Ultralow-Carbon Nanotube-Toughened Epoxy: The Critical Role of a Double-Layer Interface

Understanding the chemistry and structure of interfaces within epoxy resins is important for studying the mechanical properties of nanofiller-filled nanocomposites as well as for developing high-performance polymer nanocomposites. Despite the intensive efforts to construct nanofiller/matrix interfaces, few studies have demonstrated an enhanced stress-transferring efficiency while avoiding unfavorable deformation due to undesirable interface fractures. Here, we report an optimized method to prepare epoxy-based nanocomposites whose interfaces are chemically modulated by poly(glycidyl methacrylate)-block-poly(hexyl methacrylate) (PGMA-b-PHMA)-functionalized multiwalled carbon nanotubes (bc@fMWNTs) and also offer a fundamental explanation of crack growth behavior and the toughening mechanism of the resulting nanocomposites. The presence of block copolymers on the surface of the MWNT results in a promising double-layered interface, in which (1) the outer-layered PGMA segment provides good dispersion in and strong interface bonding with the epoxy matrix, which enhances load transfer efficiency and debonding stress, and (2) the interlayered rubbery PHMA segment around the MWNT provides the maximum removable space for nanotubes as well as triggering cavitation while promoting local plastic matrix deformation, for example, shear banding to dissipate fracture energy. An outstanding toughening effect is achieved with only a 0.05 wt % carbon nanotube loading with the bc@fMWNT, that is, needing only a 20-times lower loading to obtain improvements in fracture toughness comparable to epoxy-based nanocomposites. The enhancements of their corresponding ultimate mode-I fracture toughnesses and fracture energies are 4 times higher than those of pristine MWNT-filled epoxy. These results demonstrate that a MWNT/epoxy interface could be optimized by changing the component structure of grafted modifiers, thereby facilitating the transfer of both mechanical load and energy dissipation across the nanofiller/matrix interface. This work provides a new route for the rational design and development of polymer nanocomposites with exceptional mechanical performance.