Crystal Orientation Behavior and Shape-Memory Performance of Poly(vinylidene fluoride)/Acrylic Copolymer Blends

The crystal orientation behavior and shape-memory performance of miscible poly(vinylidene fluoride) (PVDF)/acrylic copolymer blends in various ratios have been investigated. With the incorporation of amorphous acrylic copolymer into the gallery of PVDF lamellae, the molecular connection (tie molecule concentration) between the neighboring PVDF crystals decreases gradually. For the blends with more than 80 wt % PVDF, most of the PVDF α-crystals are transformed into β-crystals upon deformation, and the molecular chains of the β-crystals are aligned along the stretching direction because tie molecules transfer the loading effectively. For the blends with less than 30 wt % PVDF, almost all of the PVDF crystals are isolated from each other with very few tie molecules. Mechanical deformation induces the perpendicular crystal molecular chain arrangement with no crystal form transitions. For the blends with 40 wt % to 70 wt % PVDF, the <i>c</i>-axis-oriented β-phase and the tilt-oriented α-phase coexist in the uniaxially stretched blends. The shape-memory properties of the blends were also evaluated over the same blend composition range. The maximum shape-memory recovery properties were observed for the blend sample containing 50 wt % PVDF, in which a small amount of tie molecules connect the PVDF crystallites to form a deformable elastic network. This network contributes to the good shape-memory properties of the blend. For the blends with very few tie molecules or high tie molecule concentrations, the deformation induces the slipping of the amorphous molecules or the large fibrillar crystal structure, respectively; thus, these samples exhibit relatively low shape-memory performance

Programmable Structure Control in Cigarlike TiO₂ Nanofibers and UV-Light Photocatalysis Performance of Resultant Fabrics

Novel cigarlike nanofibers with an outer-shell and inner-continuous-pore structure and resultant fabrics have been fabricated by coupling the self-assembly of polystyrene-<i>block</i>-poly­(ethylene oxide) (PS-<i>b</i>-PEO) containing titanium precursors with the electrospinning technique in our previous work [You et al. ACS Appl. Mater. Interfaces 2013, 5, 2278]. In the current work, the structure control in these nanofibers has been investigated in detail using scanning electron microscopy, focused ion beam, and small angle X-ray scattering. Our results indicate that electrospinning conditions, the adopted solvent, the volume fraction of PS-<i>b</i>-PEO block copolymer, and the amount of titanium tetraisopropoxide in the mixture produce significant effects on both outer-shell and inner-continuous structures in the nanofibers. The parameters discussed above make it possible to achieve programmable structure control in the aspect of the diameter, thickness of the outer shell, and inner continuous pore. As a result, both micropores among fibers and nanopores in certain fibers are under their control. Furthermore, the photocatalytic activity of resultant TiO₂ fabrics was investigated by taking the photodegradation of Rhodamine B as an example. The results suggest that the degradation efficiency and rate constant exhibit sensitivity on the structure of nanofibers

Novel Cigarlike TiO₂ Nanofibers: Fabrication, Improved Mechanical, and Electrochemical Performances

By coupling the self-assembly of polystyrene-block-poly­(ethylene oxide) (PS-b-PEO) containing titanium precursors with the electrospinning technique, novel cigarlike nanofibers with an outer-shell and inner-continuous-pore structure and resultant fabrics were fabricated. Different from typical porous metal oxides, the prepared high-surface-area nonwoven fabrics show excellent mechanical properties. Not only are these fabrics self-supporting over a large area, but they can also be cut using scissors, which is important for large-scale applications. Furthermore, as electrode materials in Li-ion batteries, these fabrics exhibit much higher charge/discharge capacity and cycle stability compared with the commercially available nanosized TiO₂ (P25). The improved mechanical and electrochemical performances are attributed to the presence of an outer-shell, inner-bicontinuous structures (including continuous TiO₂ frame and continuous nanopores) and hierarchical pores from the cigarlike nanofibers