Electrospinning Ethanol–Water Solutions of Poly(Acrylic Acid): Nonlinear Viscosity Variations and Dynamic Taylor Cone Behavior

Electrospinning of polymer solutions is a multifaceted process that depends on the careful balancing of many parameters to achieve a desired outcome, in many cases including mixtures of multiple solvents. A systematic study of how the solution viscosity η$\eta $—a good probe of solvent–polymer interactions—and the electrospinnability change when poly(acrylic acid) (PAA) is dissolved in ethanol–water mixtures at varying mixing ratio is carried out. A pronounced maximum is found in η$\eta $ at a water‐to‐ethanol molar ratio of about 2:1, where the solvent mixture deviates maximally from ideal mixing behavior and partial deprotonation of carboxyl groups by water coincides synergistically with dissolution of the uncharged protonated PAA fraction by ethanol. The PAA concentration is tuned as a function of water–ethanol ratio to obtain a common value of η$\eta $ for all solvent mixtures that is suitable for electrospinning. For high PAA content, the Taylor cone grows in volume over time despite minimum solution flow rate, even experiencing surface gelation for ethanol‐rich solutions. This is attributed to the hygroscopic nature of PAA, drawing excess water into the Taylor cone from the air during spinning. When electrospinning solutions of poly(acrylic acid) (PAA) in mixtures of water and ethanol, both the Taylor cone behavior and the final fiber morphology vary nonlinearily with water–ethanol ratio. Viscosity measurements indicate maximally poor solvent quality at 2:1 molar ratio, further complications arising from water condensation driven by cooling as ethanol evaporates and by the hygroscopic nature of PAA.