On the Effect of Ultralow Loading of Microwave-Assisted Bifunctionalized Graphene Oxide in Stereolithographic...

Surface functionalization of graphene oxide (GO) is one of the best ways to achieve homogeneous dispersions of GO within polymeric matrices and composites. Nonetheless, studies regarding how the level of GO functionalization affects the macroscopic properties of three-dimensional (3D) printed nanocomposites are still few. Furthermore, the bifunctionalization of GO with the NH₂/NH₃⁺ groups to obtain improved thermomechanical macroscopic properties at ultralow loads has not been reported. In this paper, fast and straightforward surface bifunctionalization of GO with a controlled ratio of NH₂/NH₃⁺ groups at low, medium, and high functionalization levels (AGOL, AGOM, and AGOH) in a one-step microwave-assisted synthesis is reported for the first time. The functionalization mechanism was disclosed, wherein three graft densities (G_φ) were obtained. A plateau of maximum functionalization (G_φ = 4.9 μmol/m² = 2.9 molecules/nm²) was reached, suggesting that full coverage of the GO surface is achievable. Also, an increase in the exfoliation of functionalized layers was obtained, ranging from d₀₀₂ = 8.6 Å up to d₀₀₂ = 15.8 Å. X-ray photoelectron spectroscopy (XPS) reveals the successful functionalization of GO, as well as an atomic relationship NH₂/NH₃⁺ of about 50/50% in all functionalized samples. Stereolithographic (SLA) 3D-printed nanocomposites (AGOL/R, AGOM/R, and AGOH/R) were obtained using ultralow loads (0.01 wt %) of each bifunctionalized material. This ultralow amount was sufficient to enhance thermal stability (up to 4 °C) and a significant increase in the glass transition temperature (93 °C ≤ T_g ≤ 120 °C). Interestingly, we found that low and medium grafting density promotes a ductile material (ε > 5%); meanwhile, a high graft density produces brittle materials. Also, we observe that the toughness can be tuned as a function of the graft density (AGOH: 24 MPa, AGOM: 342 MPa, AGOL: 562 MPa) at ultralow loadings. The 3D-printed nanocomposites using GO with low graft density (AGOL) increase their tensile strain by 90% in comparison with the control sample (without filler). Finally, the underlying mechanisms were discussed to explain the findings.