Diffusion in Metallic Glasses and Supercooled Melts

Diffusion in metallic glasses and in the supercooled liquid state is of considerable interest not only from the technological point of view but also in terms of fundamental science, particularly in connection with the glass transition. Within the framework of the mode coupling theory the glass transition is a kinetic phenomenon characterized by the arrest of viscous flow at a critical temperature Tc well above the calorimetric glass transition temperature Tg. Below Tc the theory predicts cooperative hopping processes. We present results from isotope effect measurements which indeed confirm the highly collective nature of diffusion in metallic glasses and suggest cooperative hopping processes to be closely related to the universal low-frequency excitations as observed in recent molecular dynamic simulations. In accord with the mode coupling scenario these cooperative hopping processes are also observed in the supercooled liquid state of the new bulk metallic glasses well above Tg. The reported kink in the Arrhenius plot for diffusion of various elements is shown to be related to structural changes above Tg, e.g., an increase in free volume as probed by positron annihilation, but not to a change in the diffusion mechanism. Measurements of the activation volume of diffusion indicate that, depending on the structure of the glass, cooperative hopping may take place without assistance of thermally generated defects or via delocalized thermal defects. Moreover, we provide evidence of the existence of an opposite Kirkendall effect in interdiffusion between certain amorphous alloys that combine slow diffusion via thermal defects and fast direct diffusion.