Separating Geometric and Diffusive Contributions to the Surface Nucleation of Dislocations in Nanoparticles.

While metal nanoparticles are widely used, their small size makes them mechanically unstable. Extensive prior research has demonstrated that nanoparticles with sizes in the range of 10-50 nm fail by the surface nucleation of dislocations, which is a thermally activated process. Two different contributions have been suggested to cause the weakening of smaller particles: first, geometric effects such as increased surface curvature reduce the barrier for dislocation nucleation; second, surface diffusion happens faster on smaller particles, thus accelerating the formation of surface kinks which nucleate dislocations. These two factors are difficult to disentangle. Here we use in situ compression testing inside a transmission electron microscope to measure the strength and deformation behavior of platinum particles in three groups: 12 nm bare particles, 16 nm bare particles, and 12 nm silica-coated particles. Thermodynamics calculations show that, if surface diffusion were the dominant factor, the last two groups would show equal strengthening. Our experimental results refute this, instead demonstrating a 100% increase in mean yield strength with increased particle size and no statistically significant increase in strength due to the addition of a coating. A separate analysis of stable plastic flow corroborates the findings, showing an order-of-magnitude increase in the rate of dislocation nucleation with a change in particle size and no change with coating. Taken together, these results demonstrate that surface diffusion plays a far smaller role in the failure of nanoparticles by dislocations as compared to geometric factors that reduce the energy barrier for dislocation nucleation.