Bio-based epoxy adhesives face significant challenges due to their relatively poor mechanical properties compared to their petroleum-based competitors, including low fracture toughness and abrupt failure. By mimicking the molecular structure of spider silk, which is one of the toughest materials in nature, 3D-printed polymer overlapping curls consisting of coiling fibers with sacrificial bonds and hidden lengths, were impregnated into a bio-based epoxy adhesive to improve its mode I fracture toughness. Such bio-inspired structures were designed specifically to toughen and improve the crack resistance of adhesive joints. These overlapping curls were embedded in the bio-based epoxy bondline with various adhesion patterning strategies, aiming to architect the fracture scenario and increase mode I energy dissipation. Double cantilever beam test results show that an extrinsic bridging is triggered by the embedded curls that promote progressive failure and delay crack growth, which improved the mean energy release rate by 133% and enhanced the mean peak energy release rate up to 313%. The proposed 3D-printed coiling fibers successfully improved the mechanical performance of the bio-based epoxy and retarded the crack growth within the bondline, opening new horizons for their use as carriers of bondlines in structural applications to control crack growth in adhesively bonded joints.

In this study, a 3D-printed biomimetic overlapping curl structure inspired by spider silk molecular structure, containing sacrificial bonds and hidden lengths, is studied as a toughening mechanism for a bio-based epoxy. Experimental results of the fracture phenomena of the overlapping curl-reinforced bio-based epoxy identify three toughening mechanisms triggered by the overlapping curl: (1) crack re-initiation, (2) overlapping curl bridging, and (3) epoxy ligament. First, the integrated overlapping curl creates a void within the epoxy matrix. As the crack tip reaches the end of this void, the crack re-initiates. Then, as the hidden length of overlapping curl unfolds, it leads to a bridging effect in resisting crack growth. In addition, for the smallest hidden length, an epoxy ligament is formed due to crack branching, significantly improving the energy release rate. The epoxy fracture energy release rate increased by 13 %. The overall modest improvement is attributed to the large plastic dissipation energy of the epoxy and the relatively low overlapping curl load-capacity. However, when expanding the design space numerically, it was shown that as the failure load of the overlapping curl increases, the bridging effect increases progressively. The introduction of the bio-inspired overlapping curl structure into bio-based epoxy proves the concept of a toughening strategy for developing high-performance sustainable composite materials.

Spider silk is known for its excellent strength and fracture resistance properties due to its molecular design structure, characterized by sacrificial bonds and hidden lengths. These structures have inspired reinforcements of synthetic polymer materials to enhance toughness. In this study, we mimic these natural toughening mechanisms by designing and manufacturing 3D-printed polymeric structures incorporating overlapping curls consisting of coiling fiber with sacrificial bonds and hidden lengths. Utilizing the liquid rope coiling effect, we manufactured overlapping curls using three polymers: polylactic acid (PLA), liquid crystal polymer (LCP), and polyamide 6 (PA6). Uniaxial tensile tests were performed to characterize the mechanical properties of overlapping curl as a function of geometries, post-treatments, and material constitutive parameters. Our results show that single-sided overlapping curls can fully unfold while double-sided curls are prone to premature failure. Heat-pressure post-treatment was found to significantly increase the load-capacity of the sacrificial bonds by up to [Formula presented] due to increased contact area. However, the defects introduced in the fibre after the break of the sacrificial bonds, make the structure more susceptible to premature failure, limit the complete unfolding of the hidden length, and lead to a decrease up to [Formula presented] of the toughness. To guarantee the complete unfolding of the hidden lengths and improve the toughness, we demonstrate that selecting a polymer material with either high fracture strength (e.g., LCP, [Formula presented]) or high fracture strain (e.g., PA6, >2) is crucial, and increase toughness up to [Formula presented] and [Formula presented], respectively.