Crystalline Langmuir–Blodgett copolymer films of vinylidene fluoride with trifluoroethylene (70%:30% and 80%:20%) absorb water. Water absorption is accompanied by film swelling, as indicated by an increase in lattice spacing, sometimes by as much as 5%. This water absorption, between 0 and 40 °C, is a result of intercalation or occupation of interstitial sites between the layers of the film, not just water molecules filling voids and defect sites alone. An increase in the film capacitance is observed, although the polymer chains retain all trans configuration of the ferroelectric phase.
Core-shell structures of oxide nanoparticles having a high dielectric constant, and organic shells with large breakdown field are attractive candidates for large electrical energy storage applications. A high growth temperature, however, is required to obtain the dielectric oxide nanoparticles, which affects the process of core-shell formation and also leads to poor control of size, shape, and size-distribution. In this communication, we report a new synthetic process to grow core-shell nanoparticles by means of an experimental method that can be easily adapted to synthesize core-shell structures from a variety of inorganic-organic or inorganic-inorganic materials. Monodisperse and spherical TiO2 nanoparticles were produced at room temperature as a collimated cluster beam in the gas phase using a cluster-deposition source and subsequently coated with uniform paraffin nanoshells using in situ thermal evaporation, prior to deposition on substrates for further characterization and device processing. The paraffin nanoshells prevent the TiO2 nanoparticles from contacting each other and also act as a matrix in which the volume fraction of TiO2 nanoparticles was varied by controlling the thickness of the nanoshells. Parallel-plate capacitors were fabricated using dielectric core-shell nanoparticles having different shell thicknesses. With respect to the bulk paraffin, the effective dielectric constant of TiO2-paraffin core-shell nanoparticles is greatly enhanced with a decrease in the shell thickness. The capacitors show a minimum dielectric dispersion and low dielectric losses in the frequency range of 100 Hz-1 MHz, which are highly desirable for exploiting these core-shell nanoparticles for potential applications.
The absorption of water in Langmuir-Blodgett fi lms of ferroelectric copolymers of polyvinylidene fl uoride with trifl uoroethylene is shown to depend upon the fi lm thickness. This water absorption can have a profound effect on the dielectric properties of the copolymer fi lms. (P.A. Dowben)
The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO(2) nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO(2)-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO(2) nanoparticles serve two purposes, namely to prevent the TiO(2) nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO(2)-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO(2)-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.
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