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.

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.

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The feasibility of soft mechanochemical synthesis was studied here for hydroxyapatite with various types of substitution. It was shown that this method allows obtaining hydroxyapatites substituted with copper or iron cations and hydroxyapatites cosubstituted with zinc cations and silicate groups. Thermal stability of the synthesized samples was evaluated. It was found that to preserve phase homogeneity of the material, the temperature during the preparation of ceramic products and coatings should not exceed 600–800 °C. An exception is the hydroxyapatite where a hydroxyl group is expected to be replaced by a copper cation during the synthesis at a degree of substitution x = 0.5. For this sample, the temperature of the the heat treatment can be increased to 1100–1200 °C because copper cations return to the hydroxyapatite crystal lattice at these temperatures, and the material becomes single-phase.

Hydroxyapatite (HA), the major mineral component of tooth enamel and natural bones, is a good candidate for bone tissue engineering. Synthetic HA is used for making coatings on metallic implants intended for medical applications. A HA coating renders the implant biocompatible and osteoinductive. In addition, it improves fixation and the overall performance of the implanted object. In the present work, HA coatings were deposited on a medical titanium alloy implant with mesh geometry and a developed surface by detonation spraying. The feedstock powder was HA obtained by the dry mechanochemical method. Single-phase HA coatings were obtained. The coatings were formed not only on the surfaces normal to the particle flow direction, but also on the sides of the mesh elements. Despite partial melting of the powder, no decomposition of HA occurred. This work demonstrates the prospects of detonation spraying for the production of HA coatings on metallic implants with complex geometries.