Ultrasonic-assisted conversion of limestone into needle-like hydroxyapatite nanoparticles

Needle-like hydroxyapatite nanoparticles were successfully synthesized via a reaction between calcium oxide (CaO) that was obtained from calcined limestone and orthophosphoric acid (H₃PO₄) under ultrasonic irradiation at 25 °C. The reaction systems were exposed to ultrasonic waves of 20 kHz for various times ranging from 0 to 4 h. The initial and final pH values of the mixtures of CaO and H₃PO₄ solution were continuously observed (pH < 4.0) after ultrasonic irradiation. The powder was then dried at 60 °C and calcined at 300 °C for 3 h (3 °C/min). The products were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The results showed that the formation of needle-like hydroxyapatite (HAp) nanoparticles was substantially accelerated compared with the reaction without ultrasonic irradiation. The HAp phase was increasingly visible with longer ultrasonic irradiation time compared with the monetite phase (CaHPO₄). This suggests that ultrasonic waved induced a phase transition from the monetite to HAp phase. A smaller needle-like structure of HAp (diameter ∼ 7.4 nm) with a lower contamination of monetite phase was obtained following sonication for 3 h. This study shows that Thai limestone can used as a starting material for synthesizing needle-like HAp nanoparticles with the aid of ultrasonic methods.