Publication Date:
2015-04-24
Description:
As an analogue of the mineral pollucite (CsAlSi 2 O 6 ), CsTiSi 2 O 6.5 is a potential host phase for radioactive Cs. However, as 137 Cs and 135 Cs transmute to 137 Ba and 135 Ba, 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 x Ba (1− x )/2 TiSi 2 O 6.5 and Cs x Ba 1− x TiSi 2 O 7−0.5 x , ( 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 x Ba (1− x )/2 TiSi 2 O 6.5 samples are phase-pure, Cs x Ba 1− x TiSi 2 O 7−0.5 x samples contain Cs 3 x /(2+ x ) Ba (1− x )/(2+ x ) TiSi 2 O 6.5 pollucites (i.e., also two-Cs-to-one-Ba substitution) and a secondary phase, fresnoite (Ba 2 TiSi 2 O 8 ). Thus, the Cs x Ba 1− x TiSi 2 O 7−0.5 x series is energetically less favorable than Cs x Ba (1− x )/2 TiSi 2 O 6.5 . To study the stability systematics of Cs x Ba (1− x )/2 TiSi 2 O 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.
Print ISSN:
0002-7820
Electronic ISSN:
1551-2916
Topics:
Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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