The addition of expansive agents could overcome the main disadvantages of raw concrete including high brittleness and low tensile strength. Few studies have investigated the early hydration kinetics of expansive cementitious binders, though the findings from the early hydration kinetics are helpful for understanding their technical performances. In this study, mixtures of 3CaO•3Al2
(i.e., ZY-type™ expansive agent) with different proportions of mineral admixtures (e.g., fly ash and slag) were added into cement pastes to investigate the early hydration kinetics mechanism of expansive cementitious binders. Early hydration heat evolution rate and cumulative hydration heat were measured by isothermal calorimeter. Kinetic parameters were estimated based on the Krstulovic–Dabic model and Knudsen equations. Mechanical performances of expansive cementitious binders were tested in order to evaluate if they met the basic requirements of shrinkage-compensating materials in technical use. The early hydration heat released from cementitious binders containing ZY-type™ expansive agent was much greater than that released by pure cement, supporting the idea that addition of the expansive agent would improve the reaction of cement. The early hydration kinetic rates were decreased due to the reactions of the mineral admixture (e.g., fly ash or slag) and the ZY-type™ expansive agent in the cement system. The hydration reaction of cementitious binders containing ZY-type™ expansive agent obeyed the Krstulovic–Dabic model well. Three processes are involved in the hydration reaction of cementitious binders containing ZY-type™ expansive agent. These are nucleation and crystal growth (NG), interactions at phase boundaries (I), and diffusion (D). The 14-day expansion rates of cementitious binders containing ZY-type™ expansive agent are in the range of 2.0 × 10−4
to 3.5 × 10−4
, which could meet the basic requirements of anti-cracking performances in technical use according to Chinese industry standard JGJ/T 178-2009. This study could provide an insight into understanding the effects of expansive agents on the hydration and mechanical performances of cementitious binders.
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