Grain boundary evolution in nanoparticles

Abstract: Grain boundary evolution is a key dynamical process that enables structural rearrangements in nanoparticles and drives them towards low energy configurations. Grain boundaries can also enhance catalytic properties, making it important to understand the elementary processes underlying their evolution for grain boundary engineering in nanoparticles. Compared with bulk materials, nanoparticles have additional rotational and translational degrees of freedom, can accommodate structural changes through shape relaxation, and grain boundaries terminate at free surfaces. However, the atomic-scale mechanisms of GB evolution under these less constrained conditions remain comparatively less understood than in bulk materials. Here, using atomistic simulations, we focus on low energy $\Sigma3$ (coherent twin boundary) and $\Sigma11$ grain boundaries, which are among the persistent compact GB structures that emerge during nanoparticle structural evolution. We identify two fundamental atomic displacements, column shift (C) and screw shift (S), that recur during the evolution of these grain boundaries and their junctions. These displacements occur through different atomic pathways and combine in different ways to generate grain boundary migration, structural transformations, and junction evolution. In particular, the same initial and final grain boundary configurations can be connected through different atomic pathways, and a column shift can occur either as a full shift or through disconnection kinks. C and S remain identifiable even when the grain boundary character changes, for example during a $\Sigma11$ to $\Sigma3$ transformation. An understanding of these elementary GB processes can help identify strategies to control grain boundary evolution and thereby engineer GB structures in nanoparticles.