The influence of roughness and the way it affects the adhesion properties and surface free energy (SFE) of polysiloxanes hydrophobised basalt fibres–reinforced cement mortars were determined in this article. The physical properties of mortars were investigated in the experimental part, which also explored the impact of hydrophobisation and basalt fibres (BF) addition on SFE, frost resistance, contact angle (CA), and roughness. A device capable of calculating all parameters was used to indicate the surface roughness and 3D topography. Prior to and after conducting surface and weight hydrophobisation, the contact angle of mortars was specified. Subsequently, it was used for carrying out SFE calculation by means of Neumann’s method, enabling us to characterize the adhesion properties and wettability of mortars. The research indicated that the surface roughness was substantially decreased, in turn raising the frost resistance. The corrosion resistance drops when the surface roughness, water absorption, and number of fibres in the mortar increase. The SEM images presenting the structure of polysiloxane coating and mortars were provided.
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