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Haüyne: phase transition and high-temperature structures obtained from synchrotron radiation and Rietveld refinements

Published online by Cambridge University Press:  05 July 2018

I. Hassan ,
S. M. Antao  and
J. B. Parise
I. Hassan*
Affiliation:
Department of Chemistry, University of the West Indies, Mona, Kingston 7, Jamaica
S. M. Antao
Affiliation:
Mineral Physics Institute & Department of Geosciences, State University of New York, Stony Brook, NY 11794-2100, USA
J. B. Parise
Affiliation:
Mineral Physics Institute & Department of Geosciences, State University of New York, Stony Brook, NY 11794-2100, USA
*
*E-mail: [email protected]
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Abstract

The structural behaviour of a haüyne with a chemical composition of Na4.35Ca2.28K0.95[Al6Si6O24]- (SO4)2.03, at room pressure and from 33 to 1035°C on heating, was determined by using in situ synchrotron X-ray powder diffraction data (λ = 0.92249(5) Å). The satellite reflections in haüyne are lost at ∼400°C and a true substructure results because of this phase transition. There is a discontinuity in the a unit-cell parameter at ∼585°C. The α parameter increases rapidly and non-linearly to 585°C, but above 585°C, the expansion rate decreases. The percent volume change between 33 and 576°C is 2.0(3)%, and 0.6(3)% between 593 and 1035°C. Between 33 and 1035°C, the Al–O, Si–O and S–O distances are constant. Between 33 and 576°C, the angle of rotation of the AlO4 tetrahedron, jAl, changesfrom 11.5 to 5.8°, while the angle of rotation of the SiO4 tetrahedron, φSi, changesfrom 12.4 to 6.3°. The Al–O–Si bridging angle changesfrom 150.05(2) to 153.08(1)° from 33 to 576°C. Beyond 585°C, φAl and φSi angles remain nearly constant even though the maximum rotation of the tetrahedra is not achieved. Moreover, the Al–O–Si angle continues to increase at a slower rate from 585 to 1035°C by 1.05(2)°. From 33 to ∼585°C, the K atom position migrates at a slower rate than the Na and Ca atoms, and the structure expands at a high rate. Beyond 585°C, all the atomic positions of the interstitial cations (Na+, K+, Ca2+) remain nearly constant and the expansion of the structure is retarded.

Keywords

haüynephase transitionhigh-temperature structuressynchrotron radiationRietveld refinement
Type
Research Article
Information
Mineralogical Magazine , Volume 68 , Issue 3 , June 2004 , pp. 499 - 513
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2004

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References

Antao, S.M., Hassan, I. and Parise, J.B. (2003) The structure of danalite at high temperature obtained from synchrotron radiation and Rietveld refinements. The Canadian Mineralogist, 41, 1413–1422.CrossRefGoogle Scholar
Antao, S.M., Hassan, I. and Parise, J.B. (2004) Tugtupite: high temperature structures obtained from in situ synchrotron diffraction and Rietveld refinements. American Mineralogist, 89, 492–497.CrossRefGoogle Scholar
Hammersley, J. (1996) Fit2d user manual. ESRF publication, Grenoble, France.Google Scholar
Hassan, I. (2000) Transmission electron microscopy and differential thermal studies of lazurite polymorphs. American Mineralogist, 85, 1383–1389.CrossRefGoogle Scholar
Hassan, I. and Buseck, P.R. (1989a) Incommensuratemodulated structure of nosean, a sodalite-group mineral. American Mineralogist, 74, 394–410.Google Scholar
Hassan, I. and Buseck, P.R. (1989b) Cluster ordering and antiphase domain boundaries in haüyne. The Canadian Mineralogist, 27, 173–180.Google Scholar
Hassan, I. and Grundy, H.D. (1984) The crystal structures of sodalite-group minerals. Acta Crystallographica, B40, 6–13.CrossRefGoogle Scholar
Hassan, I. and Grundy, H.D. (1991) The crystal structure of haüyne at 293 and 153 K. The Canadian Mineralogist, 29, 123–130.Google Scholar
Hassan, I., Peterson, R.C. and Grundy, H.D. (1985) The crystal structure of lazurite, ideally Na6Ca2[Al6Si6O2 4]S2, a member of the sodalite group. Acta Crystallographica, C41, 827–832.Google Scholar
Hassan, I., Antao, S.M. and Parise, J.B. (2004) Sodalite: high temperature structures obtained from synchrotron radiation and Rietveld refinements. American Mineralogist, 89, 359–364.CrossRefGoogle Scholar
Henderson, C.M.B. and Taylor, D. (1978) The thermal expansion of synthetic aluminate-sodalites. Physics and Chemistry of Minerals, 2, 337–347.CrossRefGoogle Scholar
Larson, A.C. and Von Dreele, R.B. (2000) General Structure Analysis System (GSAS). Los Alamos National Laboratory Report, LAUR 86–748.Google Scholar
Morimoto, N. (1978) Incommensurate superstructures in transformation of minerals. Recent Progress of Natural Sciences in Japan, 3, 183–206.Google Scholar
Saalfeld, H. (1961) Strukturbesonderheiten des Hauyngitters. Zeitschift für Kristallographie, 115, 132–140.CrossRefGoogle Scholar
Schulz, H. (1970) Struktur und Überstrukturuntersuchungen an Nosean-einkristallen. Zeitschift für Kristallographie, 131, 114–138.CrossRefGoogle Scholar
Taylor, D. (1968) The thermal expansion of the sodalite group of minerals. Mineralogical Magazine, 36, 761–769.CrossRefGoogle Scholar
Toby, B.R. (2001) EXPGUI, a graphical user interface for GSAS. Journal of Applied Crystallography, 34, 210–221.CrossRefGoogle Scholar
Tsuchiya, N. and Takeuchi, Y. (1985) Fine texture of hauyne having a modulated structure. Zeitschift für Kristallographie, 173, 273–281.CrossRefGoogle Scholar