Factors correlating to enhanced surface diffusion in metallic glasses

The enhancement of surface diffusion (D_S) over the bulk (D_V) in metallic glasses (MGs) is well documented and likely to strongly influence the properties of glasses grown by vapor deposition. Here, we use classical molecular dynamics (MD) simulations to identify different factors influencing the enhancement of surface diffusion in MGs. MGs have a simple atomic structure and belong to the category of moderately fragile glasses that undergo pronounced slowdown of bulk dynamics with cooling close to the glass transition temperature (T_g). We observe that D_S exhibits a much more moderate slowdown compared to D_V when approaching T_g, and D_S/D_V at T_g varies by two orders of magnitude among the MGs investigated. We demonstrate that both the surface energy and the fraction of missing bonds for surface atoms show good correlation to D_S/D_V, implying that the loss of nearest neighbors at the surface directly translates into higher mobility, unlike the behavior of network-bonded and hydrogen-bonded organic glasses. Fragility, a measure of the slowdown of bulk dynamics close to T_g, also correlates to D_S/D_V, with more fragile systems having larger surface enhancement of mobility. The deviations observed in the fragility–D_S/D_V relationship are shown to be correlated to the extent of segregation or depletion of the mobile element at the surface. Finally, we explore the relationship between the diffusion pre-exponential factor (D₀) and the activation energy (Q) and compare it to a ln(D₀)–Q correlation previously established for bulk glasses, demonstrating similar correlations from MD as in the experiments and that the surface and bulk have very similar ln(D₀)–Q correlations.