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.