水热法制备的BaTiO3微晶粒的特性

本文报道了对水热法制备的ＢａＴｉＯ３纳米微粒性质和缺陷研究的结果．水热法制备的ＢａＴｉＯ３纳米微粒形貌和线度可通过改变前驱物形式和反应条件加以适度调控．在一定的条件下，水热法得到的是在常温下能稳定存在的立方相ＢａＴｉＯ３晶粒．这种“反常”结晶学特性是由于晶粒里含有一定量的Ｏ－Ｈ缺陷和钡离子空位缺陷所造成的．选择适宜的反应条件（如提高反应前驱物钡钛摩尔比等）或采用一定的处理手段（如热处理等），减少或消除这类缺陷，即可消除此“反常”结晶学特性．     

液相包裹法制备BaTiO3微粉合成机理研究

以Ｈ２ＴｉＯ３微粉为活性固相基体，Ｂａ（ＣＯＯＨ）２溶液为包裹相，采用液相包裹－界面反应的方法，进行制备ＢａＴｉＯ３微粉及其合成机理研究，提出了一套较完善且简便、适合于大生产的新的ＢａＴｉＯ３微粉制备技术与方法，初步揭示了液相包裹法制备ＢａＴｉＯ３微粉的反应过程及机理。通过这一方法，可以得到更为纯净、高分散、形貌更趋于球形的ＢａＴｉＯ３微粉。     

化学共沉淀法制备纳米级CaTiO3粉体

本文以Ｈ２ＴｉＯ３、Ｈ２Ｏ２、ＮＨ３、Ｃａ（ＮＯ３）２为主要原料，用化学共沉淀法制备了纳米级ＣａＴｉＯ３。确定了反应物Ｈ２ＴｉＯ３、Ｈ２Ｏ２、ＮＨ３的最佳摩尔比为１：８：２。用不同的退火温度和退火时间对样品处理得到相应粒径的纳米粉体，再用Ｘ－ｒａｙ和透射电镜对这些粉体进行了评估。     

柠檬酸盐溶液冷冻干燥法制备Ba_2Ti_9O_20粉体

本文通过柠檬酸盐冷冻干燥法制备了微波介质材料──Ｂａ２Ｔｉ９Ｏ２０粉体。对于由冷冻干燥法制得的柠檬酸钡钛前驱体，在７００℃～１２００℃温区范围内进行煅烧合成实验，通过Ｘ衍射定相分析表明：在１１００℃保温４ｈ的合成条件下，开始出现了Ｂａ２Ｔｉ９Ｏ２０相；在１２００℃保温４ｈ条件下，可获得只含Ｂａ２Ｔｉ９Ｏ２０和ＢａＴｉ４Ｏ９相的粉体，完全排除了ＢａＴｉ５Ｏ１１相。粉体经压片成型后，在１３４０℃保温４ｈ的烧结余件下，可获得较为致密的陶瓷样品     

NaOH-KOH熔盐中合成BaTiO3反应过程电导率的变化

用交流阻抗谱法测量了３５０℃时共晶成分的ＮａＯＨ－ＫＯＨ熔盐中加入ＴｉＯ_２和ＢａＣＯ₃时体系电导率的变化,准确给出了３５０℃共晶成分ＮａＯＨ－ＫＯＨ熔盐的电导率为１．０５３Ω－１·ｃｍ^－１,确认了在ＮａＯＨ－ＫＯＨ熔盐中ＴｉＯ_２与ＢａＣＯ_３反应,生成ＢａＴｉＯ_３时熔盐不参与反应．实验数据表明３５０℃ＴｉＯ_２与ＢａＣＯ_３在共晶成分的ＮａＯＨ－ＫＯＨ熔盐中的溶解过程可在短时间内达到平衡．     

柠檬酸盐溶液冷冻干燥法制备了Ba2Ti9o20粉体

本文通过柠檬酸盐冷冻干燥法制备了微波介质材料－Ｂａ２Ｔｉ９Ｏ２０粉体。对于由冷冻干燥法制得的柠檬酸钡然有驱体，在７００℃＝－１２００℃温区范围内进行煅烧合成实验，通过Ｘ衍射定相分析表明：在１１００℃保温４ｈ的合成条件下，开始出现了Ｂａ２Ｔｉ９Ｏ２０相；在１２００℃保温ｈ条件下，可获得了只含ＢａＴｉ９Ｏ２０和ＢａＴｉ４Ｏ９相的粉体，完全排除了ＢａＴｉ５Ｏ１１相。     

亚纳米铁电陶瓷介电性能的粒度效应

本文采用ＢａＴｉＯ３超细粉和常规陶瓷工艺制备了亚纳米铁电陶瓷，并研究了其介电性能的粒度效应。研究表明，ＢａＴｉＯ３铁电陶瓷的介电常数、居里点及介质损耗都存在很明显的粒度效应，晶粒的细化有利于性能的提高。介电常数在粒径为０．８μｍ处有一个最大值，当晶粒减至亚纳米（〈０．８μｍ）时，居里点降低，损耗因子及其温度变化率减小。     

化学法制备的（Sr,Pb）TiO3基PTCR陶瓷

通过化学工艺制备（Ｓｒ，Ｐｂ）ＴｉＯ３半导体陶瓷，首次获得了与ＢａＴｉＯ３陶瓷相类似的典型ＰＴＣ特性，样品耐压强度大，室温电阻率低于１０＾２Ω．ｃｍ，升阻比高达１０＾６．３３，烧结温度可以降低至１１００℃以下。     

颗粒表面改性法制备PTC粉体的研究

本文介绍了一种通过液相颗粒表面改性技术添加二次掺杂物来制备ＰＴＣ粉体的新方法。即将烧结助熔剂Ａｌ２Ｏ３，ＳｉＯ２以及受主杂质ＭｎＯ采用溶液形式，包裹在ＢａＴｉＯ３基粉体颗粒表面进行改性，由此可以得到二次掺杂物Ａｌ２Ｏ３、ＳｉＯ２和ＭｎＯ分布均匀的ＰＴＣ粉体。     

高容量SiO2掺杂的（Ba,Pb）TiO3基高居里温度PTCR陶瓷

在制备高质量的（Ｂａ，Ｐｂ）ＴｉＯ＿３基高居里温度ＰＴＣＲ陶瓷时，一般采用铅气氛烧结方法。但是，这种烧结工艺制成的产品的相对成本是高的。作者的实验表明，高容量ＳｉＯ＿２掺杂烧结方法也可以用于制备高质量的（Ｂａ，Ｐｂ）ＴｉＯ＿３基高居里温度ＰＴＣＲ陶瓷。本文主要报道高容量ＳｉＯ＿２对（Ｂａ，Ｐｂ）ＴｉＯ＿３基高居里温度ＰＴＣＲ陶瓷烧结工艺和电特性的影响。     

Preparation of fine powders with perovskite structure from metal alkoxides

The preparation of perovskite powders was investigated by the metal alkoxide methods. The complex alkoxide as a precursor was hydrolysed under specific conditions, and submicrometre powders of perovskite compounds differing in composition, BaTiO3, Ba(Mg1/3Nb2/3)O3, PbTiO3, and Pb(Mg1/3Nb2/3)O3, could be obtained. The simultaneous use of a dipolar aprotic solvent, such as acetone, etc., with ethanol was found to be effective for the preparation of the spherical or nearly spherical powders with submicrometre diameter. The submicrometre powders were formed through nucleation–aggregation, but not by the usual nucleation–grain growth. Such powder formation, and the affinity of the solvent for the diffusion layer surrounding the colloidal particle, are important. The powders obtained here could be crystallized to the desired crystalline phase at lower temperatures.     

溶胶凝胶法以无机锆源制备Ba(Zr,Ti)O3的成胶机理分析

为制备高性能低成本压电陶瓷材料,以无机锆为锆源,低价的乙酸与乙二醇为溶剂,采用Sol-Gel法制备Ba(Zr,Ti)O3溶胶和纳米粉体.XRD和TEM分析显示,所制备的粉体为纯钙钛矿相,近球形,粒径在40nm左右.通过IR、GC-MS分析了锆钛酸钡溶胶的形成机理,结果表明:在锆钛酸钡的溶胶过程中乙二醇、乙酸与乙酸钡、钛酸四丁酯、柠檬酸锆发生化学反应,生成以金属氧键为中心,乙二醇与冰乙酸为中间络合支架的链状聚合体,提高了溶胶凝胶的质量和稳定性.     

Microwave assisted semi-solvothermal synthesis of nanocrystalline barium titanate

In an endeavor to synthesize tetragonal nanocrystallites of BaTiO3 at much reduced reaction time, we explored the possibility of performing microwave assisted semi-solvothermal reaction by using Ba(OH)2 . 8H2O and amorphous titanium hydrous gel as precursors and 1,4-butanediol and water as solvent. Typically, such a microwave assisted reaction was accomplished within 2 hrs at 220 degrees C as against 12 hrs required in conventional approach. The crystallized BaTiO3 powders (microwave assisted as well as conventionally processed for reference) were characterized by X-ray diffraction, thermal analysis, infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. We have detected metastable cubic phase by XRD while locally symmetric tetragonal phase by Raman spectroscopy in case of conventional semi-solvothermal processing. On the contrary, we could detect co-existence of tetragonal and cubic phases by XRD and only tetragonal phase by Raman spectroscopy in case of microwave assisted semi-solvothermal processing. The TEM analysis indicates typical particle size distribution in the range of approximately 20 to 80 nm for conventionally processed powder while that in the range of approximately 20 to 50 nm for microwave processed powder. HRTEM images evince the distortion from an ideal cubic structure in case of microwave processed powder which can be correlated with anisotropic lattice contraction during the microwave induced heating. AFM analysis exhibited relatively less aggregation of nanoparticles for microwave assisted process.     

钛酸钡的制备研究进展

对钛酸钡粉末的制备方法进行了综合。传统的高温固相合成法已不能满足电子技术微型化和集成化发展对钛酸钡粉体提出的超细、高纯、单分散要求。从制备成本和操作过程来看，经过改进的共沉淀法、草酸盐法和水热法是制备高纯、亚微米级钛酸钡粉末的重要方法，在大规模生产中有较好的应用前景。在水热过程中，通过选择适当的钛源和水热条件，可以制备出高纯、单分散的亚微米级及纳米级钛酸钡粉体。低温直接合成法因其原料易得，过程简单，是一种在大规模生产上较有应用前景的制备纳米钛酸钡的方法。     

Preparation and characterization of BaSnO<Subscript>3</Subscript> powders by hydrothermal synthesis from tin oxide hydrate gel

BaSnO₃ powders have been prepared from the tin oxide hydrate gel and the Ba(OH)₂ solution via hydrothermal synthesis route. The influence of the process parameters on the characteristics of BaSnO₃ has been studied. A powder with the single-phase of BaSnO₃ can be obtained only when the concentration of Ba(OH)₂ solution is no less than 0.2 M and the ratio of Ba:Sn lies between 1.0 and 1.2. At a hydrothermal temperature of 330 °C or higher, uniform BaSnO₃ powders can be directly prepared through hydrothermal reaction. When the hydrothermal temperature is lower than 250 °C, the as-prepared powder consists of BaSn(OH)₆ that transforms through an amorphous phase into BaSnO₃ by calcination at 260 °C. In the hydrothermal temperature range of 130–250 °C, a higher temperature can promote the crystallization of BaSnO₃, increases its specific surface area and decreases the average particle size. The duration of the hydrothermal reaction affects the morphology of the powder particles. The effects of the nonaqueous solvents on the properties of powders have also been investigated.     

Grain size dependence of dielectric properties of ultrafine BaTiO3 prepared by a sol-crystal method

Ultrafine BaTiO3 prepared by a decomposition of an organometallic crystal with unity of Ba/Ti ratio (sol-crystal method) has been characterized. While the as-prepared product resulting from the decomposition of the organometallic crystal at room temperature was BaTiO3 with pseudo-cubic structure, the well-crystallized tetragonal polymorph was obtained by firing the as-prepared product above 1000°C. Residual organic compounds, CO2-3 and OH- ions in the samples prevent the grain growth and tetragonal distortion of BaTiO3. We obtained quite higher room temperature permittivity (3700) at 1 kHz for the sample fired at 1200°C than that (630) prepared by conventional solid-state reaction starting from BaCO3 and TiO2. Such a high value was probably due to the accomplishment of homogeneous cation stoichiometry, which was achieved by this preparation method via the organometallic crystal with stoichiometric Ba/Ti ratio. This revised version was published online in November 2006 with corrections to the Cover Date.     

纳米钛酸钡粉体的水热合成研究

采用氢氧化钡和四氯化钛作为钡源和钛源,氨水作矿化剂,在200～280℃保温4h条件下合成粒径为60～90nm钛酸钡粉体。TEM、XRD、钡/钛摩尔比(Ba/Ti)和比表面积的测试结果表明,在单一水介质中水热合成钛酸钡晶体的结晶过程遵循“溶解-结晶”机制,存在第II类聚集长大过程。前驱体浓度、合成温度和合成反应时间是影响粉体粒径的重要因素。粉体的Ba/Ti比过低会导致粉体中出现BaCO3杂质相,且Ba/Ti越低,钛酸钡晶体晶胞膨胀程度越大。     

钛基钙钛矿陶瓷粉体的溶胶-水热法合成机理研究

采用溶胶-水热法,在较低的温度下已成功地合成了多种结晶良好的纳米或亚微米钛基钙钛矿型陶瓷粉体.在本文中通过对溶胶-水热法合成PbTiO3的各阶段产物的X射线衍射谱(XRD)和红外光谱 (IR) 的分析研究,获得了其初步的合成机理:溶胶过程缩短了其反应扩散距离,促进了水热反应的进行.由于该方法合成温度低,可用于多种陶瓷亚微米粉、纳米粉的制备,因此对其反应机制的深入研究有利于纳米粉末合成技术的发展.     

溶剂热合成纳米钛酸钡及其表征

为满足钛酸钡纳米陶瓷的需求,本文用TiCl4和Ba(OH)2作前驱体,乙醇和乙二醇甲醚作混合溶剂,溶剂热合成了钛酸钡纳米粉体,并使用TEM、XRD和Raman光谱对产物进行了表征.结果表明,在本文条件下可以得到粒径为10~80 nm纳米粉体,通过控制反应条件可以达到控制颗粒尺寸的目的,反应时间和反应温度对颗粒尺寸有显著的影响.     

水热法在制备电子陶瓷粉体中的应用

近年来,水热法用于纳米粉体和纳米材料制备,超导材料处理等前沿课题的研究,已引起人们的高度重视,按研究对象和目的的不同,水热法可分为水热晶体生长,水热合成,水热反应,水热处理,水热燃结等,分别用来生长各种单晶,制备超细,无团聚或少团聚,结晶完好的陶瓷粉体,以及在相对较低的温度下完成某些陶瓷材料的合成等,对水热技术的原理和发展,以及该技术在电子陶瓷粉体制备中的应用进行了介绍。