Effect of Composition and Size of Crystallite on Crystal Phase in Lead Barium Titanate

Lead titanate, barium titanate, and lead barium titanate powders (>99.9% pure), the particle size of which varied from 0.03 to 0.15 μm depending on the calcination temperature and the composition, was prepared from barium lead titanyl oxalate, which was previously prepared by reacting high-purity ammonium titanyl oxalate with barium and lead acetate. The critical crystallite size of BaTiO₃ powder from the cubic to the tetragonal phase is around 1 μm. Pb_0.3Ba_0.7TiO₃ powder with an average size of 0.057 μm showed the tetragonal phase.     

Barium titanate characterization by differential scanning calorimetry

Differential scanning calorimetry (DSC) was used to characterize barium titanate formed after decomposition of barium titanyl oxalate. Three different methods of the oxalate precipitation reaction were used to prepare barium titanyl oxalate which after calcinations result in barium titanates with different barium to titanium ratio (A/B). It appears that two factors have effect on Curie temperature: barium to titanium ratio and mechanical stress introduced by milling.     

Preparation of Semiconducting Titanates by Chemical Methods

Semiconducting barium titanate has been prepared both by coprecipitating the lanthanum in the preparation of barium titanyl oxalate and by precipitation of lanthanum hydroxide in a slurry of the titanate. Partial substitution of strontium or lead for barium and zirconium for titanium has also been achieved using this oxalate process. The electrical conductivity of these materials was measured and is discussed. The effect of excess titanium on the electrical properties was also determined and an excess of 1 to 2 mole % was found to raise the positive temperature coefficient under the firing conditions employed.     

Ferroelectrics of Ultrafine Particle Size: I, Synthesis of Titanate Powders of Ultrafine Particle Size

Two methods used to synthesize high-purity ferroelectric titanate powders in controlled, narrow size distributions, with average particle diameters <1000 A, were: (1) isothermal pyrolysis of barium titanyl oxalate or mixed calcium-barium titanyl oxalates as low as 550° and 825°C, respectively, average particle sizes depending strongly on the pyrolysis temperature; and (2) hydrolysis of titanate esters in barium hydroxide. Using solvent media of controlled polarity, high-purity stoichiometric BaTiO₃ was obtained with average sizes as small as 100 A. Factors affecting stoichiometry and particle size are discussed in terms of assumed reaction mechanisms.     

液相法制备钛酸锶铅粉的研究

研究了反应温度、酸碱度、放置时间和煅烧温度对化学共沉淀法制得的钛酸锶铅粉末的影响,探讨了其热分解过程,用XRD、SEM、DTA和EPMA对粉体进行了综合分析,得到了纯度较高的钛酸锶铅粉末.     

Alternative Route for Synthesis of Barium Titanyl Oxalate: Molecular Precursor for Macrocrystalline Barium Titanate Powders

An important molecular precursor to barium titanate, namely, barium titanyl oxalate [BaTiO(C₂O₄)₂.4H₂O], has been synthesized by an alternative route. An alcoholic solution containing 1 mol of butyl titanate monomer [(C₄H₉O)₄Ti] is reacted with alcoholic solution containing 2 mol of oxalic acid (H₂C₂O₄:2H₂O) to form an intermediate soluble oxalotitanic acid [H₂TiO(C₂O₄)₂.nH₂O]. The oxalotitanic acid in alcoholic medium is subjected to cation exchange reaction with aqueous solution containing equimolar barium acetate to form an insoluble barium titanyl oxalate (BTO) in yields of 80–85% at room temperature. The pyrolysis of BTO in air at T .750°C/5 h produced barium titanate (BT) powders.     

Effect of Microstructure on the PTCR Effect in Semiconducting Barium Titanate Ceramics

The microstructural influence on the PTCR effect in semiconducting barium titanate ceramics was studied and a method for preparing the ceramic bodies exhibiting a PTCR effect of more than seven orders of magnitude was established. Commercial barium titanyl oxalate was used as a starting material and Sb₂O₃ was added as a doping substance. The average grain sizes of the ceramic bodies prepared were 2 to 5 μm over a sintering range of 60 to 92%, to examine in detail the microstructural influence on the PTCR effect. No extra element, such as Mn or Cr, was added to develop the PTCR effect in the present PTCR materials.     

Phase development of barium titanate from chemically modified-amorphous titanium (hydrous) oxide precursor

A synthesis procedure for barium titanate involving a chemically modified titanium precursor has been developed. Using a titanium isopropoxide precursor modified with acetylacetone and barium acetate, coprecipitated gels were obtained by addition to a KOH solution. Direct precipitation of cubic BaTiO₃ from such precursor suspensions was obtained under hydrothermal conditions. The pH value was found to be a critical reaction parameter such that production of phase pure BaTiO₃ required high pH (>13.0), a finding consistent with thermodynamic predictions of the Ba–Ti–H₂O stability system and prior hydrothermal syntheses. It was determined that phase-pure barium titanate can be synthesized at temperatures as low as 50 °C and that higher reaction temperatures accelerate the crystallization process. The particle size of the synthesized powder ranged from 50 to 350 nm for the synthesis conditions explored in the current work.. It was demonstrated that particle size can be controlled by proper selection of the hydrothermal synthesis conditions such as reaction concentration, temperature, and time. The chemically modified synthesis produces barium titanate more rapidly at lower reaction temperatures than previously reported for similar syntheses.     

Characterization of Barium Titanyl Oxalate Tetrahydrate

The XRD pattern and the thermal behavior of barium titanyl oxalate tetrahydrate (BTOT) were investigated. BTOT crystallizes in the monoclinic system, 2/ m , with unit cell dimensions of a = 14.954 Å, b = 19.332 Å, c = 13.947 Å, and β= 106.43°. Unit cell content ( Z ) is 12 and the Bravais lattice is P. Theoretical density is 2.31 g/cm³. At a relatively low temperature (∼60°C), BTOT starts to dehydrate, resulting in a less-than-calculated weight loss of ignition. Barium titanate powder obtained by calcining the oxalate exists as the cubic perovskite phase, instead of the tetragonal phase at low temperatures. This happens when the particle size of the crystals is smaller than ∼ 30 nm. As the crystal coarsens, barium titanate powder transforms to the tetragonal state.     

Synthesis of nanosized (Pb,Sr)TiO3 perovskite powders by coprecipitation processing

Nanosized perovskite lead strontium titanate (Pb_xSr_1−x)TiO₃ (PST) powders were successfully prepared by a simple coprecipitation method. Lead-strontium titanyl oxalate (PSTO) precursor was first synthesized at room temperature, and the precursor was then calcined at 600 °C for 1 h to produce the single phase perovskite PST powders. Characterization studies were carried out on the as-dried precursor and the calcined PST powders by various techniques. The results showed a strong dependence of the chemical composition of final PST powders on pH value in the coprecipitation reaction. PST powders with desired composition could be synthesized by adding 25 mol% excess Sr. PST particles were found to be spherical in nature with an average size of 10 nm.     

Factors Affecting the Preparation of Barium Titanyl Oxalate Tetrahydrate

Several experiments have been conducted to investigate the preparation of barium titanyl oxalate tetrahydrate (BTO). Differential thermal analysis and thermogravimetric analysis were employed to investigate the thermal decomposition, and an X-ray diffractometer and a transmission electron microscope were used to analyze the phases and crystalline states. It has been found that BTO is a nonstoichiometric compound, in which barium hydrogen oxalate hydrate was inserted by the titanium species. Moreover, it has been shown that a mixture would from rather than BTO, depending on pH, mixing order, and oxalate solution.     

水热合成技术的研究和应用──Ⅰ.钛酸盐晶体粉末的制备

应用水热合成法制备钛酸钡、钛酸锶、铁酸钙从钛酸铅晶体粉末，采用的技术路线分别以Ba（OH）2，Ca（OH）2，Sr（OH）2，Ph（OH）2及TiO（OH）2为水热合成钛酸盐的前驱物。研究了它们合成时的KOH浓度、温度和时间等影响因素。根据实验结果．按水热前驱物M（OH）2的特性分类．找出它们的共性和差异，提出了合成机理及MgTiO3和Al2（TiO3）3难以用水热合成的原因。     

Alkoxide-Hydroxide Route to Syntheltize BaTiO3-Based Powders

When preparing homogeneous, fine barium titanate powders, the major difficulty is to avoid the spontaneous self-condensation between the Ti-OH groups. In the usual way of preparing fine barium titanate powders, chelating agents (citrate, oxalate) or simply unidentate ligands (alkoxy or carboxyl groups) are used to complex titanium atoms. Another way is to mix barium and titanium precursors in a strongly basic medium. The condensation between the Ti(OH)^2-₆Ba²⁺ species directly gives the perovskite compound. Using an alkoxide-hydroxide route, a homogeneous Ba-Ti solution was prepared that completely advanced by condensation between the Ti(OH)^2-₆Ba²⁺ species and led to a controlled-stoichiometry powder. Concerning pure barium titanate, dried powders exhibited the cubic perovskite structure, and a direct sintering at 1150°C, without calcination, led to highly dense BaTiO₃ bodies with fine-grained uniform microstructure (1 μm) that exhibited a high permittivity value at room temperature ( K = 5400). The alkoxide-hydroxide method was also used to prepare dense alkaline-earth perovskite ceramics with complex compositions.     

草酸浸出Na8Ti5O14制备草酸氧钛钠的工艺

用草酸浸出多钛酸钠Na8Ti5O14,获得含钛料液,通过蒸发结晶成功制备了纯度99%的草酸氧钛钠产品,对产物进行了表征,考察了反应温度、反应浓度、反应时间、搅拌强度对钛浸出率的影响,得到了优化条件为：草酸浓度4 mol/L,反应温度80℃,反应时间2 h. 研究了浸出反应的动力学,计算得到表观活化能为43.85 kJ/mol,浸出过程属于未反应核收缩模型,速率为界面化学反应控制.     

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.     

Ultrafine Barium Titanate Powders via Microemulsion Processing Routes

Three processing routes have been used to prepare barium titanate powders, namely conventional coprecipitation, single-microemulsion coprecipitation using diether oxalate as the precipitant, and double-microemulsion coprecipitation using oxalic acid as the precipitant. A single-phase perovskite barium titanate was obtained when the double-microemulsion-derived oxalate precursor was calcined for 2 h at a temperature of as low as 550°C, compared to 600°C required by the single-microemulsion-derived precursor. A calcination for 2 h at >700°C was required for the conventionally coprecipitated precursor in order to develop a predominant barium titanate phase. It was, however, impossible to eliminate the residual TiO₂ impurity phase by raising the calcination temperature, up to 1000°C. The microemulsion-derived barium titanate powders also demonstrated much better powder characteristics, such as more refined crystallite and particle sizes and a much lower degree of particle agglomeration, than those of the conventionally coprecipitated powder, although they contained ∼0.2 wt% BaCO₃ as the impurity phase.     

反应条件对共沉淀法制备纳米钛酸钡粉体的影响

以钛酸四丁酯、草酸、草酸钠和醋酸钡为原料,采用共沉淀法制备了纳米钛酸钡粉体。通过XRD、IR和TG等检测手段,研究pH值和煅烧温度对粉体纯度的影响。结果表明,制备的前驱体为钛钡混合草酸盐沉淀。pH在3~6的范围内,随着pH值的提高,粉体的纯度下降,粒径减小。随着煅烧温度的升高,粉体的纯度提高。煅烧温度太高,钛酸钡易从立方相转变为四方相。最佳实验条件为pH=3.14,煅烧温度900℃。在此实验条件下,成功制备出均匀的粒径尺寸为37.2nm的纯相纳米钛酸钡粉体。     

纳米钛酸锶钡粉体制备及其对水中Cd2+吸附行为

采用草酸盐化学共沉淀法制备了草酸氧钛锶钡前驱体,通过905℃高温煅烧,制得了高纯纳米钛酸锶钡,并利用SEM、TEM、FT-IR和XRD对其进行了表征;并将该粉体应用于水中重金属镉离子的吸附.结果表明：该法合成的钛酸锶钡粉体为球形,钙钛矿结构,平均粒径为36 nm.对水中的镉离子具有较强的吸附能力,其吸附量与介质的pH值有密切关系,吸附动力学符合Langmuir和Bangham速率方程所描述的规律;吸附等温线较好地符合Langmuir和Freundlich等温方程,吸附行为是自发的、放热的物理吸附过程.     

空心钛酸钡的制备及其形成机理

以二氧化钛（TiO₂）和八水合氢氧化钡[Ba（OH）₂·8H₂O]为原料,采用水热合成法,成功制备出具有四方相晶型和空心形貌结构的钛酸钡粉体。利用透射式电子显微镜（TEM）和X射线衍射（XRD）对样品的形貌结构和晶型做了表征,通过研究反应过程中钛酸钡粉体的结构和晶型随时间的变化过程,对空心钛酸钡的形成机理做了详细的探讨,并考察了不同反应温度和钡浓度对钛酸钡粉体结晶和生长的影响。研究结果表明：反应温度和钡浓度会影响钛酸钡粉体的晶型和形貌,并以此提出了一种空心钛酸钡的形成机理;当反应温度为180 ℃、钡浓度为3.0 mmol/L时,能获得粒径分布均匀的四方相晶型的空心钛酸钡粉体。     

副产硫酸亚铁制备电池级草酸亚铁的研究

以钛白副产硫酸亚铁为原料制备出电池级草酸亚铁。研究了除杂、沉淀、转化反应过程中反应温度、反应时间、硫酸亚铁浓度以及反应pH等因素对产品质量的影响,并得到了优惠工艺条件。结果表明：在反应温度为 95 ℃、反应时间为6 h的条件下用铁粉对硫酸亚铁溶液除杂,得到纯净硫酸亚铁溶液;在反应温度为40 ℃、铁（Ⅱ）质量浓度为90 g/L的条件下用氨水沉淀,再用草酸于反应时间为60 min、pH=2.0条件下将氢氧化亚铁转化成草酸亚铁,制备出了纯度大于99.5%、粒径小于3.0 μm、杂质含量低的电池级草酸亚铁。为解决钛白副产硫酸亚铁的综合利用提供了一条有效的途径。