Hierarchical interfaces induce high dielectric permittivity in nanocomposites containing TiO2@BaTiO3 nanofibers

Interface issues are common and crucial in nanocomposites or nanohybrid systems since the interface area is enormous on the nanoscale. In the 0-3 dimensional polymer nanocomposites, in which nano-inclusions (0-dimension) are embedded in a 3-dimensionally connected polymer matrix, enhanced dielectric permittivity could be induced by the interfacial polarization at the interfaces between the nano-inclusions and the polymer matrix. In this contribution, we propose and demonstrate that the topological structure of the interface plays an equally important role as the area of the interface in determining the dielectric polarization of polymer nanocomposites. TiO2 nanofibers embedded with BaTiO3 nanoparticles are prepared via electrospinning and then fused with polyvinyl difluoride (PVDF) into polymer nanocomposite films. Modulation of hierarchical interfaces is thus achieved for these nanocomposites. The confinement of these additional interfaces inside the TiO2 nanofibers leads to percolated networks formed by the interfacial regions. The dielectric permittivity of the polymer nanocomposites is thus enhanced by similar to 300% over the PVDF matrix at a low filler loading of 11 vol%. A phase-field simulation study indicates that the enhanced dielectric permittivity could be attributed to the increased polarization in the percolated interfacial regions inside the TiO2 nanofibers. The instantaneous electrical breakdown of the TiO2@BaTiO3 nanofibers studied by the in situ transmission electron microscopy method further reveals the striking feature that the breakdown behavior of the nanofibers changes from semiconductive to metallic with the incorporation of insulating BaTiO3 nanoparticles.