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Crystal structure of calcium vanadate-phosphate fluoride

  • Z. L. Dong (a1) and T. J. White (a1)


Apatite-type materials AI4AII6(BO4)6X2 have two unique cations sites AI and AII, which can host large mono-, di- tri- and tetra-valent cations. The average cation radii will affect the twist angle and lattice constants. However, there are few reports on the influence of B site substitutions on the twist angle and lattice parameters. It is believed that the lattice constant variation as a function of B site substitutions may not follow the same twist-angle model as proposed for A site. This work reports our results on the crystal chemistry of synthetic apatite Ca10(VxP1−xO4)6F2 obtained through the crystal structure characterization using Rietveld refinement and high-resolution transmission electron microscopy. The quantification of vanadium/phosphorus partitioning in BO4 tetrahedra showed that equilibrium with more than 70% substitution of phosphorous by vanadium was difficult to achieve unless longer annealing (about 1 week at 900 °C) was employed. In comparison with the apatites with different ionic radii at AI and AII sites, Ca10(VxP1−xO4)6F2 apatites with different ionic radii at B site show little twist angle variation for the whole series, which indicates that the dilation of unit cell constants is mainly because of the expansions of BO4 tetrahedra when A site cation is fixed.


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Arikawa, H., Nishiguchi, H., Ishihara, T. and Takita, Y. (2000). “Oxide ion conductivity in Sr-doped La10Ge6O27 apatite oxide,” Solid State Ionics. 136–137, 3137.
Cheary, R. W. and Coelho, A. A. (1992). “A fundamental parameters approach to X-ray line-profile fitting,” J. Appl. Cryst. 25, 109121.
Cheary, R. W. and Coelho, A. A. (1998). “Axial divergence in a conventional X-ray powder diffractometer. I. Theoretical foundations,” J. Appl. Cryst. 31, 851861.
Chen, X. B., Wright, J. V., Conca, J. L. and Peurrung, M. L. (1997). “Effects of pH on heavy metal sorption on mineral apatite,” Environ. Sci. Technol. 31 (3), 624631.
Choudary, B. M., Sridhar, C., Kantam, M. L., Venkanna, G. T. and Sreedhar, B. (2005). “Design and evolution of copper apatite catalysts for N-arylation of heterocycles with chloro- and fluoroarenes,” J. Am. Chem. Soc. 127, 99489949.
Dong, Z. L. (2009). “X-ray diffraction, Rietveld crystal structure refinement and high-resolution transmission electron microscopy of nano-structured materials,” in Handbook of Nanoceramics and Their Based Nanodevices, edited by Tseng, Tseung-Yuen and Singh Nalwa, Hari (American Scientific Publishers, California), Vol. 3, pp. 303336.
Dong, Z. L. and White, T. J. (2004a). “Calcium–lead fluoro-vanadinite apatites. I. Disequilibrium structures,” Acta Crystallogr., Sect. B: Struct. Sci. 60, 138145.
Dong, Z. L. and White, T. J. (2004b). “Calcium–lead fluoro-vanadinite apatites. II. Equilibrium structures,” Acta Crystallogr., Sect. B: Struct. Sci. 60, 146154.
Dong, Z. L. and White, T. J. (2008). “Solid state synthesis and crystal structure of Ca10(VxP1−xO4)6F2 apatite,” Microsc. Microanal. 14 (Suppl 2), 210211.
Dong, Z. L., Kim, J., Lim, S. H., Laursen, K. and White, T. J. (2003). “Crystal Structure of Ca10(VxP1−xO4)6F2 Apatite Synthesised via Solid State Reaction”, Proceedings of the 2nd International Conference on Materials for Advanced Technologies, MRS Singapore, p. 736.
Druon, F., Chenais, S., Raybaut, P., Balembois, F., Georges, P., Gaume, R., Haumesser, P. H., Viana, B., Vivien, D., Dhellemmes, S., Ortiz, V. and Larat, C. (2002). “Apatite-structure crystal, Yb3+: srY4(SiO4)3O, for the development of diode-pumped femtosecond lasers,” Opt. Lett. 27 (21), 19141916.
Hench, L. L. (1991). “Bioceramics: from concept to clinic,” J. Am. Ceram. Soc. 74 (7), 14871510.
Lu, F. Y., Dong, Z. L., Zhang, J. M., White, T. J., Ewing, R. C. and Lian, J. (2013). “Tailoring the radiation tolerance of vanadate-phosphate fluorapatites by chemical composition control,” RSC Adv. 3, 1517815184.
Mercier, P. H. J., Dong, Z. L., Baikie, T., Page, Y. L., White, T. J., Whitfield, P. S. and Mitchel, L. D. (2007). “Ab initio constrained crystal-chemical Rietveld refinement of Ca10(VxP1−xO4)6F2 apatites,” Acta Crystallogr., Sect. B: Struct. Sci. 63, 3748.
Shen, Y. Q., Chen, R., Sun, H. D., Tok, A. and Dong, Z. L. (2010). “Study of the cation distributions in Eu doped Sr2Y8(SiO4)6O2 by X-ray diffraction and photoluminescent spectra,” J. Solid State Chem. 183, 30933099.
Sudarsanan, K., Mackie, P. E. and Young, R. A. (1972). “Comparison of synthetic and mineral fluroapatite, Ca5(PO4)3F, in crystallographic detail,” Mater. Res. Bull. 1, 13311338.
White, T. J. and Dong, Z. L. (2003). “Structural derivation and crystal chemistry of apatites,” Acta Crystallogr., Sect. B: Struct. Sci. 59 (1), 116.


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