Achieving Exceptional Mechanical Properties of Epoxy Resins at Ultralow Loadings via a 3DGO@TiO₂ Hybrid Filler

Epoxy resin (EP) exhibits pronounced intrinsic brittleness arising from the highly crosslinked network formed after curing, thereby restricting its application in load-bearing structures. Although TiO₂ nanoparticles possess the potential for impact-strength improvement, they are highly prone to aggregation, which compromises stress-transfer efficiency within the composite. To overcome this challenge, a ball-milling strategy is adopted to anchor TiO₂ nanoparticles onto three-dimensional graphene oxide (3DGO), leading to the successful fabrication of a 3DGO@TiO₂ hybrid filler. At an ultralow loading of 0.03 wt%, the 3DGO@TiO₂ epoxy resin composite shows a 221.5% increase in impact strength to 19.55 kJ/m² and 33.53% and 32.34% increases in tensile and flexural strength to 64.32 MPa and 96.17 MPa, respectively, relative to neat EP. Morphological analyses indicate that the 3DGO spatial confinement reduces TiO₂ aggregate characteristic length by 55.1% from 1123 nm to 504 nm. Molecular dynamics simulations show that the hybrid filler decreases fractional free volume to 17.6%, induces denser matrix packing, and increases the calculated physical interfacial energy to 1023 kcal/mol, which is 2.2 times that of the pure TiO₂ epoxy resin system. This work confirms that 3DGO simultaneously optimizes nanofiller dispersion and physical confinement, offering a novel strategy for high-performance epoxy composites at ultralow loadings.