Alignment Controlled Aramid Nanofiber‐Assembled Films

Abstract Aramid nanofibers (ANFs) are a strong and heat‐resistant nanomaterial that can be isolated from commercial para‐aramid fibers, which allow a bottom‐up self‐assembly to form ordered macroscale structures like ANF films. However, the anisotropic nature of high aspect ratio ANFs is not fully exploited when fabricating ANF films for the optimal mechanical properties. In this research, direct ink writing (DIW) is applied to produce ANF‐assembled films with arbitrary shapes, and the shear‐induced alignment of ANFs can follow the printing path direction. Therefore, controlled alignment of ANFs following the computer‐programmed printing pattern is achieved by DIW, which provides a path for the application of topology and nanofiber alignment optimization in nanofiber‐assembled films. In addition, the resulting DIW ANF films exhibit outstanding Young's modulus of 8.39 GPa, tensile strength of 198 MPa, and tensile toughness of 19.4 MJ m⁻³ in the alignment direction, together with a wide working temperature range up to 440 °C without losing 50% of its room temperature storage modulus. Moreover, the demonstrated self‐joining ability, rollability, and lamination processability of the DIW ANF films expand their potential applications toward high‐temperature ultrathin tubes, substrates for flexible printed circuit boards, and three‐dimensional all‐ANF lightweight structural parts in extreme environments.