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In order to enhance the early hydration evolution as well as improve the fluidity property of cement paste, calcium silicate hydrates (C-S-Hs)/polycarboxylate (PCE) was self-synthesised by way of the co-precipitation method, and was added into cement paste. The rheological performance and hydration process of the cement paste were analysed. Results showed that adding C-S-Hs–PCE could improve the rheological performance of cement paste. With a low amount of C-S-Hs–PCE adopted, the viscosity and shear stress reduced slightly, while a high amount of C-S-Hs–PCE led to sharply decreased viscosity and shear stress. Adding C-S-Hs–PCE could shorten the cement hydration induction period and improve the hydration heat release rate significantly. The crystalline nuclei provided by C-S-Hs–PCE promoted the nucleation growth of hydration products. When C-S-Hs–PCE content increased, the hydration reaction products in the hardened cement slurry increased remarkably, and a large number of hydration products effectively filled into the micro-pores, leading to reduced large pores and increased nanopores. Adding 1.0% C-S-Hs–PCE increased compressive strength at 1 day by 12.9%, the 3 day compressive strength by 18.2%, 7 day compressive strength by 20.5% and 28 day compressive strength by 12.6%. The findings could provide a theoretical reference for the performance regulation of cementitious materials.

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