Hexagonal-to-Monoclinic Phase-Modulated HAp Nanofibers for Enhanced Piezoelectric and Biocompatible Performance

In the present manuscript, the influence of reaction time on the hexagonal-to-monoclinic phase transition in hydroxyapatite (HAp) nanofibers synthesized via a low-temperature modified hydrothermal method at 100 °C is investigated. The resulting nanofibers were highly crystalline and stoichiometric, with a Ca/P ratio of approximately 1.67. Comprehensive structural and functional characterization, combining X-ray diffraction with Rietveld refinement, Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), and resonance-tracking piezoresponse force microscopy (RT-PFM), was employed to elucidate the role of the non-centrosymmetric monoclinic P2₁/b phase in governing HAp's structural and piezoelectric properties. The analyses indicated a time-dependent phase evolution from hexagonal (P6₃/m) to monoclinic (P2₁/b), with exclusive formation of the hexagonal phase at 6 h and a clearly dominant monoclinic fraction (73.56%) after 24 h. Nanofibers synthesized for 48 h comprised approximately 98% monoclinic HAp and exhibited elongated morphologies with an average length of 354.82 nm and diameter of 45 nm. RT-PFM measurements confirmed a pronounced piezoelectric response associated with the monoclinic phase, yielding an effective piezoelectric coefficient (<i>d</i>_eff) of 19.85 pm/V. In vitro MTT assays demonstrated that the high monoclinic content did not compromise biocompatibility, as cell viability and cytotoxicity met the requirements of ISO 10993 and ASTM F895 standards. These findings offer new insights into how monoclinic ordering governs the piezoelectric behavior of HAp and suggest a promising strategy for enhancing its performance in biomedical applications.