Hydrothermal synthesis of barium titanate fine particles from amorphous and crystalline titania

Barium titanate fine particles of cubic system were synthesized hydrothermally from aqueous barium hydroxide solutions with fine particles of either amorphous or crystalline (rutile) titania in suspension. The mean size of barium titanate particles prepared from amorphous titania ranged from 0.03 m to 0.11 m, depending on hydrothermal conditions. The particle size approximately agreed with the crystallite size (0.04–0.09 m). On the other hand, the mean size of barium titanate particles prepared from rutile titania ranged from 0.2 to 0.7 m, which was about six times as large as the crystallite size. The difference of sizes of barium titanate particles prepared might be ascribed to the difference in dissolution rates of amorphous or crystalline titania particles.Nomenclature mean particle size, m - BT barium to titanium molar ratio - d crystallite size, m - K shape factor appearing in Equation 3 - half value breadth of diffraction peak - lattice strain - Bragg diffraction angle, degree - wave length of X-ray, urn - _g geometric standard deviation defined by 84.1%-size/50%-size in a log normal size distribution     

Influence of microstructure on dielectric properties of Nd-doped barium titanate synthesized by hydrothermal method

Nd-doped barium titanates were successfully synthesized via a hydrothermal route. The as-prepared barium titanate was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transformation infrared spectroscopy (FTIR), and Vis–NIR spectroscopy respectively. The results show that pure and Nd-doped barium titanate powders have cubic perovskite structure. After sintering at a temperature of 1,250 °C for 2 h, the phase compositions of all barium titanate are tetragonal phase structure. Vis–NIR spectra well confirmed that Nd³⁺ have been doped into barium titanate. The particle diameters of Nd-doped barium titanate powders and ceramics become samller with the increase of Nd³⁺ content. When Nd/Ba molar ratio is 0.02, the dielectric loss (0.0008) of the powder measured at 1 MHz and room temperature dramatically decreases by 99 % comparing with pure barium titanate (0.083) and shows frequency independence with the frequency increasing from 40 Hz to 1 MHz. The dielectric constant and dielectric loss are 436 and 0.09 after sintering. The Nd-doped BaTiO₃ show an improvement in the dielectric quality which possess a decreased sensitivity to frequency for both the dielectric constant and dielectric loss. Such improvements are of potential importance for high energy density and low loss.     

Preparation of barium titanate nanocube particles by solvothermal method and their characterization

Barium titanate (BaTiO₃) nanocube particles below 20 nm were prepared by solvothermal method. A selection of organic solvent and inorganic materials of Ba and Ti sources was most important for the preparation of nanocubes. A nucleation and particle growth of BaTiO₃ nanoparticles led to a formation of the BaTiO₃ nanocubes with a size of 10–15 nm at temperatures above 200 °C.     

改进的sol-gel工艺制备细晶Ba0.6Sr0.4TiO3陶瓷及其介电性能的研究

用改进的sol-gel工艺制备了细晶钛酸锶钡(Ba0.6Sr0.4TiO3,BST)陶瓷块体,研究了BST陶瓷的结晶与介电性能.在这种改进sol-gel的工艺中,用传统的固相反应煅烧形成BST粉体,经高能球磨制备BST纳米陶瓷粉体,再将一定质量的纳米粉体加入到相同化学组成的BST的溶胶液中,经普球球磨12h后,制备成悬浮性好,分散均匀的浆料.浆料可用来制备BST陶瓷,并在1200℃保温2h烧结成瓷,结果显示,BST陶瓷块体结构致密,晶粒尺寸在0.15～2μm之间.分析了样品的介电性能和晶粒尺寸对材料介电性能的影响.介电温谱显示,在0℃,100kHz时,相对介电常数为2500,介电损耗为0.02;并且存在明显的弥散相变.     

Preparation of barium titanate ultrafine powders from a monomeric metallo-organic precursor by combined solid-state polymerisation and pyrolysis

A recipe has been elaborated for preparing barium titanate (BaTiO₃) particles in a nucleation route which is mediated by thermal decomposition of polymeric barium titanium methacrylate. Adjustment of particle size d in the range from 10 nm to 1.5 m is easily done by choosing appropriate reaction temperatures and tempering atmospheres. In particular, doping with paramagnetic probe ions such as Mn²⁺, Gd³⁺ or Cr³⁺ can be readily accomplished by just adding the corresponding metal acetates to the monomeric precursor. In addition to well approved standard techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC), the complementary spectroscopic methods electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), X-ray absorption near edge structure (XANES) and FT-Raman are applied to characterise the micro- and nanocrystalline BaTiO₃ powders prepared and to study the phase transition behaviour in dependence on the mean particle size. In contrast to expectation from literature, the dimensionality effect does not manifest itself in a temperature shift of the ferroelectric phase transition but, instead, the tetragonal-to-cubic phase transition is smeared out at reduced particle size and an increasing tetragonal-to-cubic phase admixture is detected.     

Preparation and properties of barium titanate glass-ceramics sintered from sol–gel-derived powders

Homogeneous Ba–Ti–B–Si, Ba–Ti–Al–Si and Ba–Ti–B gels have been successfully prepared by the sol–gel process. A novel method is presented for fabricating barium titanate glass-ceramics by sintering the gel powders with small barium titanate crystallites. The structural development, grain size, crystallization process and dielectric properties were systematically studied by differential thermal analysis, thermogravimetric analysis, X-ray diffraction techniques, scanning electron microscopy and dielectric measurements. The glass-ceramic samples were sintered at lower temperatures compared to the barium titanate ceramic sintering, and showed improved dielectric properties. It was found that the small size effect of the barium titanate grains on the dielectric constant in the glass-ceramics was quite evident. Ferroelectric hysteresis loop analyses were also performed to manifest the ferroelectric nature of the barium titanate grains in situ grown from the gels. This revised version was published online in November 2006 with corrections to the Cover Date.     

国内外水热法钛酸钡性能的对比研究

对国产的两种水热法钛酸钡和日本生产的两种水热法钛酸钡进行了对比研究.结果表明国产的两种水热法钛酸钡的介电性能比日本生产的两种水热法钛酸钡的介电性能要差,其原因主要是原始钛酸钡粉体的颗粒形貌不同日本生产的两种水热法钛酸钡颗粒棱角分明,而国产的两种水热法钛酸钡颗粒圆化非常严重,这直接导致了其烧结性能的不同.颗粒园化的原因可能是水热反应的温度过高,保温时间过长,或者碱性过强.     

Si-B-O系BST玻璃陶瓷制备及介电弥散研究

采用硝酸钡、硝酸锶、钛酸丁酯、正硅酸乙脂和硼酸三正丁脂为原料的溶胶凝胶方法制备了Si-B-O系BaxSr1-xTiO3玻璃陶瓷。通过差热分析(DTA)、热失重(TG)、X射线衍射(XRD)分析Si-B-O系BST玻璃陶瓷超细粉体合成过程及其相结构变化。采用X射线衍射(XRD)、扫描电子显微镜(SEM)描述Si-B-O系BST玻璃陶瓷烧结体的相结构和显微组织结构变化。阻抗分析仪测量Si-B-O系BST玻璃陶瓷的-50～100℃介电温谱。实验结果表明：Si-B-O系BST玻璃陶瓷粉体的相结构为立方钙钛矿相结构,其合成温度为700℃．不存在第二相。Si-B-O系BST玻璃陶瓷的烧结温度低于传统工艺。Si-B-O系BST玻璃陶瓷的显微结构呈细晶结构。Si-B-O系BST玻璃陶瓷的介电常数ε随着烧结温度升高而增大．介电损耗tgδ随测试温度的增加而降低。随着晶粒平均尺寸的减小．Si-B-O系BST玻璃陶瓷样品的介电峰变低．平坦．宽化．存在介电峰弥散化的现象。     

Microstructure,dielectric and ferroelectric properties of barium zirconate titanate ceramics prepared by microwave sintering

Barium zirconate titanate ceramics were fabricated by microwave sintering. Effects of microwave sintering time on microstructure, dielectric and ferroelectric properties of barium zirconate titanate ceramics have been investigated. The result shows that the ceramic samples sintered at 2.5 kW for 15–30 min are single phase perovskite structure and there is no secondary phase observed. As the microwave sintering time extends, barium zirconate titanate ceramics become more uniform and the grain size increases. The data of dielectric properties indicate that the samples prepared by microwave sintering for 15–30 min are the ferroelectrics with diffuse phase transition and the diffuseness of phase transition weakens with the extending of microwave sintering time. As microwave sintering time increases, the remnant polarization increases initially and then decreases. Moreover, the remnant polarization and the coercive field of the samples sintered for 15 and 20 min decrease as measuring frequency increases, but the measuring frequency has little effect on ferroelectricity of the sample sintered for 30 min. The temperature dependences of hysteresis loops further prove that the samples are ferroelectrics with diffuse phase transition.     

Photocatalytic properties of titanate nanotube powders prepared by alkaline hydrothermal method

This paper reports the photocatalytic activities of titanate nanotubes (TNTs) synthesized using different methods and compares them with that of P25. Rhodamine B was selected as the organic compound to be decomposed by the microwave/UV/photocatalyst hybrid process. The as-prepared TNT had titanate crystalline structure, whereas the TNT calcined at 723 K was phase-transformed into anatase structure. When the as-prepared TNT was ion-exchanged using HCl, Na+ content was reduced from 8.36 wt% to 0.03 wt%. The ion-exchanged TNT showed the highest photocatalytic activity among the TNTs tested in this study, but it was lower than that of P25.     

Preparation of barium titanate nanoparticle sphere arrays and their dielectric properties

Barium titanate (BaTiO3) nanoparticles from 27 to 192 nm were prepared by the 2-step thermal decomposition method from barium titanyl oxalate nanoparticles. These particles were dispersed well into 1-propanol, and dense BaTiO3 nanoparticle sphere arrays without stress-field were prepared by the meniscus method. Temperature dependence of dielectric properties was successfully measured using these dense nanoparticle sphere arrays, and size effect on dielectric properties was discussed.     

Effect of sintered temperature on structural and piezoelectric properties of barium titanate ceramic prepared by nano-scale precursors

Lead-free piezoelectric ceramics barium titanate has been successfully fabricated by a facile modified (nano-scale precursors) solid phase method. The sintered temperature was employed as the main regulatory factor to control the growth of the grain size and crystallinity of the sample. When the sintered temperature was set as 1350?°C, the pure phase barium titanate ceramics could be prepared with the grain size of about 1 μm. In addition, piezoelectric tests showed that, the samples sintered at this temperature possessed the maximum ?_r, P_r and d₃₃ values, 3533, 16.24 μC/cm² and 420 pC/N, respectively. These characteristics make them promising candidates as lead-free piezoelectric ceramic materials.     

Direct production of ultrafine amorphous Fe-P alloy particles by the plasma method

Ultrafine amorphous Fe-P alloy particles were directly synthesized by the plasma using cyclopentenyl iron and phosphorous trichloride as starting materials. The plasma gas greatly influenced the morphology, dispersion and composition.The particles were roughly spherical with a diameter of 40–200 nm and had the composition of Fe₁₀₆P₅₀. Elemental chlorine was found in the surface of the particle especially prepared under argon plasma conditions. It was bonded with phosphorus and carbon in Fe-P particles prepared in argon plasma and mainly with carbon in Fe-P particles deposited under a hydrogen plasma. Formation of Fe-P improves the stability of phosphorus in air. Phosphorus enrichment in the surface of Fe-P particles was also found. The particles were characterized by TEM, SEM, infrared-spectroscopy, X-ray photoelectron spectroscopy quantitative analysis, differential scanning colorimetry, inductively coupled plasma, X-ray diffraction and X-ray microprobe analysis. The formation mechanism of Fe-P amorphous particles was also discussed.     

The preparatory optimal conditions of barium titanate thin film from a hydrothermal method at low temperature

The preparation of barium titanate thin films on Ti substrates at low temperature using the hydrothermal process was studied. In addition, the interface relationship between film and substrate was investigated, revealing that the Ba²⁺ ion diffused into the Ti(OH)₄ gel formed by Ti in a strong alkaline solution, resulting in a homogeneous film. A 3-level orthogonal array design was utilized to optimize the experimental conditions. The effects of preparatory conditions such as the barium-concentration, NaOH concentration, reaction time and substrate surface treatment were systematically studied. Results indicate that the effects of the NaOH concentration and substrate surface treatment are the significant variables influencing the relative crystal intensity (intensity of (110) BaTiO₃ peaks in XRD spectrum/intensity of (001) Ti peak in XRD spectrum) of the films obtained. Polycrystalline, BaTiO₃-films were obtained, with improved crystallinity and a dielectric constant of about 915 at 1 MHz.     

Preparation of amino-acid-regulated hydroxyapatite particles by hydrothermal method

The hydroxyapatite nanorods (about 80 nm in length and 15 nm in width) with uniform size were achieved by hydrothermal method at 100 °C and pH 10 in the presence of alanine and glutamic acid. A special instillment order was used and the prepared powders were characterized for phase composition by X-ray diffraction and Fourier Transform infrared spectroscopy. The size and morphology of HAP nanoparticles were studied by Transmission electron microscopy. The characterization showed that the amino acid could induce the synthesis of hydroxyapatite nanoparticle and control HAP crystal growth when HAP crystal was formed. An instable monetite phase (CaPO₃OH) was found in the progress of ACP transforming to HAP.     

Preparation of barium hexaferrite by a hydrothermal method: structure and magnetic properties

Barium hexaferrite, BaFe¹²O₁₉, was obtained in hydrothermal conditions from a water suspension of -FeOOH and Ba(OH)₂ · 8H₂O at a temperature about 315° C. X-ray and Mössbauer spectroscopy as well as electron microscopy investigations demonstrated the appearance of -Fe₂O₃ as an intermediate phase in the hydrothermal process. The magnetic characteristics of the obtained isotropic magnets are the following: coercive fieldH _c 159 kA m^–1, residual inductionB _r 0.26 T, maximum energy product (BH) _max12 kJ m^–3. The hydrothermal procedure for the preparation of barium hexaferrite in comparison with the conventional one is discussed.     

Effect of lattice hydroxyl on the phase transition and dielectric properties of barium titanate particles

Presence of the hydroxyls in the lattice is believed to be the major cause of the reduced tetragonality in the barium titanate ceramic powder. Commercial barium titanate that is known to be cubic in nature has been used in this study. This sub-micron powder is treated with N-Methyl-2-Pyrrolidinon (NMP) to obtain a tetragonal powder as confirmed by X-ray diffraction analysis, differential scanning calorimetry and the c/a ratio. The dielectric constant of a single particle of this NMP treated cubic powder is reported to be around 64% higher than the as-received cubic powder. To add weight to the hypothesis mentioned hitherto, simulation experiments have been performed by aging in acidic water, with a pH ∼ 3–4 and in basic water, with a pH ∼ 12–13. The as-received cubic barium titanate powder, calcined at different temperatures, has been aged in different pH conditions, acid and basic waters. Then the powder is further used for the characterization of electrical properties. The dielectric properties of the barium titante ceramic powder that is determined does depend inversely on the lattice OH content as confirmed by FT-IR spectroscopic analysis and TGA results.