Silver Diffusion and Clustering in Oxyfluoride Glasses Investigated by Molecular Dynamics Simulations

Glasses with compositions (97 – x )[PbF 2 :GeO 2 ]–3Al 2 O 3 – x Ag 2 O, with the PbF 2 :GeO 2 ratio equals to 1.5 and x varying from 0 to 3%, form silver surface films after thermal treatment near the glass transition temperature. The NPT molecular dynamics simulations of a glass composition 56.4PbF 2 –37.6GeO 2 –3Al 2 O 3 –3Ag 2 O have been performed, where 0, 20, 40, 60, and 100% of the Ag + ions were reduced to Ag by the fluoride ions. The simulations showed that the silver atoms aggregate into clusters of increasing numbers and sizes as the silver atoms content increases. In addition, the silver atoms diffusion coefficients are at least one order of magnitude larger than the fastest ion in the matrix. These results are consistent with the rapid formation of the metallic surface film observed experimentally.