Modeling of multilayer water adsorption and condensation in slits of cement minerals by molecule simulation and adsorption isotherm

The interactions between water and multiscale pores affect significantly most of the physical and chemical properties of cementitious materials such as cement mortar, paste, and concrete. In this paper, molecular mechanism of multilayer water adsorption and condensation in micropores of typical cementitious minerals, the dicalcium silicate (C2S) and calcium silicate hydrate (C-S-H), were investigated by molecular simulations. Classical adsorption isotherm models were examined for their applicability to describe the adsorption law in molecular scales. Besides, the Kelvin equation was modified to satisfy the description of condensation at the microscale. Calculation results show that the most commonly used Brunauer-Emmett-Teller (BET) model can only describe the isotherms within a limited range of low water vapor pressures. In comparison, the modified Brunauer-Emmett-Teller-Pickett (BETP) model can describe the adsorption of water molecular on the surface of C2S and C-S-H more precisely, due to considering the adsorption layers as finite at saturation pressure and the reduced escape probability of the outermost layer of adsorbed water molecules. As for the condensation of water molecules in C2S and C-S-H slits, the traditional Kelvin equation is not applicable. Therefore, a refined Kelvin equation was proposed to describe the relationship between pore size and the pressure required for condensation accurately by considering the critical pore size, adsorption thickness, and decay rate of adsorption potential energy. Further analysis suggests that C2S releases more first-layer adsorption heat and thus shows stronger adsorption of water molecules compared to C-S-H.