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Stability at high-pressure, elastic behaviour and pressure-induced structural evolution of CsAlSi5O12, a potential host for nuclear waste

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Abstract

The elastic and structural behaviour of the synthetic zeolite CsAlSi5O12 (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V 0 = 1,155(4) Å3, K T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a 3, b 3, c 3) for the volume. The refined axial-EoS parameters are: a 0 = 16.701(44) Å, K T0a = 14(2) GPa (βa = 0.024(3) GPa−1), K′ a = 6.2(8) for the a-axis; b 0 = 13.778(20) Å, K T0b = 21(3) GPa (βb = 0.016(2) GPa−1), K′ b = 10(2) for the b-axis; c 0 = 5.018(7) Å, K T0c = 33(3) GPa (βc = 0.010(1) GPa−1), K′ c = 3.2(8) for the c-axis (K T0a:K T0b:K T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi5O12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi5O12 allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.

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Acknowledgments

This work was funded by the Italian Ministry of University and Research, MIUR-Project: 2006040119_004 (grant to Alessandro Pavese). T.A. acknowledges support by the Swiss National Science Foundation, grant 200020-112198 “Crystal Chemistry of Minerals”. The authors thank Mr Bruno Pafundi for helping in the set-up of the high-pressure laboratory of crystallography at the Dipartimento di Scienze della Terra, Università degli Studi di Milano-Italy. The Editor Milan Rieder, Mark Welch and an anonymous reviewer are thanked.

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Authors and Affiliations

  1. Dipartimento di Scienze della Terra, Università degli Studi di Milano, Via Botticelli 23, 20133, Milan, Italy

    G. Diego Gatta & Nicola Rotiroti

  2. CNR-Istituto per la Dinamica dei Processi Ambientali, Milan, Italy

    G. Diego Gatta & Nicola Rotiroti

  3. Mineralogical Crystallography, Institute of Geological Sciences, University of Bern, Freiestr. 3, 3012, Bern, Switzerland

    Martin Fisch, Milen Kadiyski & Thomas Armbruster

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  1. G. Diego Gatta
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Correspondence to G. Diego Gatta.

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Gatta, G.D., Rotiroti, N., Fisch, M. et al. Stability at high-pressure, elastic behaviour and pressure-induced structural evolution of CsAlSi5O12, a potential host for nuclear waste. Phys Chem Minerals 35, 521–533 (2008). https://doi.org/10.1007/s00269-008-0246-2

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