The characteristics of poly(vinylidene fluoride) (PVDF) nanofibers, prepared by applying the electrospinning technique from N,N‐dimethylformamide/acetone mixtures, were studied by varying the experimental conditions. The nanofiber morphology was assessed by scanning electron microscopy, while wide angle X‐ray diffraction and infrared spectroscopy were performed to study the crystallinity. The influence of the electrospinning conditions, such as kind of solvent mixture, polymer concentration, voltage tension, airflow and humidity, on nanofiber morphology was studied. In particular, the latter parameter, generally not considered, was found to modify the electrospun mat structure in a relevant way. Generally, the above technique turns out to be capable of strongly affecting the polymorphism of the polymer, namely β phase formation was higher in the electrospun mats compared with cast films, which displayed a non‐polar α crystal phase. As far as the influence of the electrospinning conditions on PVDF crystal structure is concerned, modification of the experimental parameters did not affect the α/β ratio. Nevertheless, comparing the behavior of two commercial PVDF samples with similar molecular masses, our results show that the polymer which forms a higher content of β phase in its cast films allowed electrospun mats characterized by almost complete formation of β phase to be obtained. Copyright © 2012 Society of Chemical Industry

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The effectiveness of electrospinning as a simple approach to disperse POSS into a polymer matrix at a nm‐level has been assessed. Electrospun and cast films were prepared by dissolving CA and epoxycyclohexylisobutyl POSS in the solvent mixture acetone/DMAc. The membranes were characterized by SEM, TEM and WAXD. Whereas films produced by casting showed µm‐sized POSS crystals, thus suggesting a small affinity between the polymer matrix and the POSS molecules, those prepared by electrospinning were characterized by a nanometric POSS distribution. This is explained by considering the peculiar solvent evaporation mechanism, occurring during the electrospinning process, which allows to produce nanofibers characterized by a silsesquioxane dispersion similar to that present in solution.magnified image

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Nanostructered nanofibers based on poly(vinylidene fluoride) (PVDF) and polyhedral oligomeric silsesquioxane (POSS) have been prepared by electrospinning process. The starting solutions were prepared by dissolving both the system components in the mixture N,N‐dimethylacetamide/acetone. The characteristics of the fiber prepared, studied by scanning electron microscopy, atomic force microscopy, and wide angle X‐ray diffraction, have been compared with those of PVDF fibers. Morphological characterization has demonstrated the possibility to obtain defect‐free PVDF/POSS nanofibers by properly choosing the electrospinning conditions, such as voltage, polymer concentration, humidity, etc. Conversely, in the case of fibers based on the neat polymer, it was not possible to attain the complete elimination of beads in the electrospun nanofibers. The different behavior of the two types of solutions has been ascribed to silsesquioxane molecules, which, without influencing the solution viscosity or conductivity, favor the formation of uniform structures by decreasing the system surface tension. Concerning POSS distribution in the fibers, the morphological characterization of the electrospun films has shown a submicrometric dispersion of the silsesquioxane. It is relevant to underline that cast films, prepared by the same solutions, have been found to be characterized by POSS aggregation, thus demonstrating a scarce affinity between the two‐system components. Indeed, the peculiar solvent evaporation of the electrospun solution, which is much faster than that occurring during the cast process, prevents POSS aggregation, thus leading to the formation of nanofibers characterized by a silsesquioxane dispersion similar to that present in solution. Finally, the presence of POSS improves the electrospun film mechanical properties. Copyright © 2011 John Wiley & Sons, Ltd.