The fundamental chemical hydration process of portland cement and its main mineral component, tricalcium silicate, was studied by investigating the effects of various additives. A relatively small amount (1−4 wt %) of well-dispersed calcium silicate hydrate (C−S−H), a pure form of the main hydration product, significantly increases both the early hydration rate and the total amount of hydration during the early nucleation and growth period (the first ∼24 h), as measured by calorimetry. This is attributed to a seeding effect whereby the C−S−H additive provides new nucleation sites within the pore space away from the particle surfaces. This mechanism is verified by a digital simulation of the hydration process that reproduces key features of the hydration kinetics. The results provide strong evidence that the hydration process is autocatalytic such that the C−S−H gel product stimulates its own formation. The seeding effect of C−S−H also provides a new explanation of the hydration-accelerating effects of var...