Thermal Expansion and Phase Stability Investigations on Cs-Substituted Nanocrystalline Calcium Hydroxyapatites

The high-temperature phase stability of Ca_10−x Cs _x (PO₄)₆(OH)₂, (x = 0–3) compositions synthesized by various wet chemical methods was investigated. The thermal expansion property of Ca₁₀(PO₄)₆(OH)₂ (abbreviated as CaHAp) and Cs-substituted CaHAp was measured by high-temperature XRD and dilatometry. The average crystallite size of the powders synthesized by wet chemical methods was found to be 10–50 nm range as shown by XRD and TEM. Up to 30 mol% Cs loading was observed to show only the apatite phase by XRD when the apatite powder was nanocrystalline in nature. However, high-temperature stability of the Cs-substituted system is limited to ≤5 mol%. Cs₃(PO₄) is observed to be separated out on heating the material above 773 K for compositions substituted with more than 5 mol% of Cs in the Ca-sublattice. The coefficient of thermal expansion measured by HTXRD is α_a = 12.42 × 10⁻⁶ K⁻¹, α_c = 14.98 × 10⁻⁶ K⁻¹; and α_a = 12.62 × 10⁻⁶ K⁻¹, α_c = 12.57 × 10⁻⁶ K⁻¹ for CaHAp and Ca_9.78Cs_0.2(PO₄)₆(OH)_1.96, respectively, in the temperature range of 298-1083 K. Bulk thermal expansion measurements are seen to be in agreement with the lattice expansion results.