We present a corroborative
study of the structural characterization
of lithium-substituted barium vanadate glasses using Raman and electron
paramagnetic resonance (EPR) spectroscopy. Investigation of the thermal
and physical properties of these glasses showed a gradual increase
in the concentration of nonbridging oxygen. Raman and EPR analysis
gave an insight into the changing structure of the glasses. Both the
spectroscopic techniques confirmed that vanadium is present in the
glasses as distorted VO
6
octahedra. From the analysis of
both spectroscopic techniques, it is proposed that the lithium ion
prefers to occupy planar positions of the VO
6
octahedra,
thus reducing the tetragonal distortion and making the environment
around the network-forming unit in the glass matrix more homogeneous
as we increase the lithium content. The concentration of V
4+
showed a non-monotonic variation with an increase in Li
2
O as indicated by Raman studies and confirmed by EPR, which indicates
a structural change in the distorted VO
6
octahedra.
In this communication we report the fluorine ion dynamics in mixed alkali oxyfluro vanadate glasses. We have fabricated glasses with general formula, 40V2O5 -30BaF2 -(30-x) LiF -xRbF where x = 0,5, 10,15,20,25 and 30. We have measured the electrical conductivity using impedance spectroscopy technique Room temperature conductivity falls to 5 orders of magnitude from its single alkali values at 33 mol% of rubidium concentration. We have also estimated the distance between similar mobile ions using the density values. Assuming this distance as the hopping distance between the similar ions we have estimated the anionic (Fluorine ion in our case) conductivity. It is observed that the fluorine ion dynamics mimics the mixed alkali effect and scales as the onset frequency f0.
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