Hostname: page-component-7479d7b7d-767nl Total loading time: 0 Render date: 2024-07-12T08:03:12.847Z Has data issue: false hasContentIssue false
  • English
  • Français

XAFS of Pu and Hf LIII Edge in Lanthanide-Borosilicate Glass

Published online by Cambridge University Press:  15 February 2011

A.A. Shiryaev ,
Ya.V. Zubabichus ,
S.V. Stefanovsky ,
A.G. Ptashkin  and
J.C. Marra
A.A. Shiryaev
Affiliation:
Institute of Crystallography RAS, Leninskii pr. 59, Moscow 119333, Russia
Ya.V. Zubabichus
Affiliation:
RRC “Kurchatov Institute”, Kurchatov sq. 1, Moscow, Russia
S.V. Stefanovsky
Affiliation:
SIA Radon, 7 Rostovskii lane 2/14, Moscow 119121, Russia
A.G. Ptashkin
Affiliation:
SIA Radon, 7 Rostovskii lane 2/14, Moscow 119121, Russia
J.C. Marra
Affiliation:
Savannah River National Laboratory, Aiken 29808 SC, USA
Get access

Abstract

Lanthanide-Borosilicate (LaBS) glass capable to dissolve up to ∼10 wt.% PuO2 is designed for immobilization of plutonium-bearing wastes. The sample of LaBS glass with a target chemical composition (wt %): 9.0 Al2O3, 11.8 B2O3, 12.2 Gd2O3, 6.3 HfO2, 17.2 La2O3, 13.6 Nd2O3, 9.5 PuO2, 18.1 SiO2, 2.3 SrO was prepared from PuO2 powder and mechanically activated mixture of chemicals at 1500 °C. The obtained product was visually homogeneous. Xraydiffraction of the as-prepared glass showed that it mostly consists of a vitreous phase withsmall amounts of crystalline PuO2 (or PuO2-HfO2 solid solution with minor HfO2), britholite andan oxide with a fluorite structure and a composition close to GdHfO1.75. The crystalline fractionincreased after storage for ∼1 year. Magnitude of the FT of EXAFS spectrum at Pu LIII edgeshows that the peak due to first coordination sphere is much more intense than that of the secondshell. This indicates that though some Pu entered crystalline phases (mainly distorted PuO2), itsmajor fraction remained in the vitreous phase. Fit of the spectrum (R-factor = 0.02) gives thefollowing distances: R (Pu-O1)1 = 1.98 (σ = 0.04), R (Pu-O1)2 = 2.18 (σ = 0.04), R (Pu-O1)3= 2.35, R (Pu-Pu) = 3.72 (σ = 0.04), R (Pu-O2) = 4.4 (σ = 0.06). Oxygen environment ofthe Pu4+ ions in the vitreous phase resembles axially squeezed tetragonal pyramid with acoordination number ∼5. The distances ∼2.35 and ∼4.4 correspond to the pairs Pu-O in thefirst and the second shells in the crystalline PuO2. The distance ∼3.72 corresponds to the Pu-Pu and/or Pu-M (M = Ln, Hf) distances. EXAFS spectra of Hf show that Hf is present mostly in thevitreous phase with major neighbors at 2.17 and ∼3.2 A.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1193: Scientific Basis for Nuclear Waste Management XXXIII , 2009 , 259
Copyright
Copyright © Materials Research Society 2009

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1 Bibler, N. E., Ramsey, W. G., Meaker, T. F. and Pareizs, J. M., in Scientific Basis for Nuclear Waste Management – XIX, edited by Murphy, W.M. and Knecht, D.A., (Mater. Res. Soc. Symp. Proc. 412, Pittsburgh, PA, 1996) pp. 65–70.Google Scholar
2 Veal, B. W., Mundy, J. N. and Lam, D. J., in Handbook of the Physics and Chemistry of Actinides, edited by Freeman, A.J. and Lander, G.H., (Elsevier Science Publishers B.V., 1987) pp. 271–309.Google Scholar
3 Strachan, D. M., Bakel, A. J., Buck, E. C., Chamberlain, D. B., Fortner, J. A., Mertz, C. J., Wolf, S. F., Bourcier, W. F., Ebbinghaus, B. B., Shaw, H. F., Konynenburg, R. A. Van, McGrail, B. P., Vienna, J. D., Marra, J. C. and Peeler, D. K., in Waste Management '98 Conf. (Laser Options Inc., Tucson, AZ, 1998). CD-ROM.Google Scholar
4 Peeler, D. K., Meaker, T. F. and Reamer, I. A., Proc. 3-rd Top. Meet. DOE Spent Nucl. Fuel and Fissile Mater. Manag. (American Nuclear Society, 1998). CD-ROM.Google Scholar
5 Fortner, J. A., Mertz, C. J., Bakel, A. J., Finch, R. J. and Chamberlain, D. B., in Scientific Basis for Nuclear Waste Management – XXIII, edited by Smith, R.W. and Shoesmith, D.W., (Mater. Res. Soc. Symp. Proc. 608, Pittsburgh, PA, 2000) pp. 739–744.Google Scholar
6 Yudintsev, S. V., Stefanovsky, S. V. and Ewing, R. C., in Structural Chemistry of Inorganic Actinide Compounds, edited by Krivovichev, S.V., Burns, P.C. & Tananaev, I.G., (Elsevier B.V., 2007) pp. 457–493.Google Scholar
7 Marra, J. C., Crawford, C. L. and Bibler, N. E., Glass Fabrication and Product Consistency Testing of Lanthanide Borosilicate Frit X Composition for Plutonium Disposition (WSRC-STI-2006-00318. SRNL, 2006).Google Scholar
8 Maslakov, K. I., Stefanovsky, S. V., Teterin, A.Yu., Teterin, Yu. A. and Marra, J. C., Glass Phys. Chem. 35, 1, 22 (2009).Google Scholar
9 Marra, J. C., Stefanovsky, S. V., Shiryaev, A. A., Zubavichus, Y. V. and Ptashkin, A. G., in Plutonium Futures – “The Science” 2008. Abstract Book pp. 102. (2008)Google Scholar
10 Stefanovsky, S., Shiryaev, A., Zubavichus, Y. and Marra, J., in Proc. 39emes Journees des Actinides (La Grande-Motte, France, 2009) CD-ROM.Google Scholar
11 Ravel, B. and Newville, M., J. Synchrotron Radiat., 12, 537 (2005).Google Scholar
12 Ankudinov, A. L. and Rehr, J. J., Phys. Rev., B 56, 1712 (1997).Google Scholar
13 Funke, H., Scheinost, A. C., Chukalina, M., Phys. Rev. B, 71, 094110 (2005)Google Scholar
14 Knapp, G. S., Veal, B. W., Paulikas, A. P., Mitchell, A. W., Lam, D. J. and Klippert, T. E., in EXAFS and Near Edge Structure – III. Springer Proceedings in Physics, Vol. 2, edited by Hodgson, K. O., Henner, B. and Penner-Hahn, J. E. (Springer, Berlin, 1984) pp. 305–307.Google Scholar
15 Heisbourg, G., Purans, J., Dacheux, N., Moisy, Ph. and Hubert, S., in Proc. 34emes Journees des Actinides. (Heidelberg, Germany, 2004) CD-ROM.Google Scholar
16 Conradson, S. D., Begg, B. D., Clark, D. L., Auwer, C. den, Ding, M., Dorhout, P. K., Espinosa-Faller, F. J., Gordon, P. L., Haire, R. G., Hess, N. J., Hess, R. F., Keogh, D. W., Morales, L. A., Neu, M. P., Paviet-Hartmann, P., Runde, W., Tait, C. D., Veirs, D. K., and Villella, P. M., J. Am. Chem. Soc. 126, 13443 (2004)Google Scholar