Mayenite was synthesized using the conventional solid-state reaction and two low temperature synthesis methods a self-combustion method and a polymeric precursor process. Using the low temperature methods the metastable phase 5CaO center dot 3Al(2)O(3) (C(5)A(3)) crystallizes at 1173 K (2 h) instead of C(12)A(2). After forming pure crystalline 12CaO center dot 7Al(2)O(3) (C(12)A(2)) at 1373 K (2 h) the hydration was monitored at 283 K. 288 K, 293 K, 298 K and 301 K by heat flow calorimetry. During hydration the first calorimetric peak correlates with the formation of layers around the C(12)A(2) grains and the second peak corresponds to further hydration reactions and crystallization of lamellar calcium aluminate hydrates C(2)AH(8 +/- x) showing different hydration steps of 8.2H(2)O, 8.0H(2)O and 7.5H(2)O depending on temperature. At higher temperatures the formation of hydrate shells is increased and consequently the further hydration reaction is hindered. (c) 2010 Elsevier B.V. All rights reserved.