Rietveld refinements and vibrational spectroscopic studies of Na1−xKxPb4(PO4)3 lacunar apatites (0≤x≤1)

Synthesis of apatites, Na_1−xK_xPb₄(PO₄)₃ 0≤x≤1, with anion vacancy was carried out using solid state reactions. The solid solution of apatite-type structure crystallizes in the hexagonal system, space group P6₃/m (No 176). Rietveld refinements showed that 75% of Pb²⁺ cations are located in the (6h) sites; the ninefold coordination sites (4f) are equally occupied by the other 25% lead cations and the K⁺ and Na⁺ monovalent ions.The structure can be described as built up from PO₄]³⁻ tetrahedra and Pb²⁺ of sixfold coordination cavities (6h positions), which delimit void hexagonal tunnels running along 0 0 1]. These tunnels are connected by cations of mixed sites (4f) half occupied by Pb²⁺ and half by Na⁺/K⁺ mixed cations. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit cell group analysis and by comparison with other apatites. The Raman modes of all the compositions show some linear shifts of the frequencies as a function of the composition toward lower values due the substitutions of Na⁺ by K⁺ with a larger radius.