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Polylactic acid (PLA) was blended with polyethylene glycol (PEG) and spun via a melt-electrospinning system. The effect of PEG content on the PLA melt and the thermal behaviour of the blend was studied using dynamic rheometry and differential scanning calorimetry, respectively. By fitting a rheological model, parameters such as zero-shear viscosity and the relaxation time of polymer chains were obtained. A substantial reduction of zero-shear viscosity and relaxation time by increasing the PEG content from 0 to 30 wt% was observed. Crystallisation peaks shifted to lower temperatures and the crystallinity level increased in PLA/PEG blends against PEG concentration. The results revealed enhanced polymer chain mobility because of the plasticising effect of PEG. Continuous microfibres were obtained by electrospinning of PLA/PEG blends. While neat PLA was not spinnable at the spinning temperature of 200°C, PLA/PEG blends were easily spun and the lowest fibre diameters of 3–6 μm were achieved with 30% PEG loading, at an applied voltage of 70 kV.
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