Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite
Abstract
The titanate-based hollandite structure is proposed as an effective ceramic waste form for Cs-immobilization. In this study, quantum-mechanical calculations were used to quantify the impact of A-site and B-site ordering on the structural stability of hollandite with compositions BaxCsy(MzTi8-z)O16, where M = Zn2+, Ga3+, and Al3+. The calculated enthalpy of formation agrees with experimental measurements of related hollandite phases from melt solution calorimetry. Ground state geometry optimizations show that, for intermediate compositions (e.g., CsBaGa6Ti18O48), the presence of both Cs and Ba in the A-site tunnels is not energetically favored. However, the decay heat generated during storage of the Cs-containing waste form may overcome the energetics of Ba and Cs mixing in the tunnel structure of hollandite. The ability of the hollandite structure to accommodate the radioparagenesis of Cs to Ba is critical for long term performance of the waste. For the first time, B-site ordering was observed along the tunnel direction ([001] zone axis) for the Ga-hollandite compositions, as well as the intermediate Al-hollandite composition. These compositionally dependent structural features, and associated formation enthalpies, are of importance to the stability and radiation damage tolerance of ceramic waste forms.
- Authors:
-
- Clemson Univ., SC (United States)
- Publication Date:
- Research Org.:
- Clemson Univ., SC (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1500029
- Grant/Contract Number:
- SC0012530
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Wen, Yi, Xu, Yun, Brinkman, Kyle S., and Shuller-Nickles, Lindsay. Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite. United States: N. p., 2018.
Web. doi:10.1038/s41598-018-22982-7.
Wen, Yi, Xu, Yun, Brinkman, Kyle S., & Shuller-Nickles, Lindsay. Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite. United States. https://doi.org/10.1038/s41598-018-22982-7
Wen, Yi, Xu, Yun, Brinkman, Kyle S., and Shuller-Nickles, Lindsay. Thu .
"Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite". United States. https://doi.org/10.1038/s41598-018-22982-7. https://www.osti.gov/servlets/purl/1500029.
@article{osti_1500029,
title = {Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite},
author = {Wen, Yi and Xu, Yun and Brinkman, Kyle S. and Shuller-Nickles, Lindsay},
abstractNote = {The titanate-based hollandite structure is proposed as an effective ceramic waste form for Cs-immobilization. In this study, quantum-mechanical calculations were used to quantify the impact of A-site and B-site ordering on the structural stability of hollandite with compositions BaxCsy(MzTi8-z)O16, where M = Zn2+, Ga3+, and Al3+. The calculated enthalpy of formation agrees with experimental measurements of related hollandite phases from melt solution calorimetry. Ground state geometry optimizations show that, for intermediate compositions (e.g., CsBaGa6Ti18O48), the presence of both Cs and Ba in the A-site tunnels is not energetically favored. However, the decay heat generated during storage of the Cs-containing waste form may overcome the energetics of Ba and Cs mixing in the tunnel structure of hollandite. The ability of the hollandite structure to accommodate the radioparagenesis of Cs to Ba is critical for long term performance of the waste. For the first time, B-site ordering was observed along the tunnel direction ([001] zone axis) for the Ga-hollandite compositions, as well as the intermediate Al-hollandite composition. These compositionally dependent structural features, and associated formation enthalpies, are of importance to the stability and radiation damage tolerance of ceramic waste forms.},
doi = {10.1038/s41598-018-22982-7},
journal = {Scientific Reports},
number = 1,
volume = 8,
place = {United States},
year = {Thu Mar 22 00:00:00 EDT 2018},
month = {Thu Mar 22 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Effects of ionizing radiation on the hollandite structure-type: Ba0.85Cs0.26Al1.35Fe0.77Ti5.90O16
journal, January 2008
- Abdelouas, A.; Utsunomiya, S.; Suzuki, T.
- American Mineralogist, Vol. 93, Issue 1
Thermodynamic properties of ThxU1−xO2 (0<x<1) based on quantum–mechanical calculations and Monte-Carlo simulations
journal, May 2011
- Shuller, Lindsay C.; Ewing, Rodney C.; Becker, Udo
- Journal of Nuclear Materials, Vol. 412, Issue 1
Disorder processes in A 3+ B 3+ O 3 compounds: implications for radiation tolerance
journal, February 2004
- Levy, Mark R.; Grimes, Robin W.; Sickafus, Kurt E.
- Philosophical Magazine, Vol. 84, Issue 6
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Radiation effects in nuclear waste forms for high-level radioactive waste
journal, January 1995
- Ewing, R. C.; Weber, W. J.; Clinard, F. W.
- Progress in Nuclear Energy, Vol. 29, Issue 2
Synthesis and crystal structure of BaRu6O12: An ordered stoichiometric hollandite
journal, June 1985
- Torardi, C. C.
- Materials Research Bulletin, Vol. 20, Issue 6
U( v ) in metal uranates: a combined experimental and theoretical study of MgUO 4 , CrUO 4 , and FeUO 4
journal, January 2016
- Guo, Xiaofeng; Tiferet, Eitan; Qi, Liang
- Dalton Transactions, Vol. 45, Issue 11
A DFT+U study of Pu immobilization in Gd2Zr2O7
journal, December 2015
- Zhao, F. A.; Xiao, H. Y.; Jiang, M.
- Journal of Nuclear Materials, Vol. 467
Preparation and characterization of (Ba,Cs)(M,Ti)8O16 (M=Al3+, Fe3+, Ga3+, Cr3+, Sc3+, Mg2+) hollandite ceramics developed for radioactive cesium immobilization
journal, June 2007
- Aubin-Chevaldonnet, V.; Caurant, D.; Dannoux, A.
- Journal of Nuclear Materials, Vol. 366, Issue 1-2
Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics
journal, December 2013
- Guo, Xiaofeng; Tavakoli, Amir H.; Sutton, Steve
- Chemistry of Materials, Vol. 26, Issue 2
Thermodynamics of thorium substitution in yttrium iron garnet: comparison of experimental and theoretical results
journal, January 2014
- Guo, X.; Rak, Zs.; Tavakoli, A. H.
- J. Mater. Chem. A, Vol. 2, Issue 40
First-principles simulation: ideas, illustrations and the CASTEP code
journal, March 2002
- Segall, M. D.; Lindan, Philip J. D.; Probert, M. J.
- Journal of Physics: Condensed Matter, Vol. 14, Issue 11
Multi-Phase Glass-Ceramics as a Waste Form for Combined Fission Products: Alkalis, Alkaline Earths, Lanthanides, and Transition Metals
journal, February 2012
- Crum, Jarrod V.; Turo, Laura; Riley, Brian
- Journal of the American Ceramic Society, Vol. 95, Issue 4
The structure and dielectric properties of compounds with the formula BA x (Ti 8–x Mg x )O 16
journal, January 1958
- Dryden, J. S.; Wadsley, A. D.
- Trans. Faraday Soc., Vol. 54, Issue 0
Heavy ion irradiations on synthetic hollandite-type materials: Ba1.0Cs0.3A2.3Ti5.7O16 (A=Cr, Fe, Al)
journal, July 2016
- Tang, Ming; Tumurugoti, Priyatham; Clark, Braeden
- Journal of Solid State Chemistry, Vol. 239
Supercell ordering in a hollandite-type phase: Potassium magnesium antimony oxide
journal, March 1983
- Pring, A.; Smith, David J.; Jefferson, D. A.
- Journal of Solid State Chemistry, Vol. 46, Issue 3
Cation Disorder in Pyrochlore Ceramics: 89 Y MAS NMR and First-Principles Calculations
journal, October 2009
- Reader, Simon W.; Mitchell, Martin R.; Johnston, Karen E.
- The Journal of Physical Chemistry C, Vol. 113, Issue 43
Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides
journal, February 2007
- Sickafus, Kurt E.; Grimes, Robin W.; Valdez, James A.
- Nature Materials, Vol. 6, Issue 3
Structural Evolution in Hollandite Solid Solutions Across the A‐Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16
journal, August 2016
- Xu, Yun; Feygenson, Mikhail; Page, Katharine
- Journal of the American Ceramic Society, Vol. 99, Issue 12
Substitutional doping and oxygen vacancies in La2Zr2O7 pyrochlore oxide
journal, May 2011
- Nyman, B. Joakim; Björketun, Mårten E.; Wahnström, Göran
- Solid State Ionics, Vol. 189, Issue 1
Intrinsic Structural Disorder and Radiation Response of Nanocrystalline Gd 2 (Ti 0.65 Zr 0.35 ) 2 O 7 Pyrochlore
journal, June 2010
- Zhang, Jiaming; Lian, Jie; Zhang, Fuxiang
- The Journal of Physical Chemistry C, Vol. 114, Issue 27
Crystal Structure of Hollandite
journal, December 1949
- BystrÖM, Anders; BystrÖM, Ann Marie
- Nature, Vol. 164, Issue 4183
Defect formation energy in pyrochlore: the effect of crystal size
journal, July 2014
- Wang, Jianwei; Ewing, Rodney C.; Becker, Udo
- Materials Research Express, Vol. 1, Issue 3
Using “radioparagenesis” to design robust nuclear waste forms
journal, January 2010
- Jiang, C.; Uberuaga, B. P.; Sickafus, K. E.
- Energy Environ. Sci., Vol. 3, Issue 1
Disposal of high-level nuclear wastes: a geological perspective
journal, April 1985
- Ringwood, A. E.
- Mineralogical Magazine, Vol. 49, Issue 351
Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and “minor” actinides
journal, June 2004
- Ewing, Rodney C.; Weber, William J.; Lian, Jie
- Journal of Applied Physics, Vol. 95, Issue 11
Melt processed single phase hollandite waste forms for nuclear waste immobilization: Ba1.0Cs0.3A2.3Ti5.7O16; A=Cr, Fe, Al
journal, January 2014
- Amoroso, Jake; Marra, James; Conradson, Steven D.
- Journal of Alloys and Compounds, Vol. 584
Thermochemistry of Barium Hollandites
journal, March 2013
- Costa, Gustavo C. C.; Xu, Hongwu; Navrotsky, Alexandra
- Journal of the American Ceramic Society, Vol. 96, Issue 5
A-site compositional effects in Ga-doped hollandite materials of the form BaxCsyGa2x+yTi8−2x−yO16: implications for Cs immobilization in crystalline ceramic waste forms
journal, June 2016
- Xu, Yun; Wen, Yi; Grote, Rob
- Scientific Reports, Vol. 6, Issue 1
Radiation effects in crystalline ceramics for the immobilization of high-level nuclear waste and plutonium
journal, June 1998
- Weber, W. J.; Ewing, R. C.; Catlow, C. R. A.
- Journal of Materials Research, Vol. 13, Issue 6
Incommensurate superlattice ordering in priderite
journal, March 1983
- Pring, A.; Jefferson, D. A.
- Mineralogical Magazine, Vol. 47, Issue 342
Np-incorporation into uranyl phases: A quantum–mechanical evaluation
journal, March 2013
- Shuller, Lindsay C.; Ewing, Rodney C.; Becker, Udo
- Journal of Nuclear Materials, Vol. 434, Issue 1-3
Role of iron in the incorporation of uranium in ferric garnet matrices
journal, October 2011
- Rák, Zs.; Ewing, R. C.; Becker, U.
- Physical Review B, Vol. 84, Issue 15
Works referencing / citing this record:
Thermodynamic assessment of the hollandite high‐level radioactive waste form
journal, April 2019
- Utlak, Stephen A.; Besmann, Theodore M.; Brinkman, Kyle S.
- Journal of the American Ceramic Society, Vol. 102, Issue 10
Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization
journal, December 2018
- Zhao, Mingyang; Xu, Yun; Shuller‐Nickles, Lindsay
- Journal of the American Ceramic Society, Vol. 102, Issue 7
Two new magnetic hollandites A 1.5 Ru 6.1 Cr 1.9 O 16 (A = Sr, Ba): magnetoresistance and thermopower
journal, January 2019
- Pawula, Florent; Hébert, Sylvie; Pelloquin, Denis
- Journal of Materials Chemistry C, Vol. 7, Issue 1
Compositional control of tunnel features in hollandite-based ceramics: structure and stability of (Ba,Cs)1.33(Zn,Ti)8O16
journal, September 2018
- Grote, R.; Zhao, M.; Shuller-Nickles, L.
- Journal of Materials Science, Vol. 54, Issue 2