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Abstract The covid‐19 pandemic has revealed the need for alternative production approaches with low startup costs like electrospinning for filter needs, the most imperative element of the personal protective equipment (PPE). Current attempts in advancing melt electrospinning deal with developing strategies for fiber diameter attenuation toward sub‐micron scale. Here, the attunement in the spinning‐zone temperature known as ''spin‐line temperature profile'' was utilized as a baseline for fiber diameter reduction. The mechanical performance of the melt‐electrospun linear low‐density polyethylene (LLDPE) fibers is reported to characterize their structural transformation with respect to various spin‐line temperature profiles. With an increase in the spin‐line temperature to above 100°C in the area of cone formation, an increased tensile and yield strength along with fiber diameter reduction by four‐folds was demonstrated. A significant increase in toughness, by almost three times, without compromising the stiffness and Young's modulus was observed. The dynamic mechanical analysis revealed that spinning in high temperatures produces changes in the alpha (α) relaxation, contributing to the significant increase in strain at break. These results are significant because polyolefin fibers are an imperative element of medical textiles and PPE. Therefore, developing a correlation for process‐structure‐properties for emerging production techniques like melt electrospinning becomes critical. 

Polyethylene melt conductivity was increased by adding a commercial anti-static agent, which resulted in a 20× decrease in electrospun fiber diameter and formation of a significant fraction of sub-micron diameter fibers. Two polyethylene formulations and varying additive concentrations were utilized to span the parameter space of conductivity and viscosity. The key role of conductivity in determining the jet radius (which sets the upper limit on the fiber size) is discussed in the context of fluid mechanics theory and previous simulations. Parameters which affect the conversion of the liquid jet to a solid fiber and the pertinent theory are outlined. An “unconfined” experimental configuration is utilized to both avoid potential needle clogging and enable direct observation of important characteristic length scales related to the interaction of the fluid and the applied electric field. In this approach, the fluid spontaneously forms an array of cone perturbations which act as stationary “nozzles” through which the mobile fluid flows to form the jet. The experimental data and theory considerations allow for a holistic discussion of the interaction between flow rate, viscosity, conductivity, and the resultant jet and fiber size. Information about the fluid viscosity and conductivity gained by observing the electrospinning process is highlighted. Schemes for theoretically predicting the cone-jet density, cone size, and flow rate are compared to experimental results.