Solid‐State NMR Study of Mn2+ for Ca2+ Substitution in Thermally Processed Hydroxyapatites

In the present study calcium hydroxyapatites enriched at 0.08 wt% in Mn²⁺ ions (Mn–HA) and their unsubstituted forms (HA) were synthesized using the same standard wet chemical route. Mn‐HA and HA were both calcined at 800°C to give Mn‐HAc and HAc, respectively or sintered at 1250°C, to give Mn‐HAs and HAs, respectively. The influence of the heat treatment on physicochemical properties of Mn‐HA was investigated using powder X‐ray diffraction (PXRD), scanning, and transmission electron microscopy (SEM and TEM), and solid‐state nuclear magnetic resonance (ssNMR). Mn‐HAc and Mn‐HAs were compared to each other and to HAc and HAs, respectively. Assignment of the proton ssNMR peaks from high‐temperature‐treated apatites has been revised. It was found that Mn–HAc and HAc were nanocrystalline, while Mn‐HAs and HAs comprised micrometer sized, partially fused particles (SEM and TEM). PXRD and ssNMR demonstrated that the incorporation of Mn²⁺ into the crystal lattice of hydroxyapatite significantly facilitates its dehydroxylation and decomposition to oxyhydroxyapatite during calcination at 800°C, and induces its transformation to tetracalcium phosphate (TTCP) and alpha‐tricalcium phosphate (α‐TCP) at 1250°C. Contamination by CaO has also been detected. The ¹H→³¹P NMR cross‐polarization experiments have indicated that the Mn²⁺ ions preferentially occupied the Ca(I) position in the crystallographic unit cell of Mn‐HAc. In Mn‐HAs, the Mn²⁺ ions were evenly distributed between the Ca(I) and Ca(II) positions.