The development of composite materials with functional additives proved to be an effective way to improve or supplement the required properties of polymers. Herein, mesoporous silica (SBA-15) with different pore sizes were used as functional additives to prepare SBA-15/PF (phenolic resin) nanocomposites, which were prepared by in situ polymerization and then, compression molding. The physical properties and structural parameters of SBA-15 with different pore sizes were characterized by N2 adsorption–desorption, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The thermal properties of the SBA-15/PF hybrid were investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The mechanical, friction, and dynamic mechanical properties of SBA-15/PF nanocomposites were also studied. The results revealed that the pore sizes of SBA-15 have a significant effect on the resulting SBA-15/PF hybrid and SBA-15/PF nanocomposites. The thermal stability of the SBA-15/PF hybrid was dramatically improved in comparison with pure PF. The friction and dynamic mechanical properties of the SBA-15/PF nanocomposites were enhanced significantly. Specifically, the glass transition temperature (Tg) of the nanocomposite increased by 19.0 °C for the SBA-15/PF nanocomposites modified with SBA-15-3. In addition, the nanocomposite exhibited a more stable friction coefficient and a lower wear rate at a high temperature. The enhancement in thermal and frictional properties for the nanocomposites is ascribed to the confinement of the PF chains or chain segments in the mesopores channels.
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