Preparation of a Monodispersed Suspension of Barium Titanate Nanoparticles and Electrophoretic Deposition of Thin Films

A transparent and stable monodispersed suspension of nanocrystalline barium titanate was prepared by dispersing a piece of BaTiO₃ gel into a mixed solvent of 2-methoxyethanol and acethylacetone. The results of high-resolution transmission electron microscopy (HR-TEM) and size analyzer confirmed that the BaTiO₃ nanoparticles in the suspension had an average size of ∼10 nm with a narrow size distribution. Crystal structure characterization via TEM and X-ray diffraction indicated BaTiO₃ nanocrystallites to be a perovskite cubic phase. BaTiO₃ thin films of controlled thickness from 100 nm to several micrometers were electrophoretic deposited compactly on Pt/Ti/SiO₂/Si substrates. The deposited thin film had uniform nanostructure with a very smooth surface.     

Monodispersed Polymeric Nanoparticles Fabrication by Electrospray Atomization

The feasibility of fabricating relatively monodispersed polymeric nanoparticles by the electrospray method in a modified electrospray set-up is demonstrated in this study. The polymer solution is electrosprayed in the single cone-jet regime through a nozzle. After solvent evaporation, during which particles pave from the nozzle to collector, the fabricated nanoparticles can be collected in deionized water, which plays the role of surfactant for particles, not allowing them to aggregate. The results of scanning electron microscope and dynamic light scattering analysis clearly confirm the fabrication of monodispersed spherical polymeric nanoparticles with diameter range from 80 to 120 nm with smooth surface.     

Particle Size Control of Barium Titanate Prepared from Barium Titanyl Oxalate

Barium titanates formed from decomposition of barium titanyl oxalates (BT-oxalates) exhibit the same powder state as that of the Bt-oxalates, so that controlling the particle size and shape of the starting BT-oxalates is necessary. In the present study, BT-oxalates were precipitated from aqueous solution under various aging conditions: aging fluids, temperature, and time. The particle size of the spherical BT-oxalates was controlled at 0.4 μm by aging at 25°C for 3 h, and the diameter of the barium titanate formed was similar to that of the BT-oxalates.     

Size Effects in Barium Titanate Particles and Clusters

Clustering has an important effect on the tetragonal-cubic transformation of barium titanate (BaTiO₃) particles. Small particles that would be cubic if they were by themselves can be tetragonal if they are in a cluster. The effects of clustering are shown in the behavior of the c/a ratio of the particles and the enthalpy change, Δ H , of transition as a function of particle size. The c/a ratio and the value of Δ H both decrease at a smaller particle size than those which are observed in samples where clustering is minimal. Our results are consistent with the observation that very small grains in polycrystalline samples can remain tetragonal even though the grain size is so small that it would be cubic if it were an individual particle. The transition temperature, T_C , on the other hand, is insensitive to the particle size, which is similar to the observation in polycrystalline BaTiO₃ that T_C is insensitive to the grain size. The observed clustering effect is suggested to result from the reduction of depolarization energy of particles in clusters.     

Intrinsic Size Effects in a Barium Titanate Glass-Ceramic

A series of glass ceramics have been synthesized to produce bulk materials with nanometer-sized barium titanate (BaTiO₃) crystals grown in a residue glass matrix. Structure-property relations have been made to determine the size distribution and the dielectric temperature dependence of the ceramics. Through dielectric and density mixing laws, it has been inferred that depolarization fields limit the dielectric polarizability of the particles and influence the transition temperature. The transition temperature, dielectric anomaly broadening, and peak dielectric constant all scale systematically with the mean size of the BaTiO₃ crystals, which is consistent with an intrinsic size effect. In addition, scaling the transition temperature with the Ishikawa relation predicts a critical size of 17 nm, for which BaTiO₃ cannot support a ferroelectric transition. These results are discussed in relation to other size studies on ferroelectric materials.     

单分散、小粒径纳米ZnO的制备及其表面包覆

以ZnSO4·7H2O和NaOH为原料,采用微乳法制备了单分散、小粒径ZnO纳米颗粒,并用Na2SiO3水解生成的SiO2对其进行表面包覆改性.用IR(红外光谱)、XRD(X射线衍射)、UV-vis(紫外可见光谱)等表征手段对制得的颗粒进行了袁征.结果表明:ZnO表面存在Si-O-Zn键,显示了SiO2的很好的包覆.室...     

Fabrication of Barium Titanate Single Crystals by Solid-State Grain Growth

BaTiO₃ single crystals were prepared by solid-state grain growth. The single crystals were obtained by seeding a poly-crystalline, TiO₂-excess BaTiO₃, which exhibited abnormal grain growth. The condition for single-crystal growth was essentially dependent on the grain growth behavior of the polycrystalline, sintered bodies. The annealing temperature suitable for the single-crystal growth was just below the critical temperature of abnormal grain growth in TiO₂-excess BaTiO₃, which is about 1300°C.     

Dependence of the Crystal Structure on Particle Size in Barium Titanate

The effect of the sample particle size on the crystal structure and the Curie temperature of BaTiO₃ powder has been investigated in the particle size range 0.1 to 1.0 μm. The transformation from tetragonal to cubic symmetry occurs at a critical particle size of 0.12 μm at room temperature, and the Curie temperature drops below room temperature at the critical particle size.     

Synthesis of Highly Dispersed Barium Titanate Nanoparticles by a Novel Solvothermal Method

A novel solvothermal route has been developed to synthesize highly dispersed nanocrystalline barium titanate (BaTiO₃), using a mixture of ethylenediamine and ethanolamine as a solvent. The as-synthesized BaTiO₃ nanoparticles were characterized by X-ray powder diffraction, transmission electron microscopy (TEM), high-resolution TEM, Fourier transform infrared spectroscopy, and thermal analysis. Based on the results of characterizations, the organic solvent was found to influence strongly the crystal growth and dispersibility of BaTiO₃. The BaTiO₃ nanoparticles obtained were highly dispersed and crystalline with a cubic perovskite structure. The particle size derived from the TEM ranged from 5 to 20 nm.     

Dispersion Behavior of Barium Titanate Nanoparticles Prepared by Using Various Polycarboxylic Dispersants

The effects of the polycarboxylic dispersant structures on the crystallinity and sedimentation behavior of prepared BaTiO₃ nanoparticles were analyzed using four types of dispersants—ethylenediaminetetraacetic acid dipotassium salt (EDTA), trans -aconitic acid (TAA), ammonium acrylate–methyl acrylate co-polymer (PAA50), and sodium polyacrylate (PAA100). In the case of EDTA and TAA, the adsorbed ratio of the dispersants on BaTiO₃ nanoparticles was relatively low, and only slight improvement of sedimentation behavior was observed. On the other hand, in the case of PAA50 and PAA100, the adsorbed ratio was high, and the sedimentation behavior was gratefully improved. Next, in order to analyze the relationships among the additive amount of polycarboxylic dispersants, crystallinity, and sedimentation behavior, various amounts of PAA100 or PAA50 were treated in the synthesis solution. The sedimentation behavior of BaTiO₃ nanoparticles improved with increasing amounts of PAA100 and PAA50 while their crystal phase became amorphous. Adding PAA50 at a molar ratio of COO⁻/Ba²⁺=0.266 resulted in BaTiO₃ nanoparticles with the best dispersion stability in an aqueous media.     

Neuron Compatibility and Antioxidant Activity of Barium Titanate and Lithium Niobate Nanoparticles

The biocompatibility and the antioxidant activity of barium titanate (BaTiO₃) and lithium niobate (LiNbO₃) were investigated on a neuronal cell line, the PC12, to explore the possibility of using piezoelectric nanoparticles in the treatment of inner ear diseases, avoiding damage to neurons, the most delicate and sensitive human cells. The cytocompatibility of the compounds was verified by analysing cell viability, cell morphology, apoptotic markers, oxidative stress and neurite outgrowth. The results showed that BaTiO₃ and LiNbO₃ nanoparticles do not affect the viability, morphological features, cytochrome c distribution and production of reactive oxygen species (ROS) by PC12 cells, and stimulate neurite branching. These data suggest the biocompatibility of BaTiO₃ and LiNbO₃ nanoparticles, and that they could be suitable candidates to improve the efficiency of new implantable hearing devices without damaging the neuronal cells.     

Effect of Particle Size on the Room-Temperature Crystal Structure of Barium Titanate

The room-temperature tetragonal-to-cubic transformation in BaTiO₃ powders with decreasing particle size has been carefully studied, using materials prepared mainly by hydrothermal methods. Hydrothermal BaTiO₃ powders exhibited a more uniform particle size distribution than oxalate-route powders, with X-ray diffraction and electron microscopy indicating that powders 0.19 μm in size were fully cubic while powders 0.27 μ were completely tetragonal (within a 5% detection limit for cubic material) at room temperature. The tetragonal-to-cubic transformation temperature was also found to lie in the range of 121°± 3°C for BaTiO₃ powders with room-temperature ( c/a ) values > 1.008. No transformation could be detected using differential scanning calorimetry for BaTiO₃ particles with a ( c/a ) > 1.008 at room temperature. BaTiO₃ powder with a particle size just too small (0.19 μm) to be tetragonal at room temperature remained cubic down to 80 K. Different models for the cubic-to-tetragonal room-temperature transformation are discussed. Hydroxyl ions do not appear to greatly affect the cubic-to-tetragonal transformation, which appears to be essentially dependent on particle size. It is concluded that a model based on surface free energy, as previously discussed for the monoclinic-to-tetragonal transformation at room temperature of fine ZrO₂ particles, is consistent with the experimental data.     

Nickel Nanoparticles with Narrow Size Distribution Confined in Nitrogen-Doped Carbon for Efficient Reduction of CO2 to CO

Catalysis Letters - Facilely tailored electrocatalyst with high-efficiency and durability for carbon dioxide (CO2) to carbon monoxide (CO) conversion is appealing but remains challenging. Herein,...     

Formation and Accumulation of Intragranular Pores in the Hydrothermally Synthesized Barium Titanate Nanoparticles

As highly integrated circuits are demanded for high‐performance electric devices, small sizes of barium titanate (BaTiO₃) as a dielectric material are desirable for the application of multilayer ceramic capacitors. Since the small sizes of the particles degrade the dielectric property, especially below a certain critical size, understanding the probable cause is significant for the high‐performance capacitors. Here, we have demonstrated nanosized BaTiO₃ with average size below 30 nm and a uniform size distribution. High‐resolution transmission electron microscopy (TEM) shows that the as‐synthesized BaTiO₃ contains intragranular pores. We have analyzed the correlation between the intragranular pores inside nanoparticles and their phase ratio of cubic and tetragonal. We have found that the presence of the intragranular pores affects low tetragonality of BaTiO₃ particles, and the intragranular pores are generated by the accumulation of hydroxyl groups during hydrothermal reaction. Formation and accumulation of intragranular pores have been investigated by ex‐situ synchrotron X‐ray diffraction and TEM analysis, suggesting the phase evolution model of nanosized BaTiO₃.     

Formation Mechanisms of Tetragonal Barium Titanate Nanoparticles in Alkoxide–Hydroxide Sol-Precipitation Synthesis

The early stage of barium titanate (BaTiO₃) nanoparticle formation is investigated by in situ X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) using synchrotron radiation. BaTiO₃ nanoparticles are synthesized via dissolution of barium hydroxide octahydrate and hydrolysis of titanium (IV) isopropoxide in isopropanol. In the course of raising the temperature of the alkoxide–hydroxide mixture solution to 80°C, in situ synchrotron XRD reveals that BaTiO₃ nanocrystals smaller than 6 nm begin to nucleate at 50°C without intermediate TiO₂ anatase formation, and Ti K edge absorption spectra also confirm the formation of corner-sharing TiO₆ octahedra at 60°C. The average size of BaTiO₃ precipitates increases to about 7.5 nm at 80°C. The synthesized nanopowders show an anomalously high tetragonality according to the Rietveld refinement of synchrotron XRD data.     

Fabrication of Barium Strontium Titanate Inverse Opals by the Sol–Gel Process

Barium strontium titanate (BST) inverse opal photonic crystals (PCs) were fabricated by a process of self-assembly of a polystyrene opal template in combination with infiltration of BST nanoparticles into the voids of a template. In this process, stable monodispersed BST nanoparticles were prepared by dispersing a BST gel into a mixed solvent of 2-methoxyethanol and acetylacetone. Scanning electron microscopy images show that the inverse opals possess a face-centered cubic lattice with a center-to-center distance of the air spheres of 270 nm. The X-ray diffraction result reveals that a ferroelectric perovskite phase was obtained. A photonic bandgap in the visible range is observed from reflection spectra analysis and compared with the theoretical results.     

Barium Titanate Perovskite Sintered with Lithium Fluoride

The sintering of barium titanate with, respectively, 1 and 2 wt% LiF for two stoichiometries, Ti/Ba=1 and 0.975, was studied using two calcined powders. One was pure barium titanate; the other contained BaTi0₃ plus BaC0₃ and TiO₂ that did not react when burning. The sintering chronology—intermediate phases, appearance, and disappearance of a liquid phase that has been pointed out for the first time—is directly dependent on the used calcined powder, on the LiF amount, and on the firing schedule. In the same way, the obtained perovskite symmetry varies during sintering from tetragonal to cubic and then to a second tetragonal form, whereas most of the Li and F disappear from the ceramic with two different kinetics.     

Anomalous Grain Growth in Donor-Doped Barium Titanate with Excess Barium Oxide

Grain growth and semiconductivity of donor-doped BaTiO₃ceramics with an excess of BaO and additions of SiO₂or B₂O₃were studied. The microstructures and electrical measurements on sintered samples revealed that their electrical properties are related to the microstructure development of the sintered samples. Samples heated with an excess of BaO developed a normal microstructure during sintering, as a consequence of normal grain growth (NGG), and were yellow and insulating. In contrast, samples with an excess of BaO and an addition of SiO₂or B₂O₃exhibited anomalous grain growth (AGG) and were dark blue and semiconducting after sintering. When some BaTiO₃seed grains were embedded in a sample of donor-doped BaTiO₃with an excess of BaO (without SiO₂or B₂O₃), AGG was observed, i.e., some seed grains grew into large grains and were blue and semiconducting. An explanation is given for why AGG is responsible for the oxygen release and the formation of semiconducting grains in donor-doped BaTiO₃and not NGG.     

Kinetics of Barium Titanate Synthesis

Reaction curves were obtained at various temperatures and concentrations for the formation of BaTiO₃ from particulate titania in Ba(OH)₂ solution. Kinetic analyses were performed by constructing mathematical models which took into account the particle size distribution of the reactant titania for both the topochemically-rate-controlled and the diffusion-rate-controlled reactions. At [Ba(OH)₂] > ca. 0.1 M the rate-controlling step is the Ba reaction with TiO₂ at the interface. The measured activation energy is 105.5 kJ/mol. The rates are independent of Ba(OH)₂ concentration, indicating that the TiO₂ interface is saturated. At [Ba(OH)₂] < ca. 0.1 M the rate-determining step shifts to diffusion through the product BaTiO₃ layer, the rates are concentration dependent, and the BaTiO₃ particle sizes are inversely proportional to the Ba(OH)₂ concentrations used.