime, melting points of 2-4 nm thick spherical oxide shells vary roughly in the range of 1800-2350 K, which is relatively close to the bulk melting point. Results of the present study do not indicate an enormous depression in the melting point, as the previous works suggest. This implies that the melting point depression of the oxide layer cannot fully describe the scatter in the measured ignition temperature of aluminum particles. (C) 2017 Elsevier B.V. All rights reserved.

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