Optimizing TiO2 through Water-Soluble Ti Complexes as Raw Material for Controlling Particle Size and Distribution of Synthesized BaTiO3 Nanocubes.

Barium titanate (BaTiO3) nanocubes with a narrow particle size distribution were synthesized using a three-step approach. First, a water-soluble Ti complex was synthesized using a hydrolysis method. Next, the titanium dioxide (TiO2) raw material was synthesized via a hydrothermal method using various water-soluble titanium (Ti) complexes. The TiO2 exhibited various particle sizes and crystal structures (anatase, rutile, or brookite) depending on the water-soluble Ti complex and the hydrothermal conditions used in its synthesis. Finally, BaTiO3 nanocubes were subsequently created through a hydrothermal method using the synthesized TiO2 particles and barium hydroxide octahydrate [Ba(OH)2·8H2O] as raw materials. The present study clarifies that the particle size of the BaTiO3 nanocubes depends on the particle size of the TiO2 raw material. BaTiO3 particles with a narrow size distribution were obtained when the TiO2 particles exhibited a narrow size distribution. We found that the best conditions for the creation of BaTiO3 nanocubes using TiO2 involved using lactic acid as a complexing agent, which resulted in a particle size of 166 nm on average. This particle size is consistent with an average of the width of the cubes measured from corner to corner diagonally, which corresponds to a side length of 117 nm. In addition, surface reconstruction of the BaTiO3 was clarified via electron microscopy observations, identifying the outermost surface as a Ti layer. Electron tomography using high-angle annular dark-field (HAADF)-scanning transmission electron microscopy (STEM) confirmed the three-dimensional (3D) structure of the obtained BaTiO3 nanocubes.

Stabilization of Size-Controlled BaTiO3 Nanocubes via Precise Solvothermal Crystal Growth and Their Anomalous Surface Compositional Reconstruction.

Crystal growth of barium titanate (BaTiO3) using a wet chemical reaction was investigated at various temperatures. BaTiO3 nanoparticles were obtained at an energy-efficient temperature of 80 °C. However, BaTiO3 nanocubes with a preferred size and shape could be synthesized using a solvothermal method at 200 °C via a reaction involving titanium tetraisopropoxide [(CH3)2CHO]4Ti for nucleation and fine titanium oxide (TiO2) nanoparticles for crystal growth. The BaTiO3 nanocubes showed a high degree of dispersion without the use of dispersants or surfactants. The morphology of BaTiO3 was found to depend on the reaction medium. The size of the BaTiO3 particles obtained using water as the reaction medium was the largest among the particles synthesized using various reaction media. In the case of alcohol reaction media, the BaTiO3 particle size increased in the order methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol. Furthermore, BaTiO3 powder obtained using alcohol reaction media resulted in cubic shapes as opposed to the round shapes obtained when water was used as the medium. We found that the optimal condition for the synthesis of BaTiO3 nanocubes involved the use of 1-butanol as the reaction medium, resulting in an average particle size of 52 nm, which is the average distance of the cubes measured diagonally from corner to corner, and gives an average side length of 37 nm, and a tetragonal crystal system as evidenced by the powder X-ray diffraction pattern obtained using high-energy synchrotron X-rays. The origin of the spontaneous polarization of the BaTiO3 tetragonal crystal structure was clarified by a pair distribution function analysis. In addition, surface reconstruction of BaTiO3 nanocubes led to an outermost surface comprising two layers of Ti columns.

Nanoscale structural analysis of Pb(Mg1/3Nb2/3)O3.

The determination of local atomic structure at nanoscale for inhomogeneous systems is challenging. The local arrangement of atoms needs to be studied to understand the local or short-range order structures for disordered materials with a lack of long-range order periodicity. Pair distribution function (PDF) analysis is a technique, that is used to study the short-range order structure of materials: this technique is based on the evaluation of local atomic arrangement using synchrotron and neutron sources. An attempt was made to determine the local arrangement at 20 nm-scale for a typical relaxor ferroelectric material, Pb(Mg1/3Nb2/3)O3(PMN). The PDF technique was employed owing to the limited structural coherence in this disordered material. It was determined that there are three types of structures depending on the distance. A glass-like network structure was observed as a short-range order structure owing to the large off-center shift of lead atoms. With an increase in distance, the structure of PMN changed from rhombohedral to cubic. Using the above-mentioned approach, we elucidated the process of local structure averaging.

Enhancement of tetragonal anisotropy and stabilisation of the tetragonal phase by Bi/Mn-double-doping in BaTiO3 ferroelectric ceramics.

To stabilise ferroelectric-tetragonal phase of BaTiO3, the double-doping of Bi and Mn up to 0.5 mol% was studied. Upon increasing the Bi content in BaTiO3:Mn:Bi, the tetragonal crystal-lattice-constants a and c shrank and elongated, respectively, resulting in an enhancement of tetragonal anisotropy, and the temperature-range of the ferroelectric tetragonal phase expanded. X-ray absorption fine structure measurements confirmed that Bi and Mn were located at the A(Ba)-site and B(Ti)-site, respectively, and Bi was markedly displaced from the centrosymmetric position in the BiO12 cluster. This A-site substitution of Bi also caused fluctuations of B-site atoms. Magnetic susceptibility measurements revealed a change in the Mn valence from +4 to +3 upon addition of the same molar amount of Bi as Mn, probably resulting from a compensating behaviour of the Mn at Ti4+ sites for donor doping of Bi3+ into the Ba2+ site. Because addition of La3+ instead of Bi3+ showed neither the enhancement of the tetragonal anisotropy nor the stabilisation of the tetragonal phase, these phenomena in BaTiO3:Mn:Bi were not caused by the Jahn-Teller effect of Mn3+ in the MnO6 octahedron, but caused by the Bi-displacement, probably resulting from the effect of the 6 s lone-pair electrons in Bi3+.

Magnetic and dielectric properties of InFe2O4, InFeCuO4, and InGaCuO4.

The magnetic and dielectric properties of InFe2O4, InFeCuO4, and InGaCuO4 have been investigated. All these materials are isostructural with RFe2O4 (R = Y, Ho-Lu), which shows ferroelectricity due to iron-valence ordering. InFe2O4 exhibits ferrimagnetic ordering at T(C) approximately 242 K and a dielectric constant (epsilon) of approximately 10,000 at around room temperature. These properties resemble those of RFe2O4; the origins of the magnetic and dielectric phenomena are likely common in InFe2O4 and RFe2O4. From measurements of the other two materials, we found that both T(C) and epsilon are decreased in the order of InFe2O4, InFeCuO4, and InGaCuO4. This result strongly supports the previously reported explanation based on an electron transfer between the Fe-site ions for the corresponding rare-earth systems. Therefore, we propose that the dielectric properties of the oxides isostructural with RFe2O4 are plausibly governed by electron transfer; this situation is different from that of ordinary ferroelectrics and dielectrics, in which the displacement of cations and anions is important. In addition, InFeCuO4 and InGaCuO4 exhibit large epsilon values (epsilon > approximately 1500). In consideration of this property, we discuss the possible applications of these oxides.

Simple and high-sensitivity detection of dioxin using dioxin-binding pentapeptide.

The purposes of this study are to construct a simple dioxin detection system using peptides that bind to dioxin, and to test the system on real environmental samples. In this method, dioxin and N-NBD-3-(3',4'-dichlorophenoxy)-1-propylamine (NBD-DCPPA) are competitively bound to the peptides synthesized on beads. The fluorescence intensity of the bead decreases with increasing dioxin concentration. The concentration of dioxin is determined by measuring the fluorescence intensity using a fluorescence microscope equipped with a CCD camera. The fluorescence microscope system was equipped with a motor-driven stage and could be used with 96-well microplates and analytical software that automatically measured the fluorescence intensity of the bead images in the wells. Dioxin detection conditions, reaction temperature, number of beads and concentration of the organic solvent were optimized. About 0.5 nM (150 pg mL(-1)) of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TeCDD) could be detected under the optimized conditions. Environmental soil samples were subjected to the detection system using the peptide beads. Although the results obtained correlated poorly with the toxicity equivalency quantity (TEQ) concentration obtained by a GC/MS method, our method is robust enough as a prescreening method to detect at least 250 pg-TEQ g(-1), the survey level for soil as stipulated in the law concerning special measures against dioxins in Japan.