The effects of polycarboxylate superplasticizers (PCEs) on the dispersing properties and initial hydration of cement particles with various water-to-cement (w/c) ratios was investigated, including the water film thickness (WFT), rheology, fluidity, adsorption of PCEs, zeta potential, degree of hydration, hydration products. The experimental results demonstrate that the initial rheological and fluidity parameters were more sensitive to the PCE dosage at a lower w/c because the WFT and the zeta potential on cement particles change more significantly. Moreover, the higher adsorption amounts of the PCEs at a lower w/c lead to a stronger inhibition of the initial hydration, whilst, at the same PCE dosage, the cement pastes have a more rapid fluidity loss and quicker hydration reactions at a higher w/c due to a lower adsorption amount of the PCE on cement particles.
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