▎ 摘　　要

The van der Waals (vdW) force dominated interface between graphene and polymer matrix creates weak points in the mechanical sense. Chemical functionalization was expected to be an effective approach in transfer of the outstanding performance of graphene across multiple length scales up to the macroscopic level, due to possible improvements in the interfacial adhesion. However, published works showed the contradiction that improvements, insensitivity, or even worsening of macro-mechanical performance have all been reported in graphene-based polymer nanocomposites. Particularly central cause of such discrepancy is the variations in graphene/polymer interfacial chemistry, which is critical in nanocomposites with vast interfacial area. Herein, O-3/H2O gaseous mixture was utilized to oxidize monolayer graphene sheet with controlled functionalization degrees. Hydrogen bonds (H bonds) are expected to form between oxidized graphene sheet/poly(methyl methacrylate) (PMMA) at the interface. On the basis of in situ tensile-micro Raman spectroscopy, the impacts of bonding types (vdW and H-bonds) on both key interfacial parameters (such as interfacial shear strength and critical length) and failure modes of graphene/PMMA nanocomposite were clarified for the first time at the microscopic level. Our results show that owing to improved interfacial interaction via H bonds, the interface tends to be stiffening and strengthening. Moreover, the mechanical properties of the functionalized graphene/PMMA interface will be set by the competition between the enhanced interfacial adhesion and the degraded elastic modulus of graphene, which was caused by structural defects in the graphene sheet during the functionalization process and could lead to catastrophic failure of graphene sheets in our experimental observation. Our results will be helpful to design various nanofiller-based nanocomposites with high mechanical performance.