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3D printing has gained a spot within the industry during the last decade due to the advantages it presents regarding conventional manufacturing technologies. Nevertheless, the high processing time and the material waste due to the use of printing supports are still some of the main challenges that have to be addressed. In this research work, a simple strategy to minimize the processing time and the material waste is carried out through a two-stage processing method. Here, a flat specimen is obtained using a vat photopolymerization 3D printer, presenting a low curing degree. Then, the specimen is bent and subsequent post-curing treatments are performed to increase the cross-link density, thus fixing the desired shape. Furthermore, carbon nanotubes were used as nanoreinforcement for increasing the mechanical properties and exploiting their Joule heating capabilities for the thermal post-curing treatment, being way less energy-consuming (around 1W) than using a conventional oven (around 750 W). The results obtained with a proof-of-concept evinced the suitability of the proposed two-stage processing method to enhance the efficiency and sustainability of the 3D printing process. The printing time and the material waste were reduced by 94.3 % and 16.7 % on average, respectively, with regard to printing the part directly on its final desired shape, as well as showing a shape fixity ratio of around 98 %. Furthermore, an enhancement of the mechanical properties was obtained due to the reorientation of the printed layers during the two-stage processing.

Two different self-healing approaches are studied in this work to analyze the possible contribution of each of the self-healing mechanisms at different temperatures and the possible synergetic effects between them. Thermal and mechanical properties were differently affected by the addition of each of the thermoplastic polymers. This was caused by different phase separations induced during the curing reaction in terms of size and number of the thermoplastic phase domains dispersed within the epoxy matrix and due to the different amounts of thermoplastic polymer that remain solved in the matrix. When using the vitrimeric matrix, phase separation only occurred at the nanometer scale when utilizing poly(bisphenol-A-co-epichlorohydrin) (PBAE) as a thermoplastic agent or higher contents of polycaprolactone (PCL).Self-healing capabilities showed a strong dependence on the temperature used and the type of crack. Low temperatures allowed the thermoplastic phase to flow and fill partially the cracks with moderate levels of self-healing which were only available when phases were separated. Higher temperatures allowed dynamic bonds to induce material healing reaching very high efficiencies but, more importantly, a synergic effect was observed when material was removed from the cracks. In these cases, the flow of the thermoplastic phase filled better the crack and there was an enhanced cooperation between the two healing mechanisms. At higher self-healing temperatures, materials with nanometric size phase separation enabled greater self-healing efficiencies (above 90 %) due to the vitrimeric self-healing capability while the thermoplastic phase helped fill the gaps due to material removal.

Sequential dual-cured epoxy composites, based on off-stoichiometric thiol–epoxy mixtures catalysed by 1-methylimidazole, have been developed by adding carbon nanotubes (CNT). The epoxy curing process initially consists in two thermally activated curing stages: a first thiol–epoxy reaction and later homopolymerization at a higher temperature. This system presents easy shaping/conforming and shape memory properties through thermo-mechanical treatments. Addition of the electrical CNT network into the epoxy matrix allows electrical switching, which increases its performance and in-situ applicability.The obtained results confirmed that CNTs catalyse the homopolymerization epoxy reaction, hindering the sequential curing process, due to the π–π anchoring of imidazole catalyser over the CNTs surface, enhanced by donor–acceptor interaction.Non-doped off-stoichiometric resins present relatively high thermal strength, with a glass transition temperature in the range of 73–109 °C, and high stiffness, with a storage modulus close to 2–3 GPa. They can be easily conformed at low temperature, 60 °C, before their second curing stage, showing a high shaping efficiency (around 90%) and full fixing efficiency (>98%).Nanocomposites with 0.2% CNT present efficient Joule heating, triggering the shape memory at low voltage,