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Several methods were employed to study the time dependent film formation of a self synthesized anionic latex dispersion in water and cement pore solution. First, a model carboxylated styrene/n-butyl acrylate latex dispersion possessing a minimum film forming temperature (MFFT) of 18 °C and a glass transition temperature (Tg) of 30 °C was synthesized via emulsion polymerization. Next, its film forming behaviour was studied at 40 °C, using an ESEM instrument. The analysis revealed that upon removal of water, film formation occurs as a result of particle packing, particle deformation and finally particle coalescence. Film formation is significantly hindered in synthetic cement pore solution. This effect can be ascribed to adsorption of Ca2+ ions onto the surface of the anionic latex particles and to interfacial secondary phases. This layer of adsorbed Ca2+ ions hinders interdiffusion of the macromolecules and subsequent film formation of the latex polymer.