Block copolymer compatibilization driven frustrated crystallization in electrospun nanofibers of...

The confined crystallization behaviour of poly(ethylene oxide) (PEO) has been studied in electrospun nanofibers of the phase-separated blends of polystyrene (PS) and PEO compatibilized with polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer. The PS was present as the majority component such that the electrospun nanofibers consisted of PEO domains dispersed in the PS matrix. The phase separation in the blend occurred under the radial constraint of the nanofibers which led to the formation of small-sized fibrillar PEO domains. The use of block copolymer compatibilizer resulted in a noticeable decrease in the PEO domain size in the as-spun nanofibers. Moreover, the decrease in the domain size and domain connectivity was more substantial in the thermally annealed blend nanofibers due to the suppression of the domain coalescence mechanism resulting from the localization of the PS-b-PEO block copolymer at the interface. Consequently, the fraction of PEO domains crystallizing via homogeneous nucleation increased in the compatibilized blend nanofibers due to the presence of higher number of heterogeneity free PEO domains and disruption in their spatial connectivity. Interestingly, in the compatibilized blend nanofibers consisting of low molecular weight PEO, additional crystallization event attributed to surface nucleation was observed. The surface nucleation, plausibly, resulted from the formation of wet-brush structures where the PEO homopolymers homogeneously wet the PEO blocks present at the interface. In such a scenario, the PEO crystallization occurred via surface nucleation at the domain interface. The surface nucleated crystallization was absent in the compatibilized blend nanofibers composed of high molecular weight PEO presumably due to the formation of morphology with dry-brush structures.