High-temperature powder sintering is an integral part of the dense ceramic manufacturing process. In order to find the optimal conditions for producing a ceramic product, the information about its behavior at high temperatures is required. However, the data available in the literature are very contradictory. In this work, the thermal stability of hydroxyapatite prepared by a solid-state mechanochemical method and structural changes occurring during sintering were studied. Stoichiometric hydroxyapatite was found to remain as a single-phase apatite structure with the space group P6₃/m up to 1300 °C inclusively. A further increase in the sintering temperature leads to its partial decomposition, a decrease in the crystallite size of the apatite phase, and the appearance of significant structural strains. It was shown that small deviations from stoichiometry in the Ca/P ratio upward or downward during the hydroxyapatite synthesis lead to a significant decrease in the thermal stability of hydroxyapatite. An apatite containing almost no hydroxyl groups, which is close to the composition of oxyapatite, was prepared. It was shown that the congruent melting of stoichiometric hydroxyapatite upon slow heating in a high-temperature furnace does not occur. At the same time, the fast heating of hydroxyapatite by laser radiation allows, under certain conditions, its congruent melting with the formation of a recrystallized monolayer of oxyhydroxyapatite. The data obtained in this study can be used when choosing sintering conditions to produce hydroxyapatite-based ceramics.

Simulation and computer studies of the structural and physical properties of hydroxyapatite (HAP) with different defects are presented in this review. HAP is a well-known material that is actively used in various fields of medicine, nanotechnology, and photocatalytic processes. However, all HAP samples have various defects and are still insufficiently studied. First of all, oxygen and OH group vacancies are important defects in HAP, which significantly affect its properties. The properties of HAP are also influenced by various substitutions of atoms in the HAP crystal lattice. The results of calculations by modern density functional theory methods of HAP structures with these different defects, primarily with oxygen and hydroxyl vacancies are analyzed in this review. The results obtained show that during the structural optimization of HAP with various defects, both the parameters of the crystallographic cells of the HAP change and the entire band structure of the HAP changes (changes in the band gap). This affects the electronic, optical, and elastic properties of HAP. The review considers the results of modeling and calculation of HAP containing various defects, the applied calculation methods, and the features of the effect of these defects on the properties of HAP, which is important for many practical applications.

Hydroxyapatite (HAP) is the main mineral component of bones and teeth. It is widely used in medicine as a bone filler and coating for implants to promote new bone growth. Ion substitutions into the HAP structure highly affect its properties. One of the most important substituents is magnesium. This paper presents new results obtained using high-precision hybrid density functional theory calculations for Mg/Ca substitutions in HAP in a wide magnesium concentration range within a 2 × 2 × 2 supercell model. Experimental data on the mechanochemical synthesis of HAP-Mg samples with different Mg concentrations are also presented. A comparison between the experiment and the theory showed good agreement: the HAP-Mg unit cell parameters and volume decreased with increasing degree of Mg/Ca substitution. The changes in the distances between the Ca and O, Ca and H, and Mg and O ions upon Mg/Ca substitution in different calcium positions was analyzed. The resulting asymmetry and distortion of the cell parameters were evaluated. It was shown that bulk modulus, energy levels, and band gap depend on the degree of Mg substitutions in the Ca1 and Ca2 positions. The formation energies of Mg/Ca substitutions showed non-monotonic behavior that was different for Ca1 and Ca2 positions. The Ca2 position had a slightly higher probability (~5 meV/f.u.) of substitution than Ca1 position at a Mg concentration x = 0.5. At x = 1, substitution in both positions can coexist. The simulated IR spectra for different Mg/Ca substitutions showed that Mg in the Ca2 position changes the IR spectrum more significantly than Mg in the Ca1 position. Similar changes were recorded in the IR spectra of the synthesized samples. The electronic structure is shown to be sensitive to the number and position of substitutions, which may be used to tweak the optical properties of the HAP-Mg material.

Apatite is widely used in medicine as a biomaterial for bone tissue restoration. Properties of apatite depend on its composition, including the Ca/P ratio. This paper shows what range of Ca/P ratio can be attained in apatite by the mechanochemical method of synthesis, providing fast formation of a single-phase product. The synthesis was carried out from a reaction mixture of CaHPO₄ and CaO at different Ca/P ratios in the range of 1.17–2.10. The products were studied by PXRD, FTIR and NMR spectroscopy, HRTEM, and STA. In mixtures with a low initial Ca/P ratio (1.17–1.48), directly in the mill, the formation of calcium orthophosphate with whitlockite structure containing an HPO₄²⁻ group and structural water is shown for the first time. This phosphate has structure similar to that of whitlockites of hydrothermal origin and differs from high-temperature β-tricalcium phosphate that has composition Ca₃(PO₄)₃. A series of samples of apatite was obtained with varied composition, which depends on the initial Ca/P ratio. At Ca/P < 1.67, the formation of two types of calcium-deficient apatite was documented. At Ca/P > 1.67, the existence of two types of calcium-rich apatite is confirmed.