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High-temperature behaviour of astrophyllite, K2NaFe7 2+Ti2(Si4O12)2O2(OH)4F: a combined X-ray diffraction and Mössbauer spectroscopic study

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Abstract

High-temperature X-ray powder-diffraction study of astrophyllite, K2NaFe7 2+Ti2(Si4O12)2O2(OH)4F, and investigation of the samples annealed at 600 and 700 °C, reveal the occurrence of a phase transformation due to the thermal iron oxidation coupled with (1) deprotonation according to the scheme Fe2+ + OH− → Fe3+ + O2− + ½H2 ↑, and (2) defluorination according to the scheme Fe2+ + F− → Fe3+ + O2−. The phase transformation occurs at 500 °C, it is irreversible and without symmetry changes. The mineral decomposes at 775 °C. Both astrophyllite and its high-temperature dehydroxylated (HT) modification are triclinic, P-1. The unit-cell parameters are a = 5.3752(1), b = 11.8956(3), c = 11.6554(3) Å, α = 113.157(3), β = 94.531(2), γ = 103.112(2)º, V = 655.47(3) Å3 for unheated astrophyllite, and a = 5.3287(4), b = 11.790(1), c = 11.4332(9) Å, α = 112.530(8), β = 94.539(6), γ = 103.683(7)º, V = 633.01(9) Å3 for the HT (annealed) modification of astrophyllite. The oxidation of iron is confirmed: (1) by the presence of an exothermic effect at 584 °C in the DTA/TG curves in an Ar–O atmosphere and its absence in an Ar–Ar atmosphere and (2) by ex situ Mössbauer spectroscopy that showed the oxidation of Fe2+ to Fe3+ in the samples heated to 700 °C. Deprotonation was detected by the evolution of IR spectra in the region 3600–3000 cm−1 for astrophyllite and its HT modification. Defluorination was detected by the presence of F in the electron microprobe analysis of unheated astrophyllite and the absence of F in the analysis of unpolished heated astrophyllite. The significant difference between astrophyllite and its HT modification is in the reduction of the M–O interatomic distances after heating to 500 °C and the distortion indices of the MO6 and Dφ6 octahedra. Thermal behaviour of astrophyllite in the 25–475 °C temperature range can be described as a volume thermal expansion with maximal coefficient of thermal expansion in the direction perpendicular to the plane of the HOH layers. In contrast, the HT phase experiences a strong contraction in the 600–775 °C temperature range, again in the direction perpendicular to the plane of the HOH layers.

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Acknowledgements

This work was supported by the Russian Foundation for Basic Research (Grant 14-05-31229) and the President of Russian Federation Grant for Young Candidates of Sciences (Grant MK-3296.2015.5). The XRD studies were done at the X-ray Diffraction and Geomodel Centers of St. Petersburg State University. Mössbauer facilities, FCH and YAA were supported by an NSERC Discovery Grant and Canada Foundation for Innovation Grants to FCH.

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  1. Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, Saint-Petersburg, 199034, Russia

    Elena S. Zhitova, Sergey V. Krivovichev, Maria G. Krzhizhanovskaya, Andrey A. Zolotarev & Alexey G. Goncharov

  2. Institute of Volcanology and Seismology, Russian Academy of Sciences, Piip blvd. 9, Petropavlovsk-Kamchatsky, 683006, Russia

    Elena S. Zhitova

  3. Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Fersmana Str. 14, Apatity, 184209, Russia

    Sergey V. Krivovichev, Viktor N. Yakovenchuk & Yakov A. Pakhomovsky

  4. Department of Geological Sciences, University of Manitoba, 125 Dysart Road (Wallace Building), Winnipeg, MB, R3T 2N2, Canada

    Frank C. Hawthorne & Yassir A. Abdu

  5. Department of Applied Physics and Astronomy, University of Sharjah, 27272, Sharjah, United Arab Emirates

    Yassir A. Abdu

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  1. Elena S. Zhitova
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Zhitova, E.S., Krivovichev, S.V., Hawthorne, F.C. et al. High-temperature behaviour of astrophyllite, K2NaFe7 2+Ti2(Si4O12)2O2(OH)4F: a combined X-ray diffraction and Mössbauer spectroscopic study. Phys Chem Minerals 44, 595–613 (2017). https://doi.org/10.1007/s00269-017-0886-1

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