Phase evolution during heat treatment of amorphous calcium phosphate derived from fast nitrate synthesis

The phase evolution in amorphous calcium phosphate (ACP, with a Ca/P ratio of 1 : 1), derived from the fast nitrate synthesis using different conditions, was studied in temperature range 20-980°C. ACP crystallized within 600-700°C and the phase composition depended on the synthesis duration. It was firstly revealed that for an extremely short synthesis (1min) two metastable phases α′-CPP and α′-TCP of the high-temperature calcium pyrophosphate α-CPP and tricalcium phosphate α-TCP were crystallized. For a longer synthesis (5min), α′- CPP and minor β-CPP crystallized. The metastable phases gradually transformed to stable polymorphs β-CPP and β-TCP above 800°C, and a biphasic mixture β-CPP/β-TCP or β-CPP formed at 980°C. The crystallization of the metastable phases was attributed to the Ostwald step rule. A mechanism for the formation of TCP (Ca/P = 1.5) from ACP (Ca/P = 1) was proposed. The prepared powders of β-CPP/β-TCP, β-CPP or initial ACP were fine-grained and would have enhanced sinterability. Contribution to the densification was demonstrated due to the thermal transformation of the metastable polymorphs into stable phases having higher densities