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Structural investigations, high temperature behavior and phase transition of Na6Ca4(SO4)6F2

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Abstract

Polycrystalline material of a sulfate apatite with chemical composition Na6Ca4(SO4)6F2 or (Na2Ca4)Na4(SO4)6F2 has been synthesized by solid state reactions. Basic crystallographic data are as follows: hexagonal symmetry, a = 9.3976(1) Å, c = 6.8956(1) Å, V = 527.39(1) Å3, Z = 1, space group P63/m. For structural investigations the Rietveld method was employed. Thermal expansion has been studied between 25 and 600 °C. High temperature (HT) powder diffraction data as well as thermal analysis indicate that the apatite-type compound undergoes a reconstructive phase transition in the range between 610 and 630 °C. Single-crystals of the HT-polymorph were directly grown from the melt. Structural investigations based on single-crystal diffraction data of the quenched crystals performed at −100 °C showed orthorhombic symmetry (space group Pna21) with a = 12.7560(8) Å, b = 8.6930(4) Å, c = 9.8980(5) Å, V = 1097.57(10) Å3 and Z = 2. Unit cell parameters for a quenched polycrystalline sample of the HT-form obtained at ambient conditions from a LeBail-fit are as follows: a = 12.7875(1) Å, b = 8.7255(1) Å, c = 9.9261(1) Å, V = 1107.53(2) Å3. The lattice parameters of both modifications are related by the following approximate relationships: a HT ≈ 2c RT, b HT ≈ -(½a RT + b RT), c HT ≈ a RT. The HT-modification is isotypic with the corresponding potassium compound K6Ca4(SO4)6F2. The pronounced disorder of the sulphate group even at low temperatures has been studied by maximum entropy calculations. Despite the first-order character of the transformation clusters of sulfate groups surrounding the fluorine anions can be identified in both polymorphs. Each of the three next neighbor SO4-tetrahedra within a cluster is in turn surrounded by 8–9 M-cations (M: Na,Ca) defining cage-like units. However, in the apatite structure the corresponding three tricapped trigonal prisms are symmetry equivalent. Furthermore, the central fluorine atom of each cluster is coordinated by three next M-neighbors (FM3-triangles), whereas in the HT-polymorph a four-fold coordination is observed (FM4-tetrahedra).

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Acknowledgments

The authors would like to acknowledge the helpful comments and suggestions of Lutz Nasdala (associate editor), Christian L. Lengauer as well as two other anonymous reviewers which improved the quality of this paper. Furthermore, we would like to thank Mrs. Daniela Schmidmair (University of Innsbruck) for troubleshooting graphics software errors.

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Authors and Affiliations

  1. Institute of Mineralogy and Petrography, University of Innsbruck, Innrain 52, 6020, Innsbruck, Austria

    C. Botta, V. Kahlenberg, C. Hejny & D. M. Többens

  2. RHI AG, Technology Center Leoben, Magnesitstr. 2, 8700, Leoben, Austria

    C. Botta

  3. Department Crystallography, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109, Berlin, Germany

    D. M. Többens

  4. Laboratory of Crystallography, University of Bayreuth, 95447, Bayreuth, Germany

    M. Bykov & S. van Smaalen

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  1. C. Botta
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  2. V. Kahlenberg
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  3. C. Hejny
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  4. D. M. Többens
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  5. M. Bykov
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  6. S. van Smaalen
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Correspondence to V. Kahlenberg.

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Editorial handling: L. Nasdala

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Botta, C., Kahlenberg, V., Hejny, C. et al. Structural investigations, high temperature behavior and phase transition of Na6Ca4(SO4)6F2 . Miner Petrol 108, 487–501 (2014). https://doi.org/10.1007/s00710-013-0319-x

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  • DOI: https://doi.org/10.1007/s00710-013-0319-x

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