Studies on the size effects of nano-TiO₂ on Portland cement hydration with different water to solid ratios

The effects of using different sizes of nano-TiO₂ (NT) on the hydration characteristics of Portland cement with different water to solid ratios (w/s, solid: cement + NT) were investigated in this study. Cement was partially replaced by NT with two sizes, 5 nm and 25 nm, at weight fractions of 0, 0.5%, 1.0%, 1.5% and 2.0%. The compressive strength, hydration products, hydration degree, pore structures and morphologies of the modified cement pastes were systematically evaluated. The experimental results showed that a suitable NT content effectively enhanced the compressive strength of the cement paste, and this enhancement directly depended on the NT particle size. Cement paste mixed with 5-nm NT resulted in a higher compressive strength than 25-nm NT, irrespective of the w/s ratio. The cement paste with a maximum compressive strength at all the curing ages was obtained using a 0.3 w/s ratio and 0.5 wt% of 5-nm NT (which were therefore identified as the optimal NT parameters). The compressive strength of this cement paste increased by 41.4%, 15.9%, 18.7% and 24.35% at 1, 3, 7 and 28 days, respectively, compared to a control sample. For both NT sizes, the w/s ratio and the NT content controlled the compressive strength development of the paste during the early and late ages, respectively. Compared with 25-nm NT, replacing cement by 5-nm NT within the optimum content range was more effective in accelerating cement hydration, increasing the hydration degree, decreasing the crystal size of Ca(OH)₂, refining the pore structure and densifying the cement paste at the microscale, all of which increased the compressive strength at the macroscale.