The effect of graphene properties on the extrusion of a shape memory epoxy vitrimer

• A graphene additive for direct ink writing of epoxy vitrimers has been formulated. • The graphene additives can work efficiently at very low concentrations (<6 wt%). • Printed parts retain tensile strengths of ∼37 MPa and shape memory properties. • The printed materials can be recycled and reprocessed. Thermoset polymers exhibit very appealing mechanical and functional properties. Direct ink writing (DIW) could open new possibilities in the design and fabrication of intricate thermoset parts, but it often requires the use of additives such as fumed silica or nanoclays to modify the rheology of uncured epoxies. However, relatively large concentrations are usually needed what can be detrimental to properties. Graphene-derived additives are an appealing alternative, but we need to understand the key physicochemical characteristics that define an optimum graphene rheology modifier. Here we compare the effect of three different carbon fillers on the viscoelastic response of a reprocessable epoxy vitrimer with shape memory capabilities, graphene oxide (GO), reduced graphene oxide (rGO), and graphene powder (GP), and assess the effect of their chemistry and morphology. The analysis shows that large (∼20 μm in size) rGO flakes enable the formation of strong, printable gels, through Van der Waals interactions and physical entanglement. The vitrimer could be successfully printed by incorporating 5 wt% of rGO. The printed parts exhibit tensile strengths (30–60 MPa), moduli (2–3 GPa), strength recovery after reprocessing (∼80 %), shape-memory properties comparable to the pure epoxy, and improved water resistance due to the introduction of hydrophobic rGO.