High-Strength Stereolithographic 3D Printed Nanocomposites: Graphene Oxide Metastability.

The weak thermomechanical properties of commercial 3D printing plastics have limited the technology's application mainly to rapid prototyping. In this report, we demonstrate a simple approach that takes advantage of the metastable, temperature-dependent structure of graphene oxide (GO) to enhance the mechanical properties of conventional 3D-printed resins produced by stereolithography (SLA). A commercially available SLA resin was reinforced with minimal amounts of GO nanofillers and thermally annealed at 50 and 100 °C for 12 h. Tensile tests revealed increasing strength and modulus at an annealing temperature of 100 °C, with the highest tensile strength increase recorded at 673.6% (for 1 wt % GO). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) also showed increasing thermal stability with increasing annealing temperature. The drastic enhancement in mechanical properties, which is seen to this degree in 3D-printed samples reported in literature, is attributed to the metastable structure of GO, polymer-nanofiller cross-linking via acid-catalyzed esterification, and removal of intercalated water, thus improving filler-matrix interaction as evidenced by spectroscopy and microscopy analyses.