Abstract
The oxidation states and coordination environment of iron ions in borosilicate glass used for the immobilization of iron-containing radioactive waste are studied by the methods of Mössbauer and Fourier transform IR spectroscopies. In homogeneous glass, containing no more than 50 wt % of waste oxides, iron is present in the form of Fe3+ and Fe2+ ions in octahedral coordination with oxygen. The phase of a iron-containing spinel, in which iron atoms with an oxidation number of +3 in the magnetically ordered state surrounded tetrahedrally by oxygen atoms (Fe3+O4) and iron in the two- and trivalent states in the octahedral oxygen environment (Fe3+O6 + Fe2+O6) are present, is precipitated at higher waste concentrations. Both the Mössbauer and IR spectra of glass crystalline materials are combinations of the corresponding individual spectra. The quantitative ratio of the doubly- and triply-charged iron ions in samples depends on the synthesis conditions. The maximum fraction of iron in the glass phase (about 28%) and, at the same time, the maximum fraction of the Fe3+ ions (91.3%) are observed in the sample prepared in a crucible by heating in a laboratory furnace in the air environment and subsequent quenching on a metal sheet.
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Dmitriev, S.A. and Stefanovskii, S.V., Obrashchenie s radioaktivnymi otkhodami (Radioactive Waste Management), Moscow: Mendeleyev University of Chemical Technology of Russia, 2000.
Bowan, B.W.II., Joseph, I., Matlack, K.S., Han, H., Kot, W.K., and Pegg, I.L., Test of simultaneous melt rate and waste loading enhancement for DWPF HLW streams, in Waste Management 2010 Conference, Phoenix, Arizona, Unired States, March 7–11, 2010, CDROM, ID 10254.
Stefanovsky, S.V., Nikonov, B.S., and Marra, J.C., Characterization of glassy materials for immobilization of radioactive waste with a high iron oxide content, Glass Phys. Chem., 2008, vol. 34, no. 3, pp. 292–299.
Kobelev, A.P., Stefanovsky, S.V., Lebedev, V.V., Polkanov, M.A., Knyazev, O.A., and Marra, J.C., Cold crucible vitrification of the savannah river site SB2 HLW surrogate at high waste loading, Eur. J. Glass Sci. Technol., Part A, 2009, vol. 50, no. 1, pp. 47–52.
Akatov, A.A., Nikonov, B.S., Omel’yanenko, B.I., Stefanovsky, S.V., and Marra, J.C., Structure of borosilicate glassy materials with high concentrations of sodium, iron, and aluminum oxides, Glass Phys. Chem., 2009, vol. 35, no. 3, pp. 245–259.
Stefanovsky, S.V., Kobelev, A.P., Lebedev, V.V., Polkanov, M.A., Suntsov, D.Y., and Marra, J.C., The effect of waste loading on the characteristics of borosilicate SRS SB4 waste glasses, in Proceedings of the ICEM’09/DECOM’09: The 12th International Conference on Environmental Remediation and Radioactive Waste Management, Liverpool, United Kingdom, October 11–15, 2009, Liverpool, 2009, CD-ROM, paper 16196.
Stefanovsky, S.V., Kobelev, A.P., Lebedev, V.V., Polkanov, M.A., Ptashkin, A.G., Knyazev, O.A., and Marra, J.C., in Proceedings of the ICEM’09/DECOM’09: The 12th International Conference on Environmental Remediation and Radioactive Waste Management, Liverpool, United Kingdom, October 11–15, 2009, Liverpool, 2009, CD-ROM, paper 16197.
Stefanovskii, S.V., Ptashkin, A.G., Knyazev, O.A., Stefanovskaya, O.I., Nikonov, B.S., Omel’yanenko, B.I., and Marra, Dzh.K., Vitrification of a simulator of highlevel wastes with a high content of sodium, iron, and aluminum in the cold crucible and the characterization of the product, Fiz. Khim. Obrab. Mater., 2010, no. 1, pp. 88–97.
Akatov, A.A., Nikonov, B.S., Omel’yanenko, B.I., Stefanovskaya, O.I., Stefanovsky, S.V., Suntsov, D.Yu., and Marra, J.C., Influence of the content of a surrogate of iron aluminate high-level wastes on the phase composition and structure of glassy materials for their immobilization, Glass Phys. Chem., 2010, vol. 36, no. 1, pp. 45–52.
Kobelev, A.P., Stefanovskii, S.V., Lebedev, V.V., Polkanov, M.A., Knyazev, O.A., Ptashkin, A.G., and Marra, J., Vitrification of a high-level iron-aluminate wastes simulator in a cold crucible, At. Energ., 2010, vol. 108, no. 1, pp. 33–39.
Stefanovsky, S.V., Nikonov, B.S., Omelyanenko, B.I., and Marra, J.C., Phase composition and elemental distribution in the vitrified U-bearing HLW surrogate, Mater. Res. Soc. Symp. Proc., 2010, vol. 1265, pp. 121–126.
Stefanovsky, S.V., Lebedev, V.V., Suntsov, D.Yu., Nikonov, B.S., Omel’yanenko, B.I., Akatov, A.A., and Marra, J.C., Influence of the content of radioactive wastes with high concentrations of aluminum, sodium, and iron oxides on the phase composition and structure of glassy materials prepared in a “cold crucible,” Glass Phys. Chem., 2010, vol. 36, no. 4, pp. 419–430.
Kobelev, A.P., Stefanovsky, S.V., Lebedev, V.V., Suntsov, D.Y., Polkanov, M.A., Knyazev, O.A., and Marra, J.C., Cold crucible vitrification of SRS SB4 HLW surrogate at high waste loadings, Ceram. Trans., 2010, vol. 222, pp. 91–103.
Glagolenko, Yu.V., Drozhko, E.G., and Rovnyi, S.I., The main directions of the solution of the environmental problems associated with the current and past activities of the FSUE PA “Mayak,” Vopr. Radiats. Bezop., 2006, no. 1, pp. 23–34.
Stefanovsky, S.V., Sorokaletova, A.N., Malinina, G.A., and Nikonov, B.S., The effect of waste loading on phase composition, structure and chemical durability of glassy materials for immobilization of high-sodium aluminum waste, in Proceedings of the Waste Management 2011 Conference, Phoenix, Arizona, United States, February 27–March 3, 2011, CD-ROM, ID 11475.
Lebedev, V.V., Shvetsov, S.Yu., Suntsov, D.Yu., Sorokaletova, A.N., and Stefanovskii, S.V., Development of the process of vitrification of high-level wastes from the PA “Mayak” using the IMCC technology, Vopr. Radiats. Bezop., 2011, no. 3, pp. 36–44.
Stefanovskii, S.V., Shiryaev, A.A., and Zubavichus, Ya.V., Structural state of iron in glasses and glass-crystalline materials for the immobilization of radioactive wastes with a high content of sodium and aluminum, Fiz. Khim. Obrab. Mater., 2012, no. 3, pp. 70–78.
Stefanovsky, S.V., Fox, K.M., Marra, J.C., Shiryaev, A.A., and Zubavichus, J.V., Structural features of high-Fe2O3 and high-Al2O3/Fe2O3 SRS HLW glasses, Eur. J. Glass Sci. Technol., Part B, 2012, vol. 53, no. 4, pp. 158–166.
Stefanovsky, S.V., Sorokaletova, A.N., and Nikonov, B.S., Phase composition and elemental partitioning in glass-ceramics containing high-Na/Al high level waste, J. Nucl. Mater., 2012, vol. 424, nos. 1–3, pp. 75–81.
Matsnev, M.E. and Rusakov, V.S., SpectrRelax: An application for Mössbauer spectra modeling and fitting, AIP Conf. Proc., 2012, vol. 1489, pp. 178–185.
Menil, F., Systematic trends of the 57Fe Mössbauer isomer shifts in (FeOn) and (FeFn) polyhedra: Evidence of a new correlation between the isomer shift and the inductive effect of the competing bond T–X(→ Fe) (where X is O or F and T any element with a formal positive charge), J. Phys. Chem. Solids, 1985, vol. 46, pp. 763–789.
Vandenberghe, R.E. and Grave, E., Mössbauer effect studies of oxidic spinels, in Mössbauer Spectroscopy Applied to Inorganic Chemistry, Long, G.J. and Grandjean, F., Eds., New York: Plenum, 1989, vol. 3, pp. 59–182.
Kolesova, V.A., Vibrational spectra and structure of alkali borate glasses, Fiz. Khim. Stekla, 1986, vol. 12, no. 1, pp. 4–13.
McMillan, P., Piriou, B., and Navrotsky, A., A Raman spectroscopic study of glasses along the joins silica–calcium aluminate, silica–sodium aluminate, and silica–potassium aluminate, Geochim. Cosmochim. Acta, 1982, vol. 46, pp. 2021–2037.
Anfilogov, V.N., Bykov, V.N., and Osipov, A.A., Silikatnye rasplavy (Silicate Melts), Moscow: Nauka, 2005.
Plyusnina, I.I., Infrakrasnye spektry mineralov (Infrared Spectra of Minerals), Moscow: Moscow State University, 1977.
Wong, J. and Angell, C.A., Glass Structure by Spectroscopy, New York: Marcell Dekker, 1976.
Nakamoto, K., Infrared and Raman Spectra of Inorganic and Coordination Compounds: Part A. Theory and Applications in Inorganic Chemistry, 6th ed., Hoboken, New Jersey, United States: Wiley, 2009.
Van De Leest, R.E. and Roozeboom, F., Iron-silicate glassy films by sol–gel conversion induced by rapid thermal processing, Mater. Res. Soc. Symp. Proc., 1998, vol. 525, pp. 351–358.
Mysen, B.O., Seifert, F., and Virgo, D., Structure and redox equilibria of iron-bearing silicate melts, Am. Mineral., 1980, vol. 65, pp. 867–884.
Dyer, M.D., A review of Mössbauer data on inorganic glasses: The effects of composition on iron valency and coordination, Am. Mineral., 1985, vol. 70, pp. 304–316.
Holland, D., Mekki, A., Gee, I., McConville, C.F., Johnson, J.A., Johnson, C.E., Appleyard, P., and Thomas, M., The structure of sodium iron silicate glass—A multi-technique approach, in Proceedings of the 33rd International Congress on Glass, San Francisco, California, United States, July 5–10, 1998, Choudhary, M.K., Huff, N.T., and Drummond, III, C.H., Eds., CD-ROM.
Kukkadapu, R.K., Li, H., Smith, G.L., Crum, J.D., Jeoung, J.-S., Poisl, W.H., and Weinberg, M.C., Mössbauer and optical spectroscopic study of temperature and redox effects on iron local environments in a Fedoped (0.5 mol % Fe2O3) 18Na2O–72SiO2 glass, J. Non-Cryst. Solids, 2003, vol. 317, pp. 301–318.
Wang, Z., Cooney, T.F., and Sharma, S.K., In situ structural investigation of iron-containing silicate liquids and glasses, Geochim. Cosmochim. Acta, 1995, vol. 59, pp. 1571–1577.
Bugaev, L., Farges, F., Rusakova, E., Sokolenko, A., Latokha, Ya., and Avakyan, L., Fe coordination environment in Fe(II)and Fe(III)-silicate glasses via the Fourier-transform analysis of Fe K-XANES, Phys. Scr., 2005, vol. T115, pp. 215–217.
Farges, F., Rossano, S., Lefrére, Y., Wilke, M., and Brown, Jr, G.E., Iron in silicate glasses: A systematic analysis of pre-edge, XANES, and EXAFS features, Phys. Scr., 2005, vol. T115, pp. 957–959.
Wilke, M., Farges, F., Partzsch, G.M., Schmidt, C., and Behrens, H., Speciation of Fe in silicate glasses and melts by in-situ XANES spectroscopy, Am. Mineral., 2007, vol. 92, pp. 44–56.
Hannant, O.M., Bingham, P.A., Hand, R.J., and Forder, S.D., A Mössbauer study of iron in vitrified wastes, Mater. Res. Soc. Symp. Proc., 2008, vol. 1107, pp. 215–222.
Goldman, D.S. and Bewley, D.E., Ferrous/ferric Mössbauer analysis of simulated nuclear waste glass with and without computer fitting, J. Am. Ceram. Soc., 1985, vol. 68, pp. 691–695.
Hunter, R.T., Edge, M., Kalivretenos, A., Brewer, K.M., Brock, N.A., Hawkes, A.E., and Fanning, J.C., Determination of the Fe2+/Fe3+ ratio in nuclear waste glasses, J. Am. Ceram. Soc., 1989, vol. 72, pp. 943–947.
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Original Russian Text © Ya.S. Glazkova, S.N. Kalmykov, I.A. Presnyakov, O.I. Stefanovskaya, S.V. Stefanovsky, 2015, published in Fizika i Khimiya Stekla.
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Glazkova, Y.S., Kalmykov, S.N., Presnyakov, I.A. et al. The structural state of iron in multicomponent aluminum iron borosilicate glass depending on their composition and synthesis conditions. Glass Phys Chem 41, 367–377 (2015). https://doi.org/10.1134/S1087659615040057
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DOI: https://doi.org/10.1134/S1087659615040057