Effect of molar volume on the interaction between mobile ions in mixed alkali oxyfluoro vanadate glasses: An Electrical modulus analysis

TL;DR

This study investigates how molar volume influences ion interactions in mixed alkali vanadate glasses using electrical modulus analysis, revealing the effects of alkali composition on relaxation behavior and ion coupling.

Contribution

It introduces a detailed analysis of mixed alkali effects on ion relaxation using electrical modulus and fits the data with the Bergman equation, highlighting the role of molar volume and ion concentration.

Findings

Coupling between ions is optimal at 50 mol% alkali mixture.

Rubidium glasses show weaker ion coupling than lithium or mixed compositions.

Relaxation mechanisms vary with alkali concentration and temperature.

Abstract

Electrical modulus analysis of the frequency dependent conductivity data over the range from 100 Hz to 10 MHz and at temperature range of 140 oC to 300 oC were carried out on the mixed alkali vanadate glass samples having lithium and rubidium as alkali elements. The analysis of the data is done using Kohlrausch-Williams-Watts (KWW) equation which describes the relaxation behavior of the mobile species. We have used the Bergman equation (R. Bergman, J. Apl. Phys. 88 (2000) 1356.) for fitting the imaginary part of the electrical modulus. The stretching parameter beta derived from this fit shows a nonlinear variation with respect to alkali content which is attributed to mixed alkali effect. The variations of beta with respect to alkali element concentration is analyzed on the basis of alkali ion distance and molar volume. It is found that the coupling between the mobile ions is better at 50 mol percentage of the alkali mixture when compared to single alkali concentrations. It is observed that coupling between the ions are weak in case of all Rubidium glass than all Lithium or Lithium-Rubidium mixture, even though the alkali concentration is on the higher (30 mol percentage) side. The contributions from fast and slow types of relaxation mechanisms were determined. It again shows that at low concentrations of Rubidium ions, there exists a good coupling between alkali ions and contribute to a macroscopic relaxation time responsible for the stretching, whereas at high concentrations of Rubidium ions the relaxing sites decouple and relax with a microscopic relaxation time. A scaling of modulus spectra with respect to frequency shows that stretching parameter beta is slightly dependent on temperature.