Crystal Structure and Thermodynamic Stability of Ba/Ti-Substituted Pollucites for Radioactive Cs/Ba Immobilization

Xu, Hongwu; Chavez, Manuel E.; Mitchell, Jeremy N.; Garino, Terry J.; Schwarz, Haiqing L.; Rodriguez, Mark A.; Rademacher, David X.; Nenoff, Tina Maria

doi:10.1111/jace.13608

Title: Crystal Structure and Thermodynamic Stability of Ba/Ti-Substituted Pollucites for Radioactive Cs/Ba Immobilization

Journal Article · Thu Apr 23 00:00:00 EDT 2015 · Journal of the American Ceramic Society

DOI:https://doi.org/10.1111/jace.13608· OSTI ID:1183100

Xu, Hongwu ^[1]; Chavez, Manuel E. ^[1]; Mitchell, Jeremy N. ^[1]; Garino, Terry J. ^[2]; Schwarz, Haiqing L. ^[2]; Rodriguez, Mark A. ^[2]; Rademacher, David X. ^[2]; Nenoff, Tina Maria ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

As an analogue of the mineral pollucite (CsAlSi₂O₆), CsTiSi₂O_6.5 is a potential host phase for radioactive Cs. However, as ¹³⁷Cs and ¹³⁵Cs transmute to ¹³⁷Ba and ¹³⁵Ba, respectively, through the beta decay, it is essential to study the structure and stability of this phase upon Cs → Ba substitution. In this work, two series of Ba/Ti-substituted samples, Cs_xBa_(1-x)/2TiSi₂O_6.5 and Cs_xBa_1-xTiSi₂O_7-0.5x, (x = 0.9 and 0.7), were synthesized by high-temperature crystallization from their respective precursors. Synchrotron X-ray diffraction and Rietveld analysis reveal that while Cs_xBa_(1-x)/2TiSi₂O_6.5 samples are phase-pure, Cs_xBa_1-xTiSi₂O_7-0.5x samples contain Cs_3x/(2+x)Ba_(1-x)/(2+x)TiSi₂O_6.5 pollucites (i.e., also two-Cs-to-one-Ba substitution) and a secondary phase, fresnoite (Ba₂TiSi₂O₈). Thus, the Cs_xBa_1-xTiSi₂O_7-0.5x series is energetically less favorable than Cs_xBa_(1-x)/2TiSi₂O_6.5. To study the stability systematics of Cs_xBa_(1-x)/2TiSi₂O_6.5 pollucites, high-temperature calorimetric experiments were performed at 973 K with or without the lead borate solvent. Enthalpies of formation from the constituent oxides (and elements) have thus been derived. The results show that with increasing Ba/(Cs + Ba) ratio, the thermodynamic stability of these phases decreases with respect to their component oxides. Hence, from the energetic viewpoint, continued Cs → Ba transmutation tends to destabilize the parent silicotitanate pollucite structure. However, the Ba-substituted pollucite co-forms with fresnoite (which incorporates the excess Ba), thereby providing viable ceramic waste forms for all the Ba decay products.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5); USDOE

Grant/Contract Number:: AC04-94AL85000; AC52-06NA25396; DE‐AC52‐06NA25396

OSTI ID:: 1183100

Alternate ID(s):: OSTI ID: 1321745; OSTI ID: 1401387

Report Number(s):: SAND2014-17035J; LA-UR-14-25570; 536967; TRN: US1600455

Journal Information:: Journal of the American Ceramic Society, Vol. 98, Issue 8; ISSN 0002-7820

Publisher:: American Ceramic SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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