Electrospinning is growing as a production technology for many applications, particularly in membranes and tissue engineering. One challenge in electrospinning is the need for high molecular weight polymers, a requirement that often prevents formation of fibers with high proportions of functional materials that may include particles, surfactants, cells, etc. Molecular interactions between lower molecular weight polymers or molecules can provide similar cohesion in the electrospinning jet as entanglements from high molecular weight polymers. This review covers the existing studies of molecular interactions in electrospinning, providing a comprehensive analysis of the different approaches and outlook for the future. Three major categories are discussed: polymer–polymer molecular interactions (such as electrospinning of coacervates or interacting polymer blends), polymer–small molecule interactions (including cross-linking agents or particles mixed with the polymer), and supramolecular polymer electrospinning (cycodextrins, micelles, etc.). Significant attention is paid to the rheology of the polymer solutions and the electrospinning phase diagrams as well as to how these advances expand the use of electrospinning for target applications.

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Ultrafine fibers manufactured through electrospinning are a frontrunner for advanced fiber applications, but transitioning from potential to commercial applications for ultrafine fibers requires a better understanding of the behavior of polymer solutions in electrospinning to enable the design of more complex spinning dopes. In complex fluids, there are viscoelastic stresses and microstructural transitions that alter free surface flows. These may not be seen in shear rheology; therefore, an in-depth analysis of the extensional rheological behavior must be performed. In this work, we use dripping-onto-substrate rheometry to characterize the extensional viscosities of electrospinning dopes from four polymer solutions commonly used in electrospinning (low- and high-molecular-weight polyvinylpyrrolidone in methanol and water as well as poly­(ethylene oxide) and poly­(vinyl alcohol) in water). We link the electrospinnability, characterized through fiber morphology, to the extensional rheological properties for semidilute and entangled polymer solutions and show that high-surface-tension solvents require higher extensional viscosities and relaxation times to form smooth fibers and that the Deborah and Ohnesorge numbers are a promising method of determining electrospinnability. Through this tie between solvent characteristics, viscoelasticity, and electrospinnability, we will enable the design of more complex spinning dopes amenable to applications in wearable electronics, pharmaceuticals, and more.

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This research aims to develop multilayer sandwich-structured electrospun nanofiber (ENF) membranes using biodegradable polymers. Hydrophilic regenerated cellulose (RC) and hydrophobic poly (lactic acid) (PLA)-based novel multilayer sandwich-structures were created by electrospinning on various copper collectors, including copper foil and 30-mesh copper gauzes, to modify the surface roughness for tunable wettability. Different collectors yielded various sizes and morphologies of the fabricated ENFs with different levels of surface roughness. Bead-free thicker fibers were collected on foil collectors. The surface roughness of the fine fibers collected on mesh collectors contributed to an increase in hydrophobicity. An RC-based triple-layered structure showed a contact angle of 48.2°, which is comparable to the contact angle of the single-layer cellulosic fabrics (47.0°). The polar shift of RC membranes on the wetting envelope is indicative of the possibility of tuning the wetting behavior by creating multilayer structures. Wettability can be tuned by creating multilayer sandwich structures consisting of RC and PLA. This study provides an important insight into the manipulation of the wetting behavior of polymeric ENFs in multilayer structures for applications including chemical protective clothing.

Polymer-based thermoelectric generators hold great appeal in the realm of wearable electronics as they enable the utilization of body heat for power generation. Fibers produced from conducting polymers for use in thermoelectric generators have high porosity and good flexibility, providing comfort-based performance advantages over thin films for wearable electronics. Some fiber processing techniques have been explored to produce textile-based thermoelectric generators; however, they fail to approach the conductivities of polymeric thin films. Ultrafine fibers solution processed through electrospinning yield fiber diameters on the nanoscale, allowing for high surface area to volume ratios and thus low thermal conductivity; however, a number of processing challenges in electrospinning conducting polymers limit the success of preparing high performing thermoelectric textiles. In this work, the specific processing challenges inherent to electrospinning conducting polymers are addressed for both n- and p-type materials. For the p-type polymer, 63 wt % PEDOT:PSS fibers are fabricated through solution formulation improvements yielding a conductivity of 3 S/cm and a power factor of 0.1 μW/mK2. The first of their kind n-type poly­(NiETT)/PVA electrospun fibers were created yielding a conductivity of 0.11 S/cm and a power factor of 0.0036 μW/mK2. These nonwoven ultrafine fiber mats show progress toward achieving textile-based thermoelectric materials with equivalent performance of comparable polymeric thin films. This work shows the feasibility of creating ultrafine fibers for use in thermoelectric generators through electrospinning including the first demonstration of poly­(NiETT)/PVA fibers.