Formation of Lead Zirconate Titanate Powders by Spray Pyrolysis

Twin-fluid atomization spray pyrolysis (SP) has been investigated for the production of lead zirconate titanate (PZT) powders, using aqueous solutions of lead acetate and zirconium and titanium alkoxide precursor reagents. The particle size distribution of the PZT powder showed a d ₅₀ value of 0.3 μm, but with a small fraction of relatively large particles, several micrometers in size. Most particles were spherical but many of the largest particles, in the size range ca. 1–5 μm, were irregular. It was demonstrated that the morphology of the final PZT powder was controlled by decomposition processes occurring during the initial drying stages, at ≤200°C. A pyrochlore or fluorite-type intermediate crystalline phase was present in the final powders, but when the maximum reactor temperature was raised, and/or when the levels of excess lead in the starting solutions were increased, the proportion of the desired perovskite phase increased. However, at the highest process temperatures studied, ∼900°C, small crystallites of another phase formed on the surface of the PZT particles; these were probably lead oxide carbonate particles. Overall, a starting solution composition containing around 5 mol% excess Pb, and a maximum reactor temperature of 800°C, were selected as offering the most suitable conditions for producing PZT (52/48) powder, with minimal secondary phases(s). Preliminary densification studies showed that the powders could be sintered at 1150°–1200°C to give pellets of 95%–96% theoretical density.     

Crystallization of Fine, Chemically Prepared Lead Lanthanum Zirconate Titanate Powders at Low Temperature

Fine, homogeneous lead lanthanum zirconate titanate (PLZT) powder prepared by the hydrolysis of an aqueous nitrate solution with ammonia gas exhibits high reactivity when calcined. The minimum temperature for crystal formation in PLZT is 400°C. The kinetics of crystallization between 400° and 600°C are studied isothermally by XRD. The isothermal crystallization process is best fitted to a first-order equation derived for a random, nucleation-controlled system on a large number of small particles with an activation energy of 297 kJ/mol. Characterization of the powder by XRD line-broadening and BET surface-area examination in the range 400° to 500°C shows a microstructure consisting of ∼20-nm subunits agglomerated into ∼60-nm particles. Each subunit evidently generates a single nucleus, which grows within that subunit.     

热水溶液中钛酸锶晶粒的结晶过程

研究了以TiCl4水解得到的H4TiO4胶体作为钛源,在热水溶液中制备SrTiO3晶粒的结晶过程,TEM和XRD结果表明,其结晶过程主要包括3个阶段,第1阶段主要是SrTiO3晶核的形成过程;第2阶段主要是SrTiO3晶粒的配向聚集生长过程;第3阶段主要是SrTiO3晶粒的溶解结晶过程,其中第1阶段的控制步骤为H4TiO4胶体的溶解,第2阶段中晶粒的配向聚集生长在短时间内即可完成,很快进入第3阶段小晶粒的溶解和大晶粒的重结晶过程,该阶段反应速度慢,需要较长时间才能得到结晶完好的晶粒,在热水溶液中以H4TiO4胶体作为钛源制备SrTiO3晶粒关键在于控制结晶过程的第1阶段和第2阶段。     

Topotatic-Like Phase Transformation of Amorphous Lead Titanate to Cubic Lead Titanate

The crystallization process of lead titanate (PT) prepared using the polymeric precursor method was investigated using X-ray diffractometry, Raman spectroscopy, electron microscopy, and X-ray absorption spectroscopy techniques. The results showed that amorphous PT was formed by an O–Ti–O structure composed of fivefold and sixfold oxygen-coordinated titanium. The local structure of the amorphous PT phase was similar to that of the cubic PT phase, i.e., similar coordination number and similar bond lengths, leading to a topotactic-like transformation during the phase transformation from amorphous to cubic perovskite PT. Because of the low crystallization temperature, every transformation observed during the crystallization process was associated with a short-range rearrangement process.     

水热法制备BiFeO3粉体

以FeC l3.6H2O和B i(NO3)3.5H2O为原料,氨水为沉淀剂,KOH为矿化剂,采用共沉淀法制备前驱物,水热法合成了纯相的B iFeO3粉体。X射线衍射结果表明,在160℃,碱浓度仅为0.15 mol/L的水热条件下,即可合成纯相的B iFeO3粉体。该工艺大大降低了水热温度,减小了碱浓度,从而节约了能源,降低了成本,减轻了碱对水热设备的腐蚀。扫描电镜显示,前驱沉淀物陈化时间为1 d时,水热制备的B iFeO3粉体中有发育良好的六方短柱状晶体形成;陈化时间增加到3 d时,所得B iFeO3粉体呈双层板状。差热-失重分析表明,所得B iFeO3粉体的尼尔温度(TN)为301℃,居里温度(TC)为828℃,分解温度为964℃。     

Synthesis of Ferroelectric Lead Titanate Nanohoneycomb Arrays via Lead Supplement Process

Here, we demonstrate a novel process to convert TiO₂ nanotubes into ferroelectric nanohoneycombs, comprised of vertically aligned PbTiO₃ nanotubes. Tube bottom opening process enabled effective infiltration of lead acetate precursor into the nanotubes. Nanohoneycombs, which were converted via additional lead supplement process, showed uniform conversion and well‐defined ferroelectric properties with the effective piezoelectric coefficient of approximately 20 pm/V, which was measured by piezoresponse force microscopy.     

钡钛醋酸盐凝胶制备BaTiO3粉体

本文报道了用ｓｏｌ－ｇｅｌ法制备钡醋酸盐凝胶，并分别作高灼烧和水热处理制备ＢａＴｉＯ３粉体。通过对产物的表征，比较了这两种处理过程，进而对水热条件下陶瓷粉体的形成机理作了探讨。由于水热条件，凝胶在反应介质中溶解，进而结晶形成晶粒，因此所形成的ＢａＴｉＯ３晶粒线度小；线度分布范围窄。晶粒形貌完整，明显优于高温灼烧处理后得到的粉体。     

Direct Amorphous-to-Cubic Perovskite Phase Transformation for Lead Titanate

The phase evolution of lead titanate processed by the polymeric precursor method was investigated by thermal analysis, X-ray diffraction, and high-resolution transmission electron microscopy. The results showed that the cubic perovskite PbTiO₃ (PT) phase is formed from an inorganic amorphous precursor at a temperature of 444°C. A gradual transition from cubic to tetragonal perovskite PT was observed with the increase of calcination time at this temperature. HRTEM results showed that the cubic PT particles have a size of around 5 nm. The identification of cubic PT as an intermediate phase supports the hypothesis that the chemical homogeneity was kept at the molecular level during the synthesis process, with no cation segregation.     

Preparation of Tetragonal Barium Titanate Thin Film on Titanium Metal Substrate by Hydrothermal Method

Tetragonal BaTiO₃ thin films were prepared directly on Ti metal substrates in Ba(OH)₂ solutions by a hydrothermal method at temperatures 400° to 800°C for 5 to 240 min. The film thickness estimated from weight gain of Ti plate was in the range from 0.5 to 2.5 μm, and it increased with increasing treatment temperature, treatment time, and Ba(OH)₂ concentration. Rectangular crystals having {100} and {001} faces grew idiomorphically with approximate crystal size of 0.3 to 2.0 μm. The tetragonality of the BaTiO₃ films became apparent when the average crystal size exceeded about 1 μm. Lattice parameters of the films were a = 3.994 Å, c = 4.035 Å, and c/a = 1.010. The films formed above 600°C had preferred orientation showing stronger XRD peaks of h 00 and 00 l than the other peaks.     

Hydrothermal Preparation of Calcium Hydroxyapatite Powders

Calcium hydroxyapatite powders were prepared by hydrothermal reactions of calcium pyrophosphate and calcium oxide. Primary particles of the hydroxyapatite obtained were spherical with diameters less than 0.2 μm, and small prismatic crystals were rarely observed in some fields. The effects of temperature, pressure, and soaking time on the structural features of the resultant powders were also studied by means of XRD and SEM and were smaller than expected for the ranges investigated.     

Fabrication of NiO Nanoparticle-Coated Lead Zirconate Titanate Powders by the Heterogeneous Precipitation Method

NiO nanoparticle-coated lead zirconate titanate (PZT) powders are successfully fabricated by the heterogeneous precipitation method using PZT, Ni(NO₃)₂·6H₂O, and NH₄HCO₃ as the starting materials. The amorphous NiCO₃·2Ni(OH)₂·2H₂O are uniformly coated on the surface of PZT particles. XRD analysis and the selected-area diffraction (SAD) pattern indicate that the amorphous coating layer is crystallized to NiO after being calcined at 400°C for 2 h. TEM images show that the NiO particles of ∼8 nm are spherical and weakly agglomerated. The thickness of the nanocrystalline NiO coating layer on the surface of PZT particle is ∼30 nm.     

BaTiO3超细粉体的溶胶-沉淀法制备及其表征

采用溶胶-沉淀工艺制备BaTiO3纳米粉体,探讨了沉淀剂NaOH溶液浓度对制备BaTiO3粉体相组成的影响,提出了溶胶-沉淀法合成纯相BaTiO3的反应机理,并对沉淀水洗后的湿凝胶进行表面改性.探讨了添加表面活性剂及有机溶剂脱水过程对粉体团聚程度的有效控制.     

Sol–Gel Preparation of Lead Zirconate Titanate Powders and Ceramics: Effect of Alkoxide Stabilizers and Lead Precursors

Lead zirconate titanate (PZT) (52/48) powders were prepared by a sol–gel process, using different raw materials to introduce the lead component together with several solvents and chemical modifying agents. A study of the effect of these variables on crystallization behavior was conducted to determine the best conditions for preparing monophasic submicrometer-sized PZT perovskite powders in the morphotropic region. In the present work, well-crystallized, submicrometer-sized single-phase perovskite PZT powders were obtained after heat treatment at 600°C for 1 h. The dependence of this crystallization temperature on the preparation conditions was observed. The sol–gel-derived submicrometer-sized PZT powders were sintered to ∼96% of relative density after 2 h at 950°–970°C. The sintered ceramics exhibited a dielectric permittivity of 1000, a piezoelectric coefficient of 135 pC·N⁻¹, a remanent polarization of 20 μC·cm⁻², and a coercive field of 10.6 kV·cm⁻¹.     

Polymorphic Phase Transformation of Lead Monoxide and Its Influence on Lead Zirconate Titanate Formation

The polymorphic phase transformation of PbO from massicot to litharge phase is easily produced by mechanical force. The transformation is relatively quick by wet ball-milling. The additions of TiO₂ and ZrO₂ tend to retard it. A second-order exponential relation is observed between the fractional conversion and the milling time for pure PbO, PbO-TiO₂, and PbO-ZrO₂-TiO₂ systems with a rutile constituent. This exponential relation is changed into a first-order logarithmic relation when anatase instead of rutile is used. Although the PbO _ss phase is observed irrespective of the phase of the PbO in the raw materials, this PbO _ss peak is more obvious when massicot PbO or anatase TiO₂ is used. The formation of PbO _ss phase is also dependent on the reactivity of the ZrO₂, and its presence can affect the formation and piezoelectric properties of PZT ceramics.     

锂离子电池负极材料钛酸锂微球的水热合成及性能

以水热法合成了尖晶石型Li4Ti5O12微球,研究了氢氧化锂用量、水热时间、热处理温度对Li4Ti5O12微球性能的影响,分析了合成机理。用X射线衍射仪分析样品结构,用扫描电子显微镜、透射电子显微镜表征产物的形貌,并研究了样品的恒流充放电性能和循环稳定性。结果表明：当0．2g水解产物与2．55mmolLiOH·H2O1...     

Hydrothermal Synthesis of Bismuth Titanate Powders

Bismuth titanate was synthesized under hydrothermal conditions from an amorphous bismuth–titanium precursor gel. The gel was formed by mixing a bismuth acetate complex with titanium butoxide and then adding the solution dropwise into 6 M NaOH. The resulting gel suspension was reacted under hydrothermal conditions at temperatures ranging from 160° to 200°C to form crystalline bismuth titanate. The gel crystallization kinetics increased with temperature, which resulted in 100% crystalline bismuth titanate in 5 h at 200°C. Wavelength-dispersive spectroscopy data indicated that sodium was incorporated into bismuth titanate during processing, and X-ray diffractometry suggested that the powder was composed of the Bi₅Ti₄O₁₅ phase. Transmission electron microscopy micrographs showed that the gel particles decomposed to 100–200 nm crystalline bismuth titanate particles during hydrothermal processing.     

水热法制备钕掺杂BaTiO3粉体及其介电性能研究

以BaCl2·2H2O、TiCl4和NdCl3为原料,采用水热法制备了掺钕的BaTiO3纳米粉体,并经高温烧结后得到瓷体。利用DTA、XRD、SEM等测试手段,分析了钕掺杂对钛酸钡粉体及其陶瓷电性能的影响。研究表明,掺杂后,钕固溶到了钛酸钡的晶格中并取代钡位或钛位。钕的掺杂有助于获得细晶高致密的陶瓷,当W(NdCl3)%为0.6时,致密度最高,常温下相对介电常数高达5650,击穿场强达到3.5kV/mm。     

一步水热法制备钛酸锂材料

采用一步水热法制备钛酸锂材料,并对制备的钛酸锂的性能进行研究。该方法与传统的水热合成法相比,具有制备工艺周期缩短,无其它试剂使用,减少环境污染等优点。结果表明,该方法制备的钛酸锂材料,在0.1 C倍率下的首次放电比容量为163 mAh·g^-1,首次效率为100%;XRD分析表明,其晶型结构与标准的钛酸锂图谱一致;SEM表征显示其颗粒形貌规则、分布均匀;循环伏安法测试表明,其具有良好的充放电可逆性能。     

Microwave Effects in Lead Zirconium Titanate Synthesis: Enhanced Kinetics and Changed Mechanisms

A novel, simple, and fast solid-state procedure has been demonstrated for the synthesis of Pb(Zr,Ti)O₃ (PZT), using microwave radiation. The process consists of starting with the respective oxides mixed in the required proportions and exposing the charge to the microwaves. By making one or more of the constituent oxides slightly nonstoichiometric, enormous enhancement in reaction rates has been achieved, and single-phase PZT can be synthesized at temperatures as low as 600°C. Moreover, it has been shown that the combined use of nonstoichiometric precursors and microwave irradiation leads to different reaction pathways for the formation of PZT. Further, the microwave method diminishes PbO loss.     

二乙醇胺辅助溶胶-凝胶法低温合成锆钛酸铅纳米粉体

以醋酸铅[Pb（CH3COO）2^-33H20]、硝酸锆[Zr（N03）4^-5H2O]和钛酸四丁酯[Ti（C4H90）4]为原料,以二乙醇胺（diethanolamine,DEA）为聚合剂．用溶胶-凝胶法制备了锆钛酸铅（PbZrxTil-x03,PZT）纳米陶瓷粉体。研究了DEA对溶胶-凝胶法合成PZT陶瓷粉体的影响...