Thermodynamic Interpretation of the Meyer-Neldel Rule Explains Temperature Dependence of Ion Diffusion in Silicate Glass.

Abstract

We study the temperature-dependent diffusion of many types of metal and semimetal ions in soda-lime glass using thermal relaxation ion spectroscopy, a technique that provides an electrical readout of thermally activated diffusion of charge carriers driven by built-in concentration gradients and electric fields. We measure the temperature of the onset of the motion, relevant to the long term storage of radioactive elements. We demonstrate the unique behavior of silver in soda-lime glass, enabling a thermal battery with rapid discharge of stored energy above a threshold temperature. We show that the Meyer-Neldel rule applies when comparisons of temperature-dependent diffusion rates are made between related measurements on one sample or between the same measurements on related samples. The results support a thermodynamic interpretation of the Meyer-Neldel rule as an enthalpy-entropy correlation where the Meyer-Neldel temperature (T_{MN}) is the temperature that enables liquidlike, barrier-free motion of the ions, with an upper limit set by the melting point of the host medium. This interpretation explains the observed reduction in T_{MN} by built-in electric fields in depletion layers and why the upper limit for T_{MN} for all ions is set by the glass transition temperature.