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Structural characteristics of belite incorporating various amount of BaO and their reactivity with water was investigated by means of XRD, FT-IR and calorimetry.The results indicates that the incorporating amount of BaO in belite lead to high temperature polymorphic forms of belite stabilized to room temperature, at the same time reactivity of belite increased.The internal reason for BaO stabilizing high temperature polymorphs can be assigned to coordinate number of M increasing which lead to more stable of high temperature phases and transformation from high temperature polymophs to low temperature polymorphs hindered when Ca2+ substituted by Ba2+ in belite crystal structure.At the same time, M-O distance increases, which leads to an decrease of bonding strength between M-O, therefore the crystal structure becomes easier to attacked by protons and results in more reactive with water.