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Local environment of iron and uranium ions in vitrified iron phosphate glasses studied by Fe K and U LIII-edge x-ray absorption fine structure spectroscopy

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Abstract

The local structure of iron and uranium ions in a series of iron phosphate glasses with the general composition (40 – x)Fe2O3–xUO2–60P2O5 and (1–x–y)(40Fe2O3–60P2O5)– xUO2–y(Na2O or CaO) was investigated using Fe K-edge and U LIII-edge x-ray absorption fine structure spectroscopy. Replacing Fe2O3 by UO2 in the glass caused more distortion in the coordination environment of Fe(III) ions. Extended x-ray absorption fine structure fits revealed that the Fe–P bonds observed in the base glass also existed in all the waste-loaded glasses. X-ray absorption near-edge structure showed that the uranium ions were predominantly present as U(IV) in the glasses. Uranium ions were coordinated to approximately 8 ± 1 oxygen atoms and 2.5 ± 0.6 phosphorus atoms at an average distance of 2.47 ± 0.02 and 3.8 ± 0.02 Å, respectively. There were no Fe–U or U–Fe neighbors observed, indicating that uranium ions occupied voids in the glass away from the PO4 units. These conclusions were supported by Mössbauer, x-ray photoelectron, and Raman spectroscopic data.

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Author notes

  1. M. Karabulut

    Present address: Graduate Center For Materials Research, University of Missouri-Rolla, MO, 1870 Miner Circle, 65409-1170, Rolla, USA

Authors and Affiliations

  1. Department of Physics and Graduate Center for Materials Research, University of Missouri–Rolla, Missouri, 65409–1170, Rolla, USA

    M. Karabulut

  2. Department of Physics, University of Kafkas, Kars, Turkey

    G. K. Marasinghe, C. S. Ray, D. E. Day & G. D. Waddill

  3. Analytical and Nuclear Chemistry Division, Lawrence Livermore National Laboratory, California, 94551, Livermore, USA

    P. G. Allen

  4. Chemical Sciences Division, The Glenn T. Seaborg Center, Lawrence Berkeley National Laboratory, California, 94720, Berkeley, USA

    C. H. Booth, J. J. Bucher, D. L. Caulder & D. K. Shuh

  5. Materials Science Division, Argonne National Laboratory, Illinois, 60439, Argonne, USA

    M. Grimsditch & M-L. Saboungi

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  1. M. Karabulut
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Correspondence to M. Karabulut.

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Karabulut, M., Marasinghe, G.K., Ray, C.S. et al. Local environment of iron and uranium ions in vitrified iron phosphate glasses studied by Fe K and U LIII-edge x-ray absorption fine structure spectroscopy. Journal of Materials Research 15, 1972–1984 (2000). https://doi.org/10.1557/JMR.2000.0284

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