Charge-coupled substituted garnets (Y 3–x Ca 0.5x M 0.5x )Fe₅O₁₂ (M = Ce, Th): Structure and stability as crystalline nuclear waste forms

Guo, Xiaofeng; Kukkadapu, Ravi K.; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Sutton, Stephen R.; Navrotsky, Alexandra

doi:10.1021/acs.inorgchem.5b00444

Charge-coupled substituted garnets (Y _3–x Ca _0.5x M _0.5x )Fe₅O₁₂ (M = Ce, Th): Structure and stability as crystalline nuclear waste forms

Journal Article · Mon Apr 20 00:00:00 EDT 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b00444· OSTI ID:1193657

Guo, Xiaofeng ^[1]; Kukkadapu, Ravi K. ^[2]; Lanzirotti, Antonio ^[3]; Newville, Matthew ^[3]; Engelhard, Mark H. ^[2]; Sutton, Stephen R. ^[3]; Navrotsky, Alexandra ^[4]

Univ. of California, Davis, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Chicago, Chicago, IL (United States)
Univ. of California, Davis, CA (United States)

The garnet structure has been proposed as a potential crystalline nuclear waste form for accommodation of actinide elements, especially uranium (U). In this study, yttrium iron garnet (YIG) as a model garnet host was studied for the incorporation of U analogs, cerium (Ce) and thorium (Th), incorporated by a charge-coupled substitution with calcium (Ca) for yttrium (Y) in YIG, namely, 2Y³⁺ = Ca²⁺ + M⁴⁺, where M⁴⁺ = Ce⁴⁺ or Th⁴⁺. Single-phase garnets Y_3–xCa_0.5xM_0.5xFe₅O₁₂ (x = 0.1–0.7) were synthesized by the citrate–nitrate combustion method. Ce was confirmed to be tetravalent by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. X-ray diffraction and ⁵⁷Fe–Mössbauer spectroscopy indicated that M⁴⁺ and Ca²⁺ cations are restricted to the c site, and the local environments of both the tetrahedral and the octahedral Fe³⁺ are systematically affected by the extent of substitution. The charge-coupled substitution has advantages in incorporating Ce/Th and in stabilizing the substituted phases compared to a single substitution strategy. Enthalpies of formation of garnets were obtained by high-temperature oxide melt solution calorimetry, and the enthalpies of substitution of Ce and Th were determined. The thermodynamic analysis demonstrates that the substituted garnets are entropically rather than energetically stabilized. This suggests that such garnets may form and persist in repositories at high temperature but might decompose near room temperature.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-06NA25396; SC0001089

OSTI ID:: 1193657

Alternate ID(s):: OSTI ID: 1178827
OSTI ID: 1182881

Report Number(s):: LA-UR--15-22411

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 8 Vol. 54; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (48)

Progress and new directions in high temperature calorimetry Navrotsky, Alexandra Physics and Chemistry of Minerals, Vol. 2, Issue 1-2 https://doi.org/10.1007/BF00307526	journal	January 1977
Yttrium iron garnet Donnerberg, Hansjörg Atomic Simulation of Electrooptic and Magnetooptic Oxide Materials, 165–190 https://doi.org/10.1007/BFb0109516	book	January 1999
Progress and new directions in high temperature calorimetry revisited Navrotsky, Alexandra Physics and Chemistry of Minerals, Vol. 24, Issue 3 https://doi.org/10.1007/s002690050035	journal	April 1997
Mössbauer Study of Ferrite-garnets as Matrixes for Disposal of Highly Radioactive Waste Products Rusakov, V. S.; Urusov, V. S.; Kovalchuk, R. V. Hyperfine Interactions, Vol. 164, Issue 1-4 https://doi.org/10.1007/s10751-006-9239-z	journal	July 2006
Effect of lanthanum ions on magnetic properties of Y3Fe5O12 nanoparticles Cheng, Zhongjun; Cui, Yuming; Yang, Hua Journal of Nanoparticle Research, Vol. 11, Issue 5 https://doi.org/10.1007/s11051-008-9501-1	journal	September 2008
Voigt-based methods for arbitrary-shape static hyperfine parameter distributions in Mössbauer spectroscopy Rancourt, D. G.; Ping, J. Y. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 58, Issue 1 https://doi.org/10.1016/0168-583X(91)95681-3	journal	May 1991
Synthesis and characterization of charge-substituted garnets YCaLnGa5O12 (LnCe, Pr, Tb) Gramsch, Stephen A.; Morss, Lester R. Journal of Alloys and Compounds, Vol. 207-208 https://doi.org/10.1016/0925-8388(94)90257-7	journal	June 1994
Actinide host phases as radioactive waste forms Yudintsev, Sergey V.; Stefanovsky, Sergey V.; Ewing, Rodney C. Structural Chemistry of Inorganic Actinide Compounds https://doi.org/10.1016/B978-044452111-8/50014-4	book	September 2007
Enthalpies of formation of Ce-pyrochlore, Ca0.93Ce1.00Ti2.035O7.00, U-pyrochlore, Ca1.46U4+0.23U6+0.46Ti1.85O7.00 and Gd-pyrochlore, Gd2Ti2O7: three materials relevant to the proposed waste form for excess weapons plutonium Helean, K. B.; Navrotsky, A.; Vance, E. R. Journal of Nuclear Materials, Vol. 303, Issue 2-3 https://doi.org/10.1016/S0022-3115(02)00795-X	journal	June 2002
Ion irradiation-induced amorphization and nano-crystal formation in garnets Utsunomiya, S.; Wang, L. M.; Yudintsev, S. Journal of Nuclear Materials, Vol. 303, Issue 2-3 https://doi.org/10.1016/S0022-3115(02)00802-4	journal	June 2002
Enthalpies of formation of U-, Th-, Ce-brannerite: implications for plutonium immobilization Helean, K. B.; Navrotsky, A.; Lumpkin, G. R. Journal of Nuclear Materials, Vol. 320, Issue 3 https://doi.org/10.1016/S0022-3115(03)00186-7	journal	August 2003
Redox properties of water on the oxidized and reduced surfaces of CeO2 Henderson, M. A.; Perkins, C. L.; Engelhard, M. H. Surface Science, Vol. 526, Issue 1-2 https://doi.org/10.1016/S0039-6028(02)02657-2	journal	February 2003
Ion irradiation effects in natural garnets: Comparison with zircon Utsunomiya, S.; Wang, L. M.; Ewing, R. C. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 191, Issue 1-4 https://doi.org/10.1016/S0168-583X(02)00618-3	journal	May 2002
Pertechnetate (TcO4−) reduction by reactive ferrous iron forms in naturally anoxic, redox transition zone sediments from the Hanford Site, USA Peretyazhko, T. S.; Zachara, J. M.; Kukkadapu, R. K. Geochimica et Cosmochimica Acta, Vol. 92 https://doi.org/10.1016/j.gca.2012.05.041	journal	September 2012
Preparation and characterization of yttrium iron garnet (YIG) nanocrystalline powders by auto-combustion of nitrate-citrate gel Hosseini Vajargah, S.; Madaah Hosseini, H. R.; Nemati, Z. A. Journal of Alloys and Compounds, Vol. 430, Issue 1-2 https://doi.org/10.1016/j.jallcom.2006.05.023	journal	March 2007
Synthesis of yttrium iron garnet (YIG) by citrate–nitrate gel combustion and precursor plasma spray processes Guo, X. Z.; Ravi, B. G.; Devi, P. S. Journal of Magnetism and Magnetic Materials, Vol. 295, Issue 2 https://doi.org/10.1016/j.jmmm.2005.01.007	journal	August 2005
Radiation effects in ferrate garnet Utsunomiya, S.; Yudintsev, S.; Ewing, R. C. Journal of Nuclear Materials, Vol. 336, Issue 2-3 https://doi.org/10.1016/j.jnucmat.2004.09.020	journal	February 2005
Irradiation of synthetic garnet by heavy ions and α-decay of 244Cm Zhang, Jiaming; Livshits, Tatiana S.; Lizin, Andrey A. Journal of Nuclear Materials, Vol. 407, Issue 3 https://doi.org/10.1016/j.jnucmat.2010.09.051	journal	December 2010
The structure and ordering of zirconium and hafnium containing garnets studied by electron channelling, neutron diffraction and Mössbauer spectroscopy Whittle, Karl R.; Lumpkin, Gregory R.; Berry, Frank J. Journal of Solid State Chemistry, Vol. 180, Issue 2 https://doi.org/10.1016/j.jssc.2006.12.006	journal	February 2007
Cerium L _III -Edge XAS Investigation of the Structure of Crystalline and Amorphous Cerium Oxides Shahin, Ahmed M.; Grandjean, Fernande; Long, Gary J. Chemistry of Materials, Vol. 17, Issue 2 https://doi.org/10.1021/cm0492437	journal	January 2005
Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics Guo, Xiaofeng; Tavakoli, Amir H.; Sutton, Steve Chemistry of Materials, Vol. 26, Issue 2 https://doi.org/10.1021/cm403444f	journal	December 2013
On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël Journal of the American Chemical Society, Vol. 132, Issue 50 https://doi.org/10.1021/ja1053175	journal	December 2010
Thermodynamics of thorium substitution in yttrium iron garnet: comparison of experimental and theoretical results Guo, X.; Rak, Zs.; Tavakoli, A. H. J. Mater. Chem. A, Vol. 2, Issue 40 https://doi.org/10.1039/C4TA03683B	journal	January 2014
High resolution x‐ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies Kraft, S.; Stümpel, J.; Becker, P. Review of Scientific Instruments, Vol. 67, Issue 3 https://doi.org/10.1063/1.1146657	journal	March 1996
Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and “minor” actinides Ewing, Rodney C.; Weber, William J.; Lian, Jie Journal of Applied Physics, Vol. 95, Issue 11 https://doi.org/10.1063/1.1707213	journal	June 2004
Nuclear waste forms for actinides Ewing, R. C. Proceedings of the National Academy of Sciences, Vol. 96, Issue 7 https://doi.org/10.1073/pnas.96.7.3432	journal	March 1999
Recoilless-Fraction Ratios for Fe 57 in Octahedral and Tetrahedral Sites of a Spinel and a Garnet Sawatzky, G. A.; Van Der Woude, F.; Morrish, A. H. Physical Review, Vol. 183, Issue 2 https://doi.org/10.1103/PhysRev.183.383	journal	July 1969
XANES study on the valence transitions in cerium oxide nanoparticles Zhang, Jing; Wu, Ziyu; Liu, Tao Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016022	journal	March 2001
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Progress and New Directions in Calorimetry: A 2014 Perspective Navrotsky, Alexandra Journal of the American Ceramic Society, Vol. 97, Issue 11 https://doi.org/10.1111/jace.13278	journal	October 2014
Tetragonalization of (Ca3−x Ax)(Zr2−y Fey)Fe3O12 (A = Ce, Th, Gd) ferrite garnets as revealed by Mössbauer spectroscopy and the Rietveld analysis Urusov, V. S.; Rusakov, V. S.; Kabalov, Yu. K. Doklady Physics, Vol. 49, Issue 12 https://doi.org/10.1134/1.1848623	journal	December 2004
Magnetic collapse in yttrium iron garnet Y3Fe5O12 at high pressure Lyubutin, I. S.; Gavriliuk, A. G.; Trojan, I. A. Journal of Experimental and Theoretical Physics Letters, Vol. 82, Issue 11 https://doi.org/10.1134/1.2171723	journal	December 2005
Synthetic minerals with the pyrochlore and garnet structures for immobilization of actinide-containing wastes Laverov, N. P.; Yudintsev, S. V.; Livshits, T. S. Geochemistry International, Vol. 48, Issue 1 https://doi.org/10.1134/S0016702910010015	journal	January 2010
Natural and artificial minerals as matrices for immobilization of actinides Omel’yanenko, B. I.; Livshits, T. S.; Yudintsev, S. V. Geology of Ore Deposits, Vol. 49, Issue 3 https://doi.org/10.1134/S1075701507030014	journal	June 2007
Stability of artificial ferrite garnets with actinides and lanthanoids in water solutions Livshits, T. S. Geology of Ore Deposits, Vol. 50, Issue 6 https://doi.org/10.1134/S1075701508060056	journal	December 2008
Separations and Transmutation Criteria to Improve Utilization of a Geologic Repository Wigeland, Roald A.; Bauer, Theodore H.; Fanning, Thomas H. Nuclear Technology, Vol. 154, Issue 1 https://doi.org/10.13182/NT06-3	journal	April 2006
Crystal chemistry of the garnets* Geller, S. Zeitschrift für Kristallographie, Vol. 125, Issue 125 https://doi.org/10.1524/zkri.1967.125.125.1	journal	December 1967
Radiation Effects in Glasses Used for Immobilization of High-level Waste and Plutonium Disposition Weber, William J.; Ewing, Rodney C.; Angell, C. Austen Journal of Materials Research, Vol. 12, Issue 8 https://doi.org/10.1557/JMR.1997.0266	journal	August 1997
Enthalpy of Formation of Yttria-Doped Ceria Chen, Weiqun; Lee, Theresa A.; Navrotsky, Alexandra Journal of Materials Research, Vol. 20, Issue 1 https://doi.org/10.1557/JMR.2005.0017	journal	January 2005
Synthesis of Garnet/Perovskite-Based Ceramic for the Immobilization of Pu-Residue Wastes Burakov, B. E.; Anderson, E. B.; Knecht, D. A. MRS Proceedings, Vol. 556 https://doi.org/10.1557/PROC-556-55	journal	January 1999
Accommodation of Uranium into the Garnet Structure Yudintsev, Sergey V.; Lapina, Marya I.; Ptashkin, Alexander G. MRS Proceedings, Vol. 713 https://doi.org/10.1557/PROC-713-JJ11.28	journal	January 2002
Materials Science of High-Level Nuclear Waste Immobilization Weber, William J.; Navrotsky, Alexandra; Stefanovsky, Sergey MRS Bulletin, Vol. 34, Issue 1 https://doi.org/10.1557/mrs2009.12	journal	January 2009
The Nuclear Fuel Cycle: A Role for Mineralogy and Geochemistry Ewing, R. C. Elements, Vol. 2, Issue 6 https://doi.org/10.2113/gselements.2.6.331	journal	December 2006
Ceramic Waste Forms for Actinides Lumpkin, G. R. Elements, Vol. 2, Issue 6 https://doi.org/10.2113/gselements.2.6.365	journal	December 2006
Elbrusite-(Zr)--A new uranian garnet from the Upper Chegem caldera, Kabardino-Balkaria, Northern Caucasus, Russia Galuskina, I. O.; Galuskin, E. V.; Armbruster, T. American Mineralogist, Vol. 95, Issue 8-9 https://doi.org/10.2138/am.2010.3507	journal	August 2010
Oxide melt solution calorimetry of Fe2+-bearing oxides and application to the magnetite-maghemite (Fe3O4-Fe8/3O4) system Lilova, K. I.; Xu, F.; Rosso, K. M. American Mineralogist, Vol. 97, Issue 1 https://doi.org/10.2138/am.2012.3883	journal	January 2012
Microfluorescence and Microtomography Analyses of Heterogeneous Earth and Environmental Materials Sutton, S. R.; Bertsch, P. M.; Newville, M. Reviews in Mineralogy and Geochemistry, Vol. 49, Issue 1 https://doi.org/10.2138/rmg.2002.49.8	journal	January 2002
Alpha-recoil damage in natural zirconolite and perovskite. Sinclair, W.; Ringwood, A. E. GEOCHEMICAL JOURNAL, Vol. 15, Issue 5 https://doi.org/10.2343/geochemj.15.229	journal	January 1981

Cited By (3)

Facile incorporation of technetium into magnetite, magnesioferrite, and hematite by formation of ferrous nitrate in situ : precursors to iron oxide nuclear waste forms Lukens, Wayne W.; Saslow, Sarah A. Dalton Transactions, Vol. 47, Issue 30 https://doi.org/10.1039/c8dt01356j	journal	January 2018
Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO ₂ Guo, Xiaofeng; Boukhalfa, Hakim; Mitchell, Jeremy N. Review of Scientific Instruments, Vol. 90, Issue 4 https://doi.org/10.1063/1.5093567	journal	April 2019
Effect of calcium oxide doping on the microstructure and optical properties of YAG transparent ceramics Hua, Tengfei; Zeng, Qiang; Qi, Jianqi Materials Research Express, Vol. 6, Issue 3 https://doi.org/10.1088/2053-1591/aaf487	journal	December 2018

Similar Records

Charge-Coupled Substituted Garnets (Y_3-xCa_0.5xM_0.5x)Fe₅O₁₂ (M = Ce, Th): Structure and Stability as Crystalline Nuclear Waste Forms

Journal Article · Mon Jun 08 00:00:00 EDT 2015 · Inorg. Chem. · OSTI ID:1178827

Charge-coupled Substituted Garnets (Y3-xCa0.5xM0.5x)Fe5O12 (M = Ce, Th): Structure and Stability as Crystalline Nuclear Waste Forms

Journal Article · Mon Apr 20 00:00:00 EDT 2015 · Inorganic Chemistry, 54(8):4156-4166 · OSTI ID:1182881

Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics

Journal Article · Mon Jan 27 23:00:00 EST 2014 · Chemistry of Materials, 26(2):1133-1143 · OSTI ID:1130196

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY