The crystal structure of tetragonal tungsten bronzes, with the general formula A1 2 A2 4 C 4 B1 2 B2 8 O 30 , is flexible both from a chemical and structural viewpoint, resulting in a multitude of compositions. The A1 and A2 lattice sites, with different coordination environments, are usually regarded to be occupied by two different cations such as in Ba 4 Na 2 Nb 10 O 30 with Na + and Ba 2+ occupying the A1 and A2 sites, respectively. Here, we report on a systematic study of the lattice site occupancy on the A1 and A2 sites in the series Ba 4 M 2 Nb 10 O 30 (M = Na, K, and Rb). The three compounds were synthesized by a two-step solid-state method. The site occupancy on the A1 and A2 sites were investigated by a combination of Rietveld refinement of X-ray diffraction patterns and scanning transmission electron microscopy with simultaneous energy-dispersive spectroscopy. The two methods demonstrated consistent site occupancy of the cations on the A1 and A2 sites, rationalized by the variation in the size of the alkali cations. The cation order–disorder phenomenology in the tungsten bronzes reported is discussed using a thermodynamic model of O’Neill and Navrotsky, originally developed for cation interchange in spinels.

Ferroelectric properties of films can be tailored by strain engineering, but a wider space for property engineering can be opened by including crystal anisotropy. Here, we demonstrate a huge anisotropy in the dielectric and ferroelectric properties of BaTiO3 films. Epitaxial BaTiO3 films deposited on (100), (110), and (111) SrTiO3 substrates were fabricated by chemical solution deposition. The films were tensile-strained due to thermal strain confirmed by the enhanced Curie temperature. A massive anisotropy in the dielectric constant, dielectric tunability, and ferroelectric hysteresis loops was observed depending on the in-plane direction probed and the orientation of the films. The anisotropy was low for (111) BaTiO3, while the anisotropy was particularly strong for (110) BaTiO3, reflecting the low in-plane rotational symmetry. The anisotropy also manifested at the level of the ferroelectric domain patterns in the films, providing a microscopic explanation for the macroscopic response. This study demonstrates that the properties of ferroelectric films can be tailored not only by strain but also by crystal orientation. This is particularly interesting for multilayer stacks where the strain state is defined by the boundary conditions. We propose that other materials can be engineered in a similar manner by utilizing crystal anisotropy.

Ferroelectric properties of thin films can be enhanced by crystallographic texture. In this work, we report on how heat treatment of films can be designed to tailor the degree of preferential orientation in BaTiO3‐based thin films from aqueous chemical solution deposition. In situ synchrotron X‐ray diffraction in combination with Rietveld refinements was used to study the crystallization process of films from a single deposition and to give an in‐depth characterization of the crystallographic texture of the films. Transmission electron microscopy was employed to evaluate the microstructure and degree of preferred orientation in thicker films from multiple depositions. Texture was induced in the multilayer films by a repeated annealing process. Cube‐on‐cube growth was demonstrated to occur in both single and multi‐layered films provided the heating program was designed to give limited nucleation and growth below the threshold for where cube‐on‐cube growth is favoured, resulting in a very high degree of preferred orientation. The cube‐on‐cube grown films were relaxed with respect to the lattice unit cell mismatch between the film and the substrate, where the relaxation of stress depends on the film thickness. Texture and cube‐on‐cube growth were demonstrated on several types of single‐crystal oxide substrates. Calcium and zirconium substitution did not alter the crystallization process, but zirconium slowed down the texture formation kinetics. The ferroelectric response was strongest in the films with a high degree of preferred orientation.

Epoxy nanocomposites have demonstrated promising properties for high-voltage insulation applications. An in situ approach to the synthesis of epoxy-SiO2 nanocomposites was employed, where surface-functionalized SiO2 (up to 5 wt.%) is synthesized directly in the epoxy. The dispersion of SiO2 was found to be affected by both the pH and the coupling agent used in the synthesis. Hierarchical clusters of SiO2 (10-60 nm) formed with free-space lengths of 53–105 nm (increasing with pH or SiO2 content), exhibiting both mass and surface-fractal structures. Reducing the amount of coupling agent resulted in an increase in the cluster size (~110 nm) and the free-space length (205 nm). At room temperature, nanocomposites prepared at pH 7 exhibited up to a 4% increase in the real relative permittivity with increasing SiO2 content, whereas those prepared at pH 11 showed up to a 5% decrease with increasing SiO2 content. Above the glass transition, all the materials exhibited low-frequency dispersion effect resulting in electrode polarization, which was amplified in the nanocomposites. Improvements in the dielectric properties were found to be not only dependent on the state of dispersion, but also the structure and morphology of the inorganic nanoparticles.

A first-principles study of the tetragonal tungsten bronze (TTB) K4Bi2Nb10O30 has suggested that the Bi 6s lone pair causes in-plane polarization (within the a–b plane), corresponding to the one found in Pb5Nb10O30 (PN), in contrast to the out-of-plane polarization (along c) found in most TTBs. Replacing PN with KBN potentially opens for a lead-free analogue to morphotropic phase boundaries known in TTBs based on PN. Here, we report on the synthesis and properties of A4Bi2Nb10O30 (ABN, A = Na, K, Rb) with the objective to determine the structure and electrical properties, paying particular attention to the role of the Bi 6s lone pair. The ABN materials were synthesized via conventional solid-state synthesis in a two-step process. Convergent-beam electron diffraction demonstrated a centrosymmetric tetragonal space group for the two compounds KBN and RBN, and ferroelectric polarization–electric field measurements confirmed the lack of hysteretic behavior in line with the observed centrosymmetric symmetry. Non-ambient powder X-ray diffraction demonstrated the signature of a phase transition for KBN and RBN, as several weak satellite reflections vanished during heating and reappeared upon cooling. Dielectric spectroscopy supported the observation of an anomaly due to the presence of a weak maximum in the electrical permittivity at temperatures corresponding to the disappearance of the satellite reflections. Possible explanations for the absence of polarization in ABN TTBs are discussed with particular attention to the suppression of the 6s2 lone pair effect of Bi and the size of A-site cations in the TTB crystal structure.