Unique orientation textures formed in miscible blends of poly(vinylidene fluoride) and poly[(R)-3-hydroxybutyrate]

The oriented crystallization of poly[(R)-3-hydroxybutyrate] (PHB) in the miscible blends with poly(vinylidene fluoride) (PVDF) was investigated with various compositions. The PVDF/PHB blend films were prepared by solution casting and subsequent melt-quenching in ice water. Oriented films of the blends were prepared by uniaxially stretching the melt-quenched film at 0 °C in ice water using a hand-operated stretching apparatus. The oriented blend films were heat-treated at a fixed length in order to crystallize PHB in the oriented state. The crystal orientation and the lamellar textures of the obtained samples were studied with wide-angle X-ray diffraction (WAXD), and small-angle X-ray scattering (SAXS), respectively. The SAXS measurements showed that a considerable amount of molecular chains of PHB are excluded from the lamellar stacks of PVDF and exist in the interfibrillar regions in the oriented films of the blends. The cold crystallization of PHB in the interfibrillar region results in the orientation of PHB crystals, and the type of crystal orientation depends upon the composition of the blends. For the PVDF/PHB=4/6-7/3 blends, the crystal a-axis of PHB is highly oriented parallel to the drawing direction and the crystal c-axis (molecular chain axis) in PHB crystals is perpendicular to the drawing direction, i.e. orthogonal to the chain axis of the crystals of PVDF. It is considered that the a-axis orientation is induced by the confinement of crystal growth in the interfibrillar nano-domains. For the PVDF/PHB=2/8-3/7 blends, however, the crystal c-axis of PHB is primarily oriented in the drawing direction, suggesting that the stressed molecular chains of PHB are crystallized with the molecular orientation retained.