Effects of thermal annealing and solvent-induced crystallization on the structure and properties of poly(lactic acid) microfibres produced by high-speed electrospinning

Abstract This research concentrates on the marked discrepancies in the crystalline structure of poly(lactic acid) (PLA) nano- and microfibres, achieved by different annealing strategies. PLA nonwoven mats were produced by high-speed electrospinning. The high-speed production technique allowed the manufacturing of PLA microfibres with diameters of 0.25–8.50 µm with a relatively high yield of 40 g h−1. The crystalline content of the inherently highly amorphous microfibres was increased by two methods; thermal annealing in an oven at 85 °C was compared to immersion in absolute ethanol at 40 °C. The morphology of the fibres was examined by scanning electron microscopy; crystalline forms and thermal properties were assessed using X-ray diffractometry, Raman spectrometry, differential scanning calorimetry (DSC) as well as modulated DSC. As a consequence of 45-min heat treatment, the crystalline fraction increased up to 26%, while solution treatment resulted in 33% crystallinity. It was found that only disordered α′ crystals are formed during the conventional heat treatment; however, the ethanol-induced crystallization favours the formation of the ordered α polymorph. In connection with the different crystalline structures, noticeable changes in the macroscopic properties such as heat resistance and mechanical properties were evinced by localized thermomechanical analysis and static tensile test, respectively.