溶胶-凝胶法制备钛酸钡超细粉体的研究

钛酸钡是一种非常重要的铁电材料 ,其合成方法主要分为固相反应法和液相反应法。传统的固相反应法是以ＴｉＯ2 和ＢａＣＯ3 经高温反应制取钛酸钡粉体 ,该法产品杂质含量高 ,颗粒粗 ,均匀性差 ,粉体烧结温度高。与高温固相反应相比 ,液相法合成的钛酸钡粉体具有化学纯度高 ,颗粒细小 ,粒度分布均匀等优点。特别是以醇盐为原料 ,采用溶胶 凝胶法制备的钛酸钡粉体 ,其性能非常优异 ,已为许多研究者所关注[1,2 ] 。文献[3 ] 报道了以异丙醇钛和醋酸钡为原料 ,采用溶胶 凝胶法制备钛酸钡物体的研究 ,但未见有以钛酸丁酯及醋酸钡为原料制备钛酸钡…     

钡矿石的物相分析

关于钡的物相分析,仅见到龚美菱等制定的测定钡碳酸盐、重晶石和钡长石的物相分析方法。为配合某矿区物质成分研究,我们进行了钡矿石的化学物相分析研究,拟定了分析钡的碳酸盐、氟碳酸盐、重晶石、钡铁钛石、包头矿等五相的分析方法,经生产实践表明本方法基本上满足了地质及矿物物质成分研究的要求,比地质上原来用的颗粒矿物定量法,精     

二溴对甲基偶氮溴羧与钡显色反应的研究与应用

研究了新显色剂二溴对甲基偶氮溴羧与钡显色反应的条件。在磷酸介质中,试剂与钡形成2:1的络合物,最大吸收波长为610nm,摩尔吸光系数为2.13×10~4L·mol~(-1)·cm~(-1),钡量在0～20μg/25ml范围内符合比耳定律。两倍的锶和五倍的钛不干扰,钙的允许量较大,方法用于直接测定钛酸钡烧结物中微量钡,结果满意。     

多步法制备纳米钛酸钡

采用醋酸钡、碳酸钾、钛酸丁酯等为初始反应物，通过多步反应的方法，制得了纳米钛酸钡。所得产品采用XRD、TEM和SEM等进行了表征，并对生长机理进行了分析。研究结果表明，得到的碳酸钡为直径约100 nm的纳米棒，再经室温下钛酸丁酯水解产生二氧化钛对碳酸钡纳米棒进行包覆，可得到一维核-壳结构的碳酸钡/二氧化钛，最后于700 ℃下经固相反应而得到钛酸钡的纳米颗粒。这种制备纳米钛酸钡的方法可以有效地控制产品形貌及粒径。     

纳米钛酸钡生成的热分解机理

钛酸钡作为重要的铁电材料 ,多年来一直被研究者们所关注．传统方法制备钛酸钡大多采用固相法或草酸盐法得到微米级基料．随着纳米材料研究与应用的发展 ,溶胶 凝胶技术成为制备各种金属氧化物纳米材料的较普遍方法．溶胶 凝胶法制备纳米钛酸钡就是其中之一．该法一般采用钛的有机醇盐与钡盐反应生成溶胶 ,然后形成凝胶 ,再以凝胶为先体进行热处理制得纳米钛酸钡．虽然已有人对溶胶 凝胶技术制备纳米钛酸钡进行了研究 ,并对所得产物进行了表征［１,２］,但尚无人对该方法中凝胶的热分解过程作详细的研究．因凝胶的热分解过程对钛酸钡纳…     

均匀共沉淀法制备钛酸钡-钡铁氧体核-壳结构粒子

用均匀共沉淀法制备了钛酸钡-钡铁氧体核-壳粒子, 研究了沉淀反应温度、尿素/金属离子摩尔比值(R)和BaTiO₃浓度对核-壳粒子形貌和结构的影响, 探讨了钛酸钡-钡铁氧体核-壳粒子在焙烧时的形成过程及其磁性能. 采用透射电子显微镜(TEM)、X射线衍射(XRD)分析仪对钛酸钡-钡铁氧体前驱物核-壳粒子及钛酸钡-钡铁氧体核-壳粒子的形貌和结构进行了表征, 采用振动样品磁强计(VSM)研究了钛酸钡-钡铁氧体核-壳粒子的磁性能. 结果表明: 当沉淀反应温度为100 °C, R为180, BaTiO₃浓度为2.5 g·L^-1时, 金属离子沉淀完全, 得到的钛酸钡-钡铁氧体前驱物核-壳粒子包覆层均匀、完整、光滑, 厚度约为10 nm. 过高的温度和R值都会导致大量独立颗粒杂质的生成; 随着BaTiO₃浓度的增大, 包覆层厚度有减小的趋势. 当焙烧温度为900 °C时, 壳层中开始形成BaFe₁₂O₁₉相, 其形成过程为晶态的α-Fe₂O₃和BaCO₃首先生成中间相BaFe₂O₄, 然后由BaFe₂O₄和α-Fe₂O₃反应得到最终的BaFe₁₂O₁₉. 当焙烧温度为1000 °C时, 壳层完全转化为BaFe₁₂O₁₉相. 随着焙烧温度从900 °C升高到1000 °C, 所得BaTiO₃-BaFe₁₂O₁₉核-壳粒子的饱和磁化强度从16.5 A·m²·kg^-1增加到39.5 A·m²·kg^-1, 矫顽力从340 kA·m^-1略微降低到316 kA·m^-1.     

纳米钛酸钡及其烧结物的制备

溶胶 凝胶技术已为制备各种金属氧化物纳米材料的较普遍方法[1],其优点是产物具有超细颗粒尺寸 ,高纯度和化学均匀性 .溶胶 凝胶法制备纳米钛酸钡时一般将钛的有机醇盐与钡盐反应生成溶胶 ,然后形成凝胶 ,再进行热处理制得纳米钛酸钡[2 ,3].本文以钛酸丁酯和氢氧化钡为原料 ,采用溶胶 凝胶工艺制备出纳米钛酸钡晶体粉末 .用ＴＧ ＤＴＡ和ＦＴＩＲ技术考查了纳米晶钛酸钡凝胶先体热分解反应过程 ,用ＳＥＭ和ＸＲＤ对粉体形貌和晶型进行分析 ;并用上述粉体制成了微观组织结构仍保持纳米尺寸的陶瓷材料 .粉体制备 :称 15 7ｇ氢氧化钡 (Ｂａ(…     

溶胶-凝胶法制备Ba_(0.6)Sr_(0.4)TiO_3陶瓷纤维

首次采用乙酰丙酮为钛醇盐的稳定剂,醋酸钡、醋酸锶和钛酸丁酯为原料,无水乙醇-冰醋酸作为溶剂,利用Sol-Gel法于1100℃得到单一钙钛矿相钛酸锶钡陶瓷纤维.用TG、XRD、SEM等手段对产物进行表征.     

聚苯乙烯—钛酸钡复合材料介电性能的研究

以聚苯乙烯与化学沉淀法钛酸钡陶瓷为基本组成，采用溶液共混，溶液聚合，表面处理后溶液聚合三种方法进行复合，发现后两种复合的钛酸钡颗粒表面发生界面变化，形成活性界面，使得溶液聚合法和表面处理后溶液聚合所得到的材料具有较低的介电损耗，在高频下能保持较高的介电系数。     

亚微米级四方相钛酸钡低温固相法制备及晶型控制

以八水合氢氧化钡和α-钛酸为原料,在相对低的焙烧温度下,制备出近似球形、亚微米级的钛酸钡。通过XRD、SEM、Raman和FTIR等手段对钛酸钡样品进行表征,样品具有高结晶度,颗粒均一性良好。晶型转变的初步探究表明,立方相为主的钛酸钡可以在400℃发生晶相转变,成为以四方相为主的钛酸钡。     

Nd-doped barium titanate ceramics with various Ti/Ba ratios prepared by sol-gel method

The Nd-doped BaTiO3 nanocrystalline powders and ceramics with different Ti/Ba ratios were prepared by sol-gel method. Phases and microstructures of the Nd-doped BaTiO3 based powders and ceramics were characterized by XRD, SEM and TEM methods. The results revealed that the powders synthesized by sol-gel method were nanometer scale (30-60 nm) and were mainly composed of cubic BaTiO3 with a small amount of BaCO3. After sintering at high temperature, both cubic BaTiO3 and BaCO3 were transformed into tetrahedron BaTiO3 phase. The dielectric properties of the ceramics were also determined and the influence of Ti/Ba ratio on the dielectric properties was discussed. The Tc did not change with the variation of Ti/Ba ratio, while theεmax increased firstly and then decreased. The excess TiO2 is benefit for the modification of ceramics' microstructure and dielectric properties.     

Wet-chemical synthesis of crystalline BaTiO3 from stable chelated titanium complex: formation mechanism and dispersibility in organic solvents

Crystalline barium titanate nanoparticles were synthesized in solution at low temperature (70 degrees C) from acetylacetone chelated titanium complex and barium hydroxide. Very fine crystalline solids were characterized to cubic phase of BaTiO(3) by X-ray diffraction studies of the air-dried samples. It was observed that the crystalline barium titanate was formed in solution at Ba/Ti molar ratio > or =2.5. The dependence of the reaction temperature and the Ba(OH)(2) concentration (in terms of Ba/Ti molar ratio) on formation of crystalline BaTiO(3) in solution-phase was studied, and a plausible mechanism toward the formation of crystalline BaTiO(3) was also proposed. Crystallite sizes of the BaTiO(3) were found to be in the range 33-50 nm, while the average particle sizes, measured by dynamic light scattering method were in the range 70-100 nm. The crystalline BaTiO(3) prepared from acetylacetone chelated titanium complex was highly dispersible in organic medium such as N-methyl-2-pyrillidone (NMP) and N,N-dimethyl formamide (DMF).     

BaTiO3-BaAl2O4-Al2O3复合载体的制备、表征及其Ni基催化剂催化CH4/CO2重整反应性能

以十六烷基三甲基溴化胺为结构导向剂,采用溶胶-凝胶法制备了BaTiO3-BaAl2O4-Al2O3复合载体,采用X射线衍射、红外光谱、N2吸附-脱附、透射电子显微镜和H2程序升温还原等技术对复合载体进行了表征,并以CH4/CO2重整制合成气为探针反应,考察了不同Ni/BaTiO3-BaAl2O4-Al2O3催化剂的性能.结果表明,BaTiO3-BaAl2O4-Al2O3复合载体具有多孔织构特性和较高的比表面积,BaTiO3和BaAl2O4以晶粒状态分布在复合载体的内外表面,晶粒尺寸在20～50nm的范围,复合载体孔径为10～20nm.复合载体上BaTiO3和BaAl2O4的引入,适度削弱了Ni/BaTiO3-BaAl2O4-Al2O3催化剂中Ni物种与γ-Al2O3间的强相互作用,抑止了NiAl2O4尖晶石的生成;当载体中Ba(Ti)含量为17.33%时,其负载的Ni催化剂上CH4/CO2重整制合成气反应的活性和稳定性最高.     

Photokilling Squamous Carcinoma Cells SCCVII with Ultrafine Particles of Selected Metal Oxides

The ability of ultrafine particles of TiO₂, WO₃ and iron-doped TiO₂ to kill cancer cells in the presence of UV irradiation was investigated. The best photokilling effect on carcinoma cells SCVII cultured in vitro showed iron-doped TiO₂ ultrafine particles synthesized by the sol-gel procedure with starting chemicals Ti(IV)-isopropoxide and anhydrous Fe(II)-acetate. It was found that a small particle size and high dispersity influenced citotoxicity and photocatalytic efficiency. The remarkable photokiling effect of highly iron-doped TiO₂ ultrafine particles (the molar ratio Fe/Ti = 0.136) in the presence of UV irradiation was observed. The influence of ultrafine metal oxide particles on the inhibition of cancer cell proliferation was measured using a ³H-thymidine incorporation test. The possible mechanism involved in the photokilling of carcinoma cells with ultrafine particles of selected metal oxides was discussed.     

Hydrotherrnal synthesis, structure and property of nano-BaTiO3-based dielectric materials

A series of Ba1-xSrxTi1-yZryO3 (0≤x≤0.5, 0≤y≤0.4) and Ba1-xZnxTi1-ySnyO3 (0≤x≤0.3, 0≤y≤0.3) solid solutions were synthesized by Iow-temperature/Iow-pressure hydrothermal method below 170℃, 0.8 MPa. XRD pattern and cell parameters-composition figures of these prepared powders demonstrated that they are completely miscible solid solutions based on BaTiO3. Furthermore, TEM showed that they have a shape of uniform, substantially spherical particles with an average particle size of 70 nm in diameter. The sintered ceramics of those powders doped by Sr2+ and Zr4+ or Zn2+ and Sn4+ have dielectric constant twelve times higher than and dielectric loss 1/6 those of pure BaTiO3 phase at room temperature.     

低温-低压水热合成Ba1-xSrxTi1-ySnyO3纳米材料及其 结构与性能研究

采用低温-低压水热法,在150℃,0.5MPa以下合成了一系列Ba1-xSrxTi1-ySnyO3固溶体纳米粉末(0≤x≤0.5≤y≤0.4),经XRD物相分析和d-间距-组成图证明,产品为立方晶系的完全互溶取代固溶体,结果符合Vegard定律,TEM形貌观察,粒子为均匀球形,平均粒径80nm。通过制陶实验,分别测定了该系列固溶体的室温介电常数、介电损失以及介电常数随温度的变化。结果发现,用该方法在BaTiO3中掺入适量锶和锡,由于掺杂离子均匀进入母体晶格,引起Tc降低,介电性能改善显著,当x=0.1,y=0.08时,室温介电常数达17000,比BaTiO3纯相提高10倍,而介电损失却降低88%。     

喷雾热解制备稀土超细粉末(Ⅰ)——氧化钇粒子形态与形成机理

对Y(NO₃)₃·6H₂O的差热和热重分析表明,Y(NO₃)₃·6H₂O经脱水和热分解在580C以上完全分解为Y₂O₃.在此基础上,以Y(NO₃)₃·6H₂O为前驱体,采用喷雾热解过程制备出粒度为0.50～1.50μm的立方相球形Y₂O₃粉末.通过对产物粒子粒度的理论计算与实验结果的比较,推测Y₂O₃粒子形成机理符合液滴-粒子转变机理(One-Droplet-One-Particlemechanism).本喷雾热解过程同样适用于其它稀土超细粉末的制备,粒子粒度可以通过调节液滴尺寸和溶液浓度等操作条件进行控制.     

Grain Growth Kinetics of BaTiO3 Nanocrystals During Calcining Process

BaTiO3 nanocrystals were synthesized by sol-gel method using barium acetate (Ba(CH3COO)2) and tetrabutyl titanate (Ti(OC4H9)4) as raw materials. Xerogel precursors and products were characterized by means of thermogravimetric/differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD) and transmission electron microscope (TEM). The influence of the calcination temperature and duration on the lattice constant, the lattice distortion, and the grain size of BaTiO3 nanocrystals was discussed based on the XRD results. The grain growth kinetics of BaTiO3 nanocrystals during the calcination process were simulated with a conventional grain growth model which only takes into account diffusion, and an isothermal model proposed by Qu and Song, which takes into account both diffusion and surface reactions. Using these models, the pre-exponential factor and the activation energy of the rate constant were estimated. The simulation results indicate that the isothermal model is superior to the conventional one in describing the grain growth process, implying that both diffusion and surface reactions play important roles in the grain growth process.     

CdO掺杂对BaTiO3基半导化陶瓷PTCR效应的改善

钛酸钡基半导化陶瓷中的PTCR效应通常与材料中的施受主掺杂切相关,蒸汽掺杂能够大幅度影响材料的PTCR效应。CdO在高温下具有较高的蒸汽压,是一种适用的蒸汽掺杂剂,研究了CdO以及CdO蒸汽对掺Y^3+的Ba1-xSrxTiO3陶瓷的PTCR效应的影响,结果首次发现了Cd^2+掺杂样品的PTCR效应都有不同程度的提高,采用蒸汽掺杂时,效果更为显著。现有的理论很难解释Cd^2+掺杂能够提高钛酸钡基材料PTCR效应。我们从缺陷化学的角度,分析了Cd^2+在BaTiO3基材料中的行为,推断表明这种现象可能是由于铁电相变时,处于晶界区的Cd^2+在Ba位和Ti位之间转换造成的。     

表面修饰的钛酸钡纳米粉体的制备

采用水热法制备出表面包裹有硬脂酸的钛酸钡纳米粉体,并运用一系列手段对其微结构进行了表征.结果表明:产物粒径较小,粒度分布较窄,单分散性较好,其表面为非极性,同时表现出良好的流动性能.认为钛酸钡纳米粉体表面极性的改变是由于其表面包裹了一层硬脂酸,并且包裹层降低了粉体间的相互作用力,从而提高了粉体的流动性.