The kinetics and mechanisms of crystallization, phase transformation and grain growth in amorphous calcium pyrophosphate (ACPP) derived from the fast nitrate synthesis were studied at 600-800 degrees C. The high-temperature calcium pyrophosphate alpha-CPP crystallized as the major and metastable phase (alpha(/)-CPP), and some stable beta-CPP polymorph also formed. The activation energies were determined with 80 kJ/mol for alpha(/)-CPP grain growth, as well as with 525, 190 and 180 kJ/mol for beta-CPP nucleation, formation and grain growth during alpha(/)-CPP to beta-CPP transformation under isothermal annealing, respectively. The transformation processes were mainly proceeded by surface diffusion and additional volume diffusion as the temperature was increased. The metastable alpha(/)-CPP crystallization was associated with the Ostwald's step rule. The formation of two polymorphs from the same ACPP was assumed to occur from two different short-range order units formed in ACPP before the onset of crystallization. (C) 2017 Elsevier B.V. All rights reserved.