Regulation of protonation in aramid nanofiber films for improved mechanical properties

Abstract Aramid nanofibers (ANFs) are a strong and heat resistant nanomaterial that can be isolated from commercial poly(p-phenylene terephthalamide) (PPTA) fibers. These nanofibers allow bottom-up self-assembly to form macroscale structures in various form factors through a simple reprotonation process. However, the mechanical properties of these reassembled ANF structures often fall short of those of PPTA fibers, mainly due to insufficient packing, non-uniform microstructures, and low crystallinity. In this study, we present ANF films with improved mechanical properties prepared by a repeated spin-coating technique combined with a reprotonation process using deionized water and formic acid at concentrations ranging from 20 to 60 wt.%. Extensive analyses were performed on the resulting ANF films to evaluate their surface and cross-sectional morphologies, chemical bonds and compositions, thermal stabilities, and mechanical properties. The fabricated ANF films exhibited remarkable performance, with an elastic modulus of 6.7 GPa, tensile strength of 680 MPa, and toughness of 7.7 MJ m−³, while maintaining the inherent thermal stability of PPTA fibers. These properties significantly exceed those of previously reported ANF films, broadening the potential applications for ANF films in various fields.