Powders of alpha-tricalcium phosphate (alpha-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of alpha-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline alpha-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of alpha-TCP samples during hydration. For this purpose, three alpha-TCP powders, containing 0, 16 and 71 wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1 M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48 h of hydration at 23 degrees C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline alpha-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of alpha-TCP into CDHA. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.