Atomistic understanding of diffusion kinetics in nanocrystals from molecular dynamics simulations

作者:Wang Yun Jiang*; Gao Guo Jie J; Ogata Shigenobu
来源:Physical Review B, 2013, 88(11): 115413.


Understanding the grain size effect on diffusion in nanocrystals has been hampered by the difficulty of measuring diffusion directly in experiments. Here large-scale atomistic modeling is applied to understand the diffusion kinetics in nanocrystals. Enhanced short-circuit diffusivity is revealed to be controlled by the rule of mixtures for grain-boundary diffusion and lattice diffusion, which can be accurately described by the Maxwell-Garnett equation instead of the commonly thought Hart equation, and the thermodynamics of pure grain-boundary self-diffusion is not remarkably affected by varying grain size. Experimentally comparable Arrhenius parameters with atomic detail validate our results. We also propose a free-volume diffusion mechanism considering negative activation entropy and small activation volume. These help provide a fundamental understanding of how the activation parameters depend on size and the structure-property relationship of nanostructured materials from a physical viewpoint.

  • 出版日期2013-9-9