Effect of Nucleating Agents on the Crystallization of Calcium Phosphate Glasses

Phase evolution in calcium phosphate-based glass ceramics has been examined. Pure CaO:P₂O₅ readily formed a glass which surface nucleated upon annealing, but volume nucleation at 680°C was observed only after the addition of the nucleating agents, TiO₂ and A1₂O₃. Phase separation of Ti and Al occurred along with the nucleation and growth of a calcium phosphate phase, similar to β-Ca₂P₂O₇. Heat treatments at higher temperatures and/or for longer times resulted in crystallization of A1- and Ti-rich, phase-separated regions. A glass with a higher CaO:P₂O₅ ratio (approximately 2:1) could be prepared only when a total of 25-35 mol% of TiO₂, A1₂O₃, and SiO₂ were present in the batch. The glass phase-separated into respective SiO₂- and CaO/P₂O₅-rich regions on cooling. The SiO₂-rich regions did not influence crystallization and remained amorphous throughout the heat treatments. In the CaO/P₂O₅-rich regions, homogeneous volume nucleation of a Ti-rich phase readily occurred followed by the heterogeneous nucleation and growth on these nuclei of a calcium phosphate phase. Although this phase was macroscopically composed of spherulites, TEM revealed that they consisted of intertwined nanodendrites whose individual arms were approximately 20 nm wide and 50 nm long.