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Structural investigations of V2O5–P2O5–CaO glass system by FT-IR and EPR spectroscopies

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Abstract

xV2O5·(100 − x)[0.7P2O5·0.3CaO] glass system was obtained for 0 ≤ x ≤ 35 mol% V2O5. In order to obtain information regarding their structure, several techniques such as X-Ray diffraction, FT-IR, and EPR spectroscopies were used. X-Ray diffraction patterns of investigated samples are characteristic of vitreous solids. FT-IR spectra of 0.7P2O5·0.3CaO glass matrix and its deconvolution show the presence in the glass structure of all structural units characteristic to P2O5. Their number are increasing for x ≤ 3 mol% V2O5 then, for higher content of vanadium ions, the number of phosphate structural units are decreasing leading to a depolymerization of the structure. The structural units characteristic to V2O5 were not evidenced but their contribution to the glass structure can be clearly observed. EPR revealed a well resolved hyperfine structure (hfs) typical for vanadyl ions in a C4v symmetry for x ≤ 3 mol% V2O5. For 5 < x < 20 mol% V2O5 the spectra show a superposition of two EPR signals one due to a hfs structure and another consisting of a broad line typical for associated V4+–V4+ ions. For x ≥ 20 mol% V2O5 only the broad line can be observed. The composition dependence of the line-width suggests the presence of dipole–dipole interaction between vanadium ions up to x ≤ 5 mol% V2O5 and superexchange interactions between vanadium ions for x > 5 mol% V2O5.

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Acknowledgements

The authors would like to thank Dr. E. Indrea from National Institute for Research and Development on Isotopic and Molecular Technologies—INCDTIM, Cluj-Napoca, Romania for performing X-ray measurements on the investigated samples.

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Authors and Affiliations

  1. University of Agricultural Science and Veterinary Medicine, Calea Manastur 3-5, 400372, Cluj-Napoca, Romania

    R. Stefan

  2. INCDO-INOE 2000, Research Institute for Analytical Instrumentation, ICIA Cluj-Napoca Subsidiary, Donath Street 67, 400293, Cluj-Napoca, Romania

    D. Simedru

  3. National Institute for Research and Development on Isotopic and Molecular Technologies—INCDTIM, Donath Street 65-103, 400293, Cluj-Napoca, Romania

    A. Popa

  4. Faculty of Physics, Babes-Bolyai University, Mihail Kogalniceanu Street 1, 400084, Cluj-Napoca, Romania

    I. Ardelean

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  1. R. Stefan
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  2. D. Simedru
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  4. I. Ardelean
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Correspondence to D. Simedru.

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Stefan, R., Simedru, D., Popa, A. et al. Structural investigations of V2O5–P2O5–CaO glass system by FT-IR and EPR spectroscopies. J Mater Sci 47, 3746–3751 (2012). https://doi.org/10.1007/s10853-011-6225-x

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