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Electrical conductivity and the nature of charge carriers in glasses of the Tl2O-B2O3 system

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Abstract

The concentration dependence of the electrical conductivity of glasses in the Tl2O-B2O3 system is studied. The nature of charge carriers in this system is experimentally investigated for the first time. It is demonstrated using the Hittorf, Tubandt, and Hebb-Liang-Wagner techniques and the Faraday law that neither Tl+ ions nor electrons are involved in the electricity transport. The verification of the Faraday law does not reveal the presence of thallium in the amalgam of the cathode or a change in the sample weight after electrolysis, to within the experimental error. This allows one to make the inference that protons can be charge carriers in glasses of the Tl2O-B2O3 system. It is shown using extended X-ray absorption fine structure (EXAFS) spectroscopy that Tl3+ ions and thallium Tl0 reduced to the metallic state are absent in the structure of the glasses under investigation. This means that thallium in glasses of the Tl2O-B2O3 system occurs only in the form of Tl+ ions. The analysis of the IR spectroscopic data leads to only a qualitative conclusion that the water content in the glasses insignificantly increases with an increase in the thallium oxide content. An increase in the electrical conductivity of glasses in the Tl2O-B2O3 system with an increase in the thallium oxide content is explained by the increase in the number of protons formed upon dissociation of H+[BO4/2]− structural-chemical units, because their concentration increases with increasing Tl2O content. In the structure of boron oxide, impurity hydrogen enters predominantly into the composition of H+[O2/2BO−] structural-chemical units, for which the dissociation energy is higher than that for the H+[BO4/2]− structural-chemical units. The increase in the concentration of H+[BO4/2]− structural-chemical units is accompanied by the increase in the number of dissociated protons, which are charge carriers in glasses of the Tl2O-B2O3 system.

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Authors and Affiliations

  1. St. Petersburg State University, Universitetskii pr. 2, Petrodvorets, 198504, Russia

    I. A. Sokolov, I. V. Murin & V. D. Khripun

  2. St. Petersburg State Technological Institute (Technical University), Moskovskii pr. 26, St. Petersburg, 198013, Russia

    N. A. Valova, Yu. K. Startsev & A. A. Pronkin

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  1. I. A. Sokolov
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  2. I. V. Murin
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  5. Yu. K. Startsev
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  6. A. A. Pronkin
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Correspondence to Yu. K. Startsev.

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Original Russian Text © I.A. Sokolov, I.V. Murin, V.D. Khripun, N.A. Valova, Yu.K. Startsev, A.A. Pronkin, 2008, published in Fizika i Khimiya Stekla.

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Sokolov, I.A., Murin, I.V., Khripun, V.D. et al. Electrical conductivity and the nature of charge carriers in glasses of the Tl2O-B2O3 system. Glass Phys Chem 34, 227–239 (2008). https://doi.org/10.1134/S1087659608030012

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  • DOI: https://doi.org/10.1134/S1087659608030012

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