For the first time, a porous mesh of poly(ε-caprolactone) (PCL) was electrospun directly onto carbon fiber (CF) plies and used to develop novel structural epoxy (EP) composites with electro-activated self-healing properties. Three samples, i.e., the neat EP/CF composite and two laminates containing a limited amount of PCL (i.e., 5 wt.% and 10 wt.%), were prepared and characterized from a microstructural and thermo-mechanical point of view. The introduction of the PCL mesh led to a reduction in the flexural stress at break (by 17%), of the interlaminar shear strength (by 15%), and of the interlaminar shear strength (by 39%). The interlaminar fracture toughness of the prepared laminates was evaluated under mode I, and broken samples were thermally mended at 80 °C (i.e., above the melting temperature of PCL) by resistive heating generated by a current flow within the samples through Joule’s effect. It was demonstrated that, thanks to the presence of the electrospun PCL mesh, the laminate with a PCL of 10 wt.% showed healing efficiency values up to 31%.
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