Precursor decomposition and nucleation kinetics during platelike apatite synthesis

Self-organization of calcium and phosphorus precursors in solution containing acetic acid and ethylene glycol produces a nanosized lamellar acetate-phosphonate hybrid containing two acetate and one phosphonate components. The lamellar morphology of the hybrid precursor is responsible the formation of platelike apatite product after thermal treatment at or above 400 C. However a preliminary preheating stage (300 C, 24 h) is crucial in determining the morphology of the apatite. Activation energy measurements by nonisothermal thermogravimetric analysis show that decomposition of the hybrid precursor involves at least two steps. Among the three components, it appears that the calcium acetate bidentate chelate component is stable below or at 300 C. However, the calcium phosphonate and calcium acetate monodentate components are decomposed at this temperature. Above 360 C, nuclear magnetic resonance and infrared spectroscopic data reveal the decomposition of more stable calcium acetate bidentate chelate. It is evident that the bond rupture of the bidentate calcium acetate species in the precursor results in the start of crystalline apatite formation but the other components must be decomposed by heating prior to this critical step in order to produce platelike apatite.