Improvement of Electro-Caloric Effect and Energy Storage Density in BaTiO3-Bi(Zn, Ti)O3 Ceramics Prepared with BaTiO3 Nano-Powder.

BaTiO3-Bi(Zn,Ti)O3 (BT-BZT) ceramics have been used as capacitors due to their large dielectric permittivity and excellent temperature stability and are good candidates for lead-free materials for electrocaloric and energy storage devices. However, BT-BZT ceramics often suffer from inferior properties and poor reproducibility due to heterogeneous compositional distribution after calcination and sintering. In this work, (1-x)BT-xBZT ceramics (x = 0~0.2) were fabricated with nano-sized BaTiO3 raw materials (nano-BT) by a solid-state reaction method to enhance the chemical homogeneity. The (1-x)BT-xBZT ceramics prepared from the nano-BT showed larger densities and more uniform microstructures at the lower calcination and sintering temperatures than the samples prepared from more frequently used micrometer-sized raw materials BaCO3, TiO2, Bi2O3, and ZnO. The (1-x)BT-xBZT ceramic prepared from the nano-BT displayed a phase transition from a tetragonal ferroelectric to a pseudo-cubic relaxor in a narrower composition range than the sample prepared from micro-sized raw materials. Larger adiabatic temperature changes due to the electro-caloric effect (ΔTECE) and recoverable energy storage density (Urec) were observed in the samples prepared from the nano-BT due to the higher breakdown electric fields, the larger densities, and uniform microstructures. The 0.95BT-0.05BZT sample showed the largest ΔTECE of 1.59 K at 80 °C under an electric field of 16 kV/mm. The 0.82BT-0.18BZT sample displayed a Urec of 1.45 J/cm2, which is much larger than the previously reported value of 0.81 J/cm2 in BT-BZT ceramics. The nano-BT starting material produced homogeneous BT-BZT ceramics with enhanced ECE and energy storage properties and is expected to manufacture other homogeneous solid solutions of BaTiO3 and Bi-based perovskite with high performance.

Crystal structure and spontaneous magnetism of BiFeO3 powder synthesized by hydrothermal method.

Single-phase BiFeO3 powder was successively synthesized by a low-temperature hydrothermal method. Scanning electron microscopy and transmission electron microscopy results showed that BiFeO3 powder had several hundred nanometers to micrometer-sized particles with a broad size distribution. BiFeO3 powder showed weak-ferromagnetic behavior with a small magnetization value (Ms approximately 20 memu/g) at room temperature. Rietveld refinement results for the crystal structure show the displacive disorder of the Fe-site(6a); the Fe-site(6a) splits into two pairs, Fe(1) and Fe(2) displaced by 0.9 angstroms from each other and these sites are partially occupied. Hence the O-site(18b) also splits into the two partially occupied sites forming a distorted FeO6 octahedras. The weak ferromagnetism observed in the hydrothermal BFO powder is ascribed to the displacive disorder of FeO6 octahedras resulting in an incomplete counterbalance between the antiferromagnetic sublattices of the Fe-ions.

Low-temperature solution growth of ZnO nanotube arrays.

Single crystal ZnO nanotube arrays were synthesized at low temperature in an aqueous solution containing zinc nitrate and hexamethylenetetramine. It was found that the pH value of the reaction solution played an important role in mediating the growth of ZnO nanostructures. A change in the growth temperature might change the pH value of the solution and bring about the structure conversion of ZnO from nanorods to nanotubes. It was proposed that the ZnO nanorods were initially formed while the reaction solution was at a relatively high temperature (~90 °C) and therefore enriched with colloidal Zn(OH)(2), which allowed a fast growth of ZnO nanocrystals along the [001] orientation to form nanorods. A decrease in the reaction temperature yielded a supersaturated solution, resulting in an increase in the concentration of OH(-) ions as well as the pH value of the solution. Colloidal Zn(OH)(2) in the supersaturated solution trended to precipitate. However, because of a slow diffusion process in view of the low temperature and low concentration of the colloidal Zn(OH)(2), the growth of the (001) plane of ZnO nanorods was limited and only occurred at the edge of the nanorods, eventually leading to the formation of a nanotube shape. In addition, it was demonstrated that the pH might impact the surface energy difference between the polar and non-polar faces of the ZnO crystal. Such a surface energy difference became small at high pH and hereby the prioritized growth of ZnO crystal along the [001] orientation was suppressed, facilitating the formation of nanotubes. This paper demonstrates a new strategy for the fabrication of ZnO nanotubes on a large scale and presents a more comprehensive understanding of the growth of tube-shaped ZnO in aqueous solution at low temperature.