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Hydration of alite cement paste of 0.59 waterkement ratio caused the larger pores (>SO nm) to progressively fill with calcium hydroxide and a porous calcium silicate hydrate gel. At early stages of hydration, the larger pores were directly interconnected and diffusion rates were consequently rapid. At later times, the hydrate shells around the adjacent alite grains began to intergrow, continuity of the larger pores was reduced, and diffusion rates were reduced. Beyond 70% hydration, diffusion rates diminished very rapidly with only small amounts of additional hydration. The reduction in continuity of the larger pores was monitored directly by microscopic examination of resin replicas of the pores.