Defect model for the mixed mobile ion effect

TL;DR

This paper introduces a defect-based model explaining the mixed mobile ion effect in glasses, emphasizing stress-induced defect formation and clustering that immobilizes ions and alters glass properties.

Contribution

The paper proposes a novel defect mechanism for the mixed mobile ion effect, linking stress-induced defect generation to ion immobilization and glass property changes.

Findings

Defect clustering causes ion immobilization.

Glass viscosity and Tg decrease with defect formation.

Model applicable to various ionic systems.

Abstract

This paper presents a new defect model for the mixed mobile ion effect. The essential physical concept involved is that simultaneous migration of two unlike mobile ions in mixed ionic glass is accompanied by expansion or contraction of the guest-occupied sites with distortion of surrounding glass matrix; in many cases, an intensity of the local stresses in glass matrix surrounding ionic sites occupied by foreign ions is much greater than, or at least comparable to the glass network binding energy. Hence, when the stress exceeds the breaking threshold, relaxation occurs almost immediately via the rupture of the bonds in the nearest glass matrix with generation of pairs of intrinsic structural defects. The specificity of the mechanism of defect generation leads to the clustering of negatively charged defects, so that rearranged sites act as high energy anion traps in glass matrix. This results in the immobilization of almost all minority mobile species and part of majority mobile species, so mixed mobile ion glass behaves as single mobile ion glass of much lower concentration of charge carriers. Generation of defects leads also to the depolymerization of glass network, which in turn results in the reduction of the glass viscosity and Tg as well as in the compaction of glass structure (thermometer effect). The magnitude of the mixed mobile ion effect is defined by the size mismatch of unlike mobile ions, their total and relative concentrations, the binding energy of the glass-forming network, and temperature. Although the proposed model is based upon the exploration of alkali silicate glass-forming system, the approach developed here can be easily adopted to other mixed ionic systems such as crystalline and even liquid ionic conductors.