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Valence and Local Environment of Molybdenum in Aluminophosphate Glasses for Immobilization of High Level Waste from Uranium-Graphite Reactor Spent Nuclear Fuel Reprocessing

  • Sergey V. Stefanovsky (a1), Andrey A Shiryaev (a1), Michael B. Remizov (a2), Elena A. Belanova (a2), Pavel A. Kozlov (a2) and Boris F. Myasoedov (a3)...

Two Mo-bearing glasses considered as candidate forms for high level waste (HLW) a uranium-graphite reactor spent nuclear fuel (SNF) reprocessing were characterized. Incorporation of Mo in sodium aluminophosphate (SAP) glass increases its tendency to devitrification with segregation of orthophosphate phases. Valence state and local environment of Mo in the materials containing ∼2 wt.% MoO3 were determined by X-ray absorption fine structure (XAFS) spectroscopy. In the quenched samples composed of major vitreous and minor AlPO4 nearly all Mo is located in the vitreous phase as [Mo6+О6] units whereas in the annealed samples Mo is partitioned among vitreous and one or two orthophosphate crystalline phases in favor of the vitreous phase. Mo predominantly exists in a hexavalent state in distorted octahedral environment. Four oxygen ions are positioned at a distance of ∼1.71-1.73 Å and two - at a distance of 2.02-2.04 Å. Minor Mo(V) is also present as indicated by a response in EPR spectra with g ≈ 1.911-1.915.

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1. Belanova E.A., Remizov M.B., Aloy A.S., and Koltsova T.I., Problems Radiat. Safety (Russ.) [2], 3 (2014).
2. Belanova E.A., Remizov M.B., Aloy A.S., and Koltsova T.I., Problems Radiat. Safety (Russ.) [4], 27 (2012).
3. Pinet O., Dussossoy J.L., David C., and Fillet C., J. Nucl. Mater. 377, 307 (2008).
4. Dunnett B.F., Gribble N.R., Short R., Turner E., Steele C.J., and Riley A.D., Glass. Technol.: Eur. J. Glass Sci. Technol. A, 53, 166 (2012).
5. Do Quang R., Petitjean V., Hollebecque F., Pinet O., Flament T., and Prod’homme A., in Waste Management 2003 Conf. February 23-27, 2003, Tucson, AZ (2003).
6. Morris J.B., Chidley B.E., in: Management of Radioactive Wastes from the Nuclear Fuel Cycle. Vienna, IAEA (1976).
7. Grunewald W., Koschorke H., Weisenburger S, Zeh H., in: Radioactive Waste Management. Proc. Int. Conf. Seattle, 1620 May 1984. Vienna, IAEA, 2 (1984).
8. Gaudin C., Schuller S., Cormier L., Calas G., and Kroeker S., in: ATALANTE 2012. Abstracts (2012), p. 301.
9. Stefanovsky S.V., Phys. Chem. Mater. Treat. [2], 63 (1993).
10. Poirier G., Ottoboni F.S., Kassanjes F.C., Remonte A., Messaddeq Y., and Ribeiro S.J.L., J. Phys. Chem. 112, 4481 (2008).
11. Koudelka L., Rösslerová I., Holubová J., Mošner P., Montagne L., and Revel B., J. Non-Cryst. Solids, 357, 2816 (2011).
12. Marzouk S., Abo-Naf S.M., Hammam M., El-Gendy Y.A., and Hassan N.S., J. Appl. Sci. Res. 7, 935 (2011).
13. Da N., Grassmé O., Nielsen K.H., Peters G., Wondraczek L., J. Non-Cryst. Solids. 357, 2202 (2011).
14. Camara B., Lutze W., and Lux J., “An Investigation on the Valency State of Molybdenum in Glasses with and without Fission Products,” Scientific Basis for Nuclear Waste Management, ed. Northrup C.J.M. Jr. (Plenum Press, 1980) 2, pp. 93102.
15. Kawamoto Y., Clemens K., and. Tomozawa M., J. Amer. Ceram. Soc. 64, 292 (1981).
16. Kawamoto Y., Clemens K., and. Tomozawa M., and Warden J.T., Phys. Chem. Glasses 22, 110 (1981).
17. Horneber A., Camara B., and Lutze W., Mater. Res. Soc. Symp. Proc. 11, 279 (1982).
18. Schreiber H.D., J. Geophys. Res. 92, 9225 (1993).
19. Short R.J., Hand R.J., and Hyatt N.C., Mater. Res. Soc. Symp. Proc. 757, 141 (2002).
20. Calas G., Le Grand M., Galoisy L., and Ghaleb D., J. Nucl. Mater. 322, 15 (2003).
21. Short R.J., Hand R.J., Hyatt N.C., and Möbus G., J. Nucl. Mater. 340, 179 (2005).
22. Farges F., Siewert R., Brown G.E. Jr., Guesdon A., and Morin G., Canad. Miner. 44, 731 (2006).
23. Farges F., Siewert R., Ponader C.W., Brown G.E. Jr., Pichavant M., and Behrens H., Canad. Miner. 44, 755 (2006).
24. Schuller S., Pinet O., Granjiean A., and Blisson T., J. Non-Cryst. Solids 354, 296 (2008).
25. Caurant D., Majérus O., Fadel E., Quintas A., Gervais C., Charpentier T., and Neuville D., J. Nucl. Mater. 396, 94 (2010).
26. Landry R.J., J. Chem. Phys. 48, 1422 (1968).
27. Parke S. and Watson A.C., Phys. Chem. Glasses 10, 37 (1969).
28. Baucher J. and Parke S., “ESR and Optical Studies of Mo(V) in Phosphate Glasses,” Amorphous Materials, ed. Douglas R.W. and Ellis B. (Wiley, 1971) pp. 399404.
29. Kuzmin A. and Purans J., J. Phys. IV France 7, C2–971 (1997).
30. Khattak G.D., Salim M.A., Al-Harthi A.S., Thompson D.L., and Wenger L.E., J. Non-Cryst. Solids 212, 180 (1997).
31. Cozar O., Magdas D.A., and Ardelean I., J. Non-Cryst. Solids 354, 1032 (2008).
32. Saddeek Y.B. and Abo-Naf S.M., Archives of Acoustics, 37, 341 (2012).
33. Ravel B. and Newville M., J. Synchrotron Radiat. 12 537541 (2005).
34. Ankudinov A.L. and Rehr J.J., Phys. Rev. B 56 17121716 (1997).
35. Garif’yanov N.S. and Yafaev N.R., Sov. Phys. – JETF 16, 1392 (1963).
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