Barium titanate nanoparticles embedded in flexible polymer films were synthesized using hydrothermal processing methods. The resulting films were characterized with respect to material composition, size distribution of nanoparticles, and spatial location of particles within the polymer film. Synthesis conditions were varied based on the mechanical properties of the polymer films, ratio of polymer to barium titanate precursors, and length of aging time between initial formulations of the solution to final processing of nanoparticles. Block copolymers of poly(styrene-co-maleic anhydride) (SMAh) were used to spatially separate titanium precursors based on specific chemical interactions with the maleic anhydride moiety. However, the glassy nature of this copolymer restricted mobility of the titanium precursors during hydrothermal processing. The addition of rubbery butadiene moieties, through mixing of the SMAh with poly(styrene-butadiene-styrene) (SBS) copolymer, increased the nanoparticle dispersion as a result of greater diffusivity of the titanium precursor via higher mobility of the polymer matrix. Additionally, an aminosilane was used as a means to retard cross-linking in polymer-metalorganic solutions, as the titanium precursor molecules were shown to react and form networks prior to hydrothermal processing. By adding small amounts of competing aminosilane, excessive cross-linking was prevented without significantly impacting the quality and composition of the final barium titanate nanoparticles. X-ray diffraction and X-ray photoelectron spectroscopy were used to verify nanoparticle compositions. Particle sizes within the polymer films were measured to be 108 ± 5 nm, 100 ± 6 nm, and 60 ± 5 nm under different synthetic conditions using electron microscopy. Flexibility of the films was assessed through measurement of the glass transition temperature using dynamic mechanical analysis. Dielectric permittivity was measured using an impedance analyzer.
Keywords: barium titanate; dielectric nanoparticle; functional nanocomposite; hydrothermal processing; polymer thin film.