An experimental study of symmetry lowering of analcime

Physics and Chemistry of Minerals volume 45, pages381–390(2018)Cite this article

Abstract

Single crystals of analcime were hydrothermally synthesized from a gel of analcime composition at 200 °C for 24 h. They were grown up to 100 μm in size with typical deltoidal icositetrahedron habit. The chemical composition determined by EPMA and TG analyses was Na0.84(Al0.89Si2.12)O6·1.04H2O. The single-crystal X-ray diffraction method was used to determine the symmetry and crystal structure of analcime. The analcime grown from a gel crystallized in cubic space group Ia3d with lattice parameter a = 13.713(3) Å. In the cubic analcime, Si and Al cations were totally disordered over the framework T sites with site occupancy of Si:Al = 0.6871:0.3129(14). The single crystals of analcime with cubic symmetry were hydrothermally reheated at 200 °C in ultrapure water. After the hydrothermal treatment for 24 h, forbidden reflections for the cubic Ia3d symmetry were observed. The reflection conditions led to an orthorhombic space group Ibca with lattice parameters a = 13.727(2) Å, b = 13.707(2) Å, and c = 13.707(2) Å. The unit-cell showed a slight distortion with (a + b)/2 > c, yielding a flattened cell along c. In the orthorhombic analcime, Al exhibited a site preference for T11 site, which indicates that the Si/Al ordering over the framework T sites lowers the symmetry from cubic Ia3d to orthorhombic Ibca. After the hydrothermal treatment for 48 h, reflections corresponding to orthorhombic space group Ibca were observed as well. The lattice parameters were a = 13.705(2) Å, b = 13.717(2) Å, and c = 13.706(2) Å, retaining the flattened cell shape with (a + b)/2 > c. The Si and Al cations were further ordered among the framework T sites than the case of the hydrothermal treatment for 24 h. As a consequence, the Si/Al ordering was slightly but significantly accelerated with increasing the hydrothermal treatment time. During the hydrothermal reaction, however, chemical compositions were almost unchanged. The site occupancies of Na over the extra-framework sites remained unaffected with the heating time; thus, the hydrothermal heating influences the degree of ordering of Si and Al over the framework T sites rather than that of Na among the extra-framework sites.

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Acknowledgements

We appreciate the incisive reviews by Akihiko Nakatsuka and an anonymous reviewer, which led to numerous improvements in the manuscript. We also thank Taku Tsuchiya for his editorial handling. The work was partially supported by a Grant-in-Aid for Scientific Research (C) from the Japan Society for the Promotion of Science (Project no. 26400511).

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  1. Division of Earth Evolution Sciences, Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8572, Japan

    Neo Sugano & Atsushi Kyono

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  1. Neo Sugano
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  2. Atsushi Kyono
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Correspondence to Atsushi Kyono.

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Sugano, N., Kyono, A. An experimental study of symmetry lowering of analcime. Phys Chem Minerals 45, 381–390 (2018). https://doi.org/10.1007/s00269-017-0922-1

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Keywords

  • Analcime
  • Single-crystal X-ray diffraction
  • Symmetry lowering
  • Si/Al ordering