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The phenomenon of water vapour sorption by anhydrous C3A polymorphs both in the absence and in the presence of CaSO4·0·5 H2O was studied utilising dynamic and static sorption methods. It was found that orthorhombic C3A starts to sorb water at 55% relative humidity (RH) and cubic C3A at 80% RH. Also, C3Ao sorbs a higher amount of water which is predominantly physically bound, whereas C3Ac preferentially interacts with water by chemical reaction. In the presence of calcium sulfate hemihydrate, ettringite was observed as the predominant pre-hydration product for both C3A modifications: that is, ion transport had occurred between C3A and sulfate. Environmental scanning electron microscopic imaging revealed that in a moist atmosphere, a liquid water film condenses on the surface of the phases as a consequence of capillary condensation between the particles. C3A and sulfate can then dissolve and react with each other. Seemingly, pre-hydration is mainly facilitated through capillary condensation and less through surface interaction with gaseous water molecules.

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