Formation of Oriented Polar Crystals in Bulk Poly(vinylidene fluoride)/High-Aspect-Ratio Organoclay Nanocomposites

We have investigated the formation of lamellar crystals of poly(vinylidene fluoride) (PVDF) in the presence of oriented clay particles with different aspect ratios (ARs) and surface properties. Hot-melt screw extrusion of PVDF with 5 wt % of montmorillonite (AR ≈ 12) or fluoromica (AR ≈ 27) resulted in formation of phase-separated blends. Replacing the clays with their organoclay derivatives, organomontmorillonite or organofluoromica, resulted in the corresponding intercalated nanocomposites. The organoclays induced formation of polar β- and γ-polymorphs of PVDF in contrast to the α-polymorph, which dominates in the pure PVDF and the PVDF/clay blends. Solid-state nuclear magnetic resonance revealed that the content of the α-phase in the nanocomposites was never higher than 7% of the total crystalline phase, whereas the β/γ mass ratio was close to 1:2, irrespective of the AR or crystallization conditions. X-ray diffraction showed that the oriented particles with a larger AR caused orientation of the polar lamellar crystals of PVDF. In the presence of the organofluoromica, PVDF formed a chevron-like lamellar nanostructure, where the polymer chains are extended along the extrusion direction, whereas the lamellar crystals were slanted from normal to the extrusion direction. Time-resolved X-ray diffraction experiments allowed the identification of the formation mechanism of the chevron-like nanostructure.