Electrospinning is a widely used technique for manufacturing nanofibers from polymers. The formation of continuous fibers during the drawing of a viscous solution typically depends on entanglements between polymer chains, making thermoplastics the preferred choice. In this study, we have shown that thermosetting polymers such as epoxy, which have crosslinked covalent bonds, can also be electrospun. The resulting fibers have diameters ranging from 150 nm to 6 μm. Tensile mechanical properties of fibers with diameters varying between 410 nm and 4 μm are compared with those of molded epoxy bulk. The electrospun fibers exhibit approximately 555% higher strength, 300% greater stiffness, and a strain of about 109% compared to the equivalent properties of bulk epoxy. When compared with brittle molded bulk, these fibers showed ductile properties. We also observed a correlation between the fiber diameter and the mechanical properties. The molecular morphology of the fibers was monitored and analyzed using polarized micro-Raman spectroscopy to detect molecular orientation. A comparison with epoxy fibers of different diameters from previous studies was conducted to better understand the size effect. This study shows, explains and models the evolution of epoxy molecular morphology from the solution (soft matter) to fiber (solid-state), explaining the transition from brittle to ductile in epoxy fibers, and clarifying the molecular mechanisms that lead to improved mechanical properties.

Thermoplastic polyurethanes (TPU) have attracted increasing attention due to their excellent flexibility, chemical stability, processability and greenness. The traditional processes generally limit them to civil and industrial applications, but electrospun TPU nanofibers with high porosity, high specific surface area and superior mechanical properties are promising in emerging fields. TPU nanofibers’ properties are affected by various electrospinning parameters, such as solution concentration, applied voltage, flow rate and rotational speed. Thus, 29 sets of experiments were designed here by the efficient and low-cost response surface methodology (RSM). The analysis of variance (ANOVA) revealed that the model agrees well with experimental results, and solution concentration is the most crucial parameter affecting nanofibers’ morphology and diameter. Based on it, the impacts of solution concentration and orientation on the mechanical properties of the TPU nanofiber membrane were investigated. Benefiting from the stress transfer and network deformation, the TPU nanofiber membranes parallel to the collection direction possessed the highest stress strength (23.71 MPa), while the nanofiber membranes vertical showed the widest strain range (485%). This study provides useful guidance for the preparation of high-performance TPU nanofibers, contributing to expanding its applicability in emerging fields such as biomedical, filtration and separation, and flexible sensing.

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