The effect of the hybridization of a triblock copolymer and a rigid TiO2 nanofiller on the tensile, fracture mechanics and thermo-mechanical properties of bisphenol F based epoxy resin were studied. The self-assembling block copolymer, constituted of a center block of poly (butyl acrylate) and two side blocks of poly (methyl) methacrylate-co-polar co-monomer was used as a soft filler, and TiO2 nanoparticles were employed as rigid modifiers. Toughening solely by block copolymers (BCP’s) led to the highest fracture toughness and fracture energy in the study, KIc = 2.18 MPa·m1/2 and GIc = 1.58 kJ/m2. This corresponds to a 4- and 16-fold improvement, respectively, over the neat reference epoxy system. However, a reduction of 15% of the tensile strength was observed. The hybrid nanocomposites, containing the same absolute amounts of modifiers, showed a maximum value of KIc = 1.72 MPa·m1/2 and GIc = 0.90 kJ/m2. Yet, only a minor reduction of 4% of the tensile strength was observed. The fracture toughness and fracture energy were co-related to the plastic zone size for all the modified systems. Finally, the analysis of the fracture surfaces revealed the toughening mechanisms of the nanocomposites.

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