Effect of Ag addition on the thermal characteristics and structural evolution of Ag-Cu-Ni ternary alloy nanoclusters: Atomistic simulation study

Abstract

Atomic-scale compositional variation in Ag contents across Ag-Cu-Ni alloy upon being subjected to repeated annealing cycles is shown to result in significant differences in the structure and the thermal stability of ternary alloy nanoclusters. Molecular dynamics (MD) simulations employing quantum Sutton--Chen potentials were used to investigate the effect of Ag addition on the thermal characteristics of Ag-Cu-Ni ternary alloy nanoclusters of 4-nm diameter. The initial configurations were generated using Monte Carlo simulations and comprise surface-segregated structures with the lowest surface energy component, Ag, occupying low coordination sites such as corners, edges, and faces. A compositional oscillation between the Cu and Ni atoms was observed for layers beneath the surface which transitions into a bulk alloy composition at the core. We find that the Cu-Ni binary alloys on being subjected to annealing schedules demonstrated an increase in thermal stability, as indicated by the increase in melting points. The annealed configurations of the Ag-Cu-Ni ternary alloy, on the other hand, showed a nonmonotonic behavior. For Ag compositions less than 20%, we observe an initial increase in melting point followed by a decrease in the third cycle. For higher Ag compositions (>20%), we observe a decrease in melting point with annealing; the rate of decrease is strongly correlated to the Ag composition in the alloy. Cu-Ni nanoclusters having 50% Cu showed a transition from an initial icosahedral to a cuboctahedron-like structure whereas Ag-rich Ag-Cu-Ni ternary alloys showed a transition from icosahedral to an amorphous structure. Compositional analysis based on radial distribution functions and density profiles indicate that these transitions were dependent on the distribution of the alloying elements in the nanocluster. Calculated root-mean-square displacements and diffusion coefficients indicate that the rate of mixing of Ag increases with Ag content in the Ag-Cu-Ni ternary alloy. Ternary alloys show heterogeneous melting during the first heating cycle followed by a bulk-like melting during the subsequent annealing cycles. The simulation results are consistent with available experimental studies.