Synthesis, characterization and thermochemistry of Cs-, Rb- and Sr-substituted barium aluminium titanate hollandites

Xu, Hongwu; Wu, Lili; Zhu, Jinlong; Navrotsky, Alexandra

doi:10.1016/j.jnucmat.2015.01.014

Synthesis, characterization and thermochemistry of Cs-, Rb- and Sr-substituted barium aluminium titanate hollandites

Journal Article · Fri Jan 09 00:00:00 EST 2015 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2015.01.014· OSTI ID:1471328

^[1]; Wu, Lili ^[2]; Zhu, Jinlong ^[1]; Navrotsky, Alexandra ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of California, Davis, CA (United States)

Titanate hollandites are of considerable interest for immobilization of radioactive Cs, its daughter product Ba and related radionuclides Rb and Sr. In this work, we synthesized three hollandites, Ba_1.18Cs_0.21Al_2.44Ti_5.53O₁₆, Ba_1.17Rb_0.19Al_2.46Ti_5.53O₁₆ and Ba_1.14Sr_0.10Al_2.38Ti_5.59O₁₆, using sol–gel methods. Rietveld analysis of synchrotron XRD data shows that they adopt the tetragonal structure (space group I4/m), and their cell parameters increase with increasing cation size (Sr²⁺ → Rb⁺ → Cs⁺). Standard enthalpies of formation of these hollandites were determined from drop solution calorimetric measurements with lead borate as the solvent at 973 K. Their formation enthalpies are similar, consistent with the occurrence of extensive cation substitutions in hollandites. Further energetic analysis with respect to BaTiO₃ and SrTiO₃ perovskites and other oxides reveals decreased thermodynamic stability from Cs- to Rb- to Sr-hollandite. Lastly, this trend is consistent with the phase assemblage observed in Synroc, where Cs⁺, Rb⁺ and Ba²⁺ enter into hollandite, whereas Sr²⁺ occurs in perovskite.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; AC52-06NA25396

OSTI ID:: 1471328

Alternate ID(s):: OSTI ID: 22457438
OSTI ID: 1246584

Report Number(s):: LA-UR--14-29122

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Journal Issue: C Vol. 459; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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High-temperature oxide melt solution calorimetry
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Synchrotron X-ray diffraction

Synthesis, characterization and thermochemistry of Cs-, Rb- and Sr-substituted barium aluminium titanate hollandites

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