Raman Analysis of Orientation and Crystallinity in High T_g, Low Crystallinity Electrospun Fibers

Electrospun fibers of amorphous or low-crystallinity polymers typically exhibit a low molecular orientation that can hamper their properties and application. A key stage of the electrospinning process that could be harnessed to mitigate the loss of orientation is jet rigidification, which relates closely to the solvent evaporation rate. Here, we establish quantitative Raman methods to assess the molecular orientation and crystallinity of weakly crystalline poly(2,6-dimethyl-1,4-phenylene oxide) fibers with varying diameters. Our findings demonstrate that solvent volatility can be leveraged to modulate the orientation and crystallinity through its impact on the effective glass transition temperature (T_g,eff) of the polymer jet during the electrospinning process. Specifically, a highly volatile solvent yields a higher and more sustained orientation (median ⟨P₂⟩ of 0.53 for diameters < 1.0 µm) because its fast evaporation rapidly increases T_g,eff above room temperature. This vitrification early along the jet path promotes the formation of an oriented amorphous phase and a moderate fraction of strain-induced crystals. Our data reveals that a high T_g is a crucial parameter for reaching high orientation in amorphous or low-crystallinity polymer systems.