Disruption of Electrospinning due to Water Condensation into the Taylor Cone

The well-known problems of electrospinning hygroscopic polymer fibers in humid air are usually attributed to water condensing onto the jet mid-flight: water enters the jet as an additional solvent, hindering solidification into well-defined fibers. Here, we show that fiber fusion and shape loss seen at the end of the process may actually stem from water already condensing into the Taylor cone from where the jet ejects, if the solvent is volatile and miscible with water, for example, ethanol. The addition of water can radically change the solvent character from good to poor, even if water on its own is an acceptable solvent. Moreover, and counterintuitively, the water condensation promotes solvent evaporation because of the release of heat through the phase transition as well as from the exothermic mixing process. The overall result is that the polymer solution develops a gel-like skin around the Taylor cone. The situation is significantly aggravated in the case of coaxial electrospinning to make functional composite fibers if the injected core fluid forms a complex phase diagram with miscibility gaps together with the polymer sheath solvent and the water condensing from the air. The resulting phase separation coagulates the polymer throughout the Taylor cone, as liquid droplets with different compositions nucleate and spread, setting up strong internal flows and concentration gradients. We demonstrate that these cases of uncontrolled polymer coagulation cause rapid Taylor cone deformation, multiple jet ejection, and the inability to spin coaxial fiber mats, illustrated by the example of coaxial electrospinning of an ethanolic polyvinylpyrrolidone solution with a thermotropic liquid crystal core, at varying humidities.