Synthesis, X‐ray Structural Analysis and Spectroscopic Investigations (IR and ³¹P MAS NMR) of Mixed Barium/Strontium Fluoroapatites

Abstract

Abstract Continuous solid solutions of barium/strontium fluoroapatites Ba (10− x ) Sr x (PO 4 ) 6 F 2 (Ba (10− x ) Sr x FAp; 0 ⩽ x ⩽ 10) were obtained in an aqueous medium. They were investigated by Rietveld structure‐refinement methods using powder X‐ray diffraction patterns and by chemical analysis, IR spectroscopy and 31 P MAS NMR spectroscopy. Replacement of barium by strontium induces a regular decrease of the lattice constants a and c according to Vegard’s law. The results of the powder‐fitting structure refinements indicate a clear preference of strontium for the S(1) site of the apatitic structure. A high‐wavenumber shift of the IR absorption bands characteristic of PO 4 internal modes is also observed, in agreement with the diminution of the ionic character of the M−O bonds. For increasing strontium content, a regular δ iso increase is shown in the 31 P MAS NMR spectra, from δ = 0.91 ppm for Ba 10 FAp to δ = 3.06 ppm for Sr 10 FAp. For all mixed Ba/Sr fluoroapatites, the low intensities of the spinning bands reflect the weak 31 P chemical‐shift anisotropy, in agreement with the low distortion of the PO 4 tetrahedron, as shown by Rietveld refinement. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)