Magnetic nanofibers are of great interest in basic research, as well as for possible applications in spintronics and neuromorphic computing. Here we report on the preparation of magnetic nanofiber mats by electrospinning polyacrylonitrile (PAN)/nanoparticle solutions, creating a network of arbitrarily oriented nanofibers with a high aspect ratio. Since PAN is a typical precursor for carbon, the magnetic nanofiber mats were stabilized and carbonized after electrospinning. The magnetic properties of nanofiber mats containing magnetite or nickel ferrite nanoparticles were found to depend on the nanoparticle diameters and the potential after-treatment, as compared with raw nanofiber mats. Micromagnetic simulations underlined the different properties of both magnetic materials. Atomic force microscopy and scanning electron microscopy images revealed nearly unchanged morphologies after stabilization without mechanical fixation, which is in strong contrast to pure PAN nanofiber mats. While carbonization at 500 °C left the morphology unaltered, as compared with the stabilized samples, stronger connections between adjacent fibers were formed during carbonization at 800 °C, which may be supportive of magnetic data transmission.

Electrospinning is a well-known technology used to create nanofiber mats from diverse polymers and other materials. Due to their large surface-to-volume ratio, such nanofiber mats are often applied as air or water filters. Especially the latter, however, have to be mechanically highly stable, which is challenging for common nanofiber mats. One of the approaches to overcome this problem is gluing them on top of more rigid objects, integrating them in composites, or reinforcing them using other technologies to avoid damage due to the water pressure. Here, we suggest another solution. While direct 3D printing with the fused deposition modeling (FDM) technique on macroscopic textile fabrics has been under examination by several research groups for years, here we report on direct FDM printing on nanofiber mats for the first time. We show that by choosing the proper height of the printing nozzle above the nanofiber mat, printing is possible for raw polyacrylonitrile (PAN) nanofiber mats, as well as for stabilized and even more brittle carbonized material. Under these conditions, the adhesion between both parts of the composite is high enough to prevent the nanofiber mat from being peeled off the 3D printed polymer. Abrasion tests emphasize the significantly increased mechanical properties, while contact angle examinations reveal a hydrophilicity between the original values of the electrospun and the 3D printed materials.

Electrospinning is a frequently used method to prepare air and water filters. Electrospun nanofiber mats can have very small pores, allowing for filtering of even the smallest particles or molecules. In addition, their high surface-to-volume ratio allows for the integration of materials which may additionally treat the filtered material through photo-degradation, possess antimicrobial properties, etc., thus enhancing their applicability. However, the fine nanofiber mats are prone to mechanical damage. Possible solutions include reinforcement by embedding them in composites or gluing them onto layers that are more mechanically stable. In a previous study, we showed that it is generally possible to stabilize electrospun nanofiber mats by 3D printing rigid polymer layers onto them. Since this procedure is not technically easy and needs some experience to avoid delamination as well as damaging the nanofiber mat by the hot nozzle, here we report on the reversed technique (i.e., first 3D printing a rigid scaffold and subsequently electrospinning the nanofiber mat on top of it). We show that, although the adhesion between both materials is insufficient in the case of a common rigid printing polymer, nanofiber mats show strong adhesion to 3D printed scaffolds from thermoplastic polyurethane (TPU). This paves the way to a second approach of combining 3D printing and electrospinning in order to prepare mechanically stable filters with a nanofibrous surface.