Abstract
Characterization of the behavior of zeolites at high pressures is of interest both in fundamental science and for practical applications. For example, zeolites occur as a major mineral group in tuffaceous rocks (such as those at the Nevada Nuclear Security Site), and they play a key role in defining the high-pressure behavior of tuff in a nuclear explosion event. The crystal structure, Si/Al ratio, and type of pressure-transmitting media (PTM) used in high-pressure experiments influence the compressional behavior of a given zeolitic phase. The heulandite-type (HEU) zeolites, including heulandite and clinoptilolite, are isostructural but differ in their Si/Al ratios. Thus, HEU-type zeolites comprise an ideal system in unraveling the effects of Si/Al ratio and type of PTM on their pressure-induced structural behavior. In this study, we performed in situ high-pressure angle-dispersive powder synchrotron X-ray diffraction (XRD) experiments on a natural HEU zeolite, clinoptilolite, with a Si/Al ratio of 4.4, by compressing it in a diamond anvil cell (DAC) up to 14.65 GPa using a non-penetrating pressure-transmitting medium (KCl). Unit cell parameters as a function of pressure up to 9.04 GPa were obtained by Rietveld analysis. Unit cell volumes were fit to both a second and a third-order Birch–Murnaghan equation of state. The mean bulk modulus (K0) determined from all the fittings is 32.7 ± 0.9 GPa. The zero-pressure compressibility of the a-, b-, and c-axes for clinoptilolite are 10.6 (± 0.8) × 10–3 GPa–1, 5.3 (± 0.7) × 10–3 GPa–1, and 17.1 (± 1.8) × 10–3 GPa–1, respectively. The pressure–volume equations of states of this type of zeolite are important for characterizing high-pressure behavior of the broader family of microporous materials and for developing reliable geophysical signatures for underground nuclear monitoring.
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Acknowledgements
We are grateful to the two anonymous reviewers for helpful comments. We thank Dr. Blake T. Sturtevant for allowing us to use the laboratory facilities of Dynamic Experiments Division at Los Alamos National Laboratory to prepare our diamond anvil cell. This research was funded by the Defense Nuclear Nonproliferation’s Nonproliferation Research and Development (NA-22) of the National Nuclear Security Administration (NNSA) and the Department of Energy (DOE). Los Alamos National Laboratory, an affirmative action/equal opportunity employer, is operated by Triad National Security, LLC, for the NNSA of U.S. DOE (Contract No. 89233218CNA00000). This work was also performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415) and the DOE-GeoSciences (DE-FG02-94ER14466). This research further used resources of the Advanced Photon Source; a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Los Alamos National Laboratory strongly supports academic freedom and a researcher’s right to publish; as an institution, however, the Laboratory does not endorse the viewpoint of a publication or guarantee its technical correctness.
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HX, HB, and ACS designed the project. CBC and ACS performed the TG-DSC measurements. ACS was assisted by BAC in preparing the diamond anvil cell. Synchrotron XRD measurements were performed by ACS with SC and VP supporting these measurements. Rietveld analyses were performed by ACS with HX and XG supporting these analyses. This manuscript was written through contributions of all authors. All authors have given approval to the final version of this manuscript.
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Strzelecki, A.C., Chariton, S., Cockreham, C.B. et al. Determination of P–V equation of state of a natural clinoptilolite using high-pressure powder synchrotron X-ray diffraction. Phys Chem Minerals 49, 45 (2022). https://doi.org/10.1007/s00269-022-01224-3
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DOI: https://doi.org/10.1007/s00269-022-01224-3