Structural effects on diffusion in metallic glasses: The pressure dependence of Ni diffusion in as-quenched and relaxed Co42Zr58

In order to clarify the role of thermal defects in diffusion in metallic glasses, we have measured the temperature and pressure dependences of diffusion of Ni, a probe for Co, in relaxed and non-relaxed amorphous Co₄₂Zr₅₈ alloys by means of the tracer technique in combination with secondary-ion mass spectroscopy. For the relaxed state, the activation energy and the pre-factor are Q _{= (}1:65=0:08₎ eV and D _{0 =} 2:4+3:9 10-6m2 s-1 respectively. The pressure - 1:9 dependence yields an activation volume V _{act = (}0:66 0:15₎Omega, with Omega being the average atomic volume of the alloy. This value is similar to activation volumes in crystalline materials and is indicative of diffusion via thermally generated defects. Unlike monovacancies in crystals, these defects appear to be spread out, judging from recent isotope-effect measurements. Comparison with literature data shows that the activation volume and hence the diffusion mechanism in metallic glasses clearly depend on the structure and composition even for the very same component. The activation volume in the as-quenched state was found to be _{( )} ^{0:93 0:25 Omega.}