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 T_c did not change with the variation of Ti/Ba ratio, while the ?_max increased firstly and then decreased. The excess TiO₂ is benefit for the modification of ceramics’ microstructure and dielectric properties.     

溶胶-凝胶法制备掺锰钛酸钡纳米粉体及其陶瓷

The Mn-doped barium titanate nanosized powders and ceramics were prepared via the sol-gel process. The powders and ceramics were characterized by XRD， SEM and TEM. The dielectric properties of the ceramics were also measured. The influences of calcination temperature and Mn concentration on the microstructure， dielectric properties and phase composition of BaTiO₃ nano-powders and ceramics were discussed. The results indicated that the BaTiO₃-based powders doped with 1.0mol% Mn were mainly in cubic BaTiO₃ phase， but the tetragonal phase became more evident when the calcination temperature increased. After sintering， Mn-doped ceramics were mainly composed of cubic BaTiO₃. Specially， a new phase of hexagonal crystal BaTiO₃ and BaMnO₃ existed in the ceramics doped with 5.0mol% Mn and the ceramic grains were in ‘clintheriform’. The structure of ‘clintheriform’ led to the poor densification of ceramics， reducing the dielectric constant obviously. The dielectric constants of BaTiO₃ ceramics first increased and then decreased as the Mn concentration increased. The room temperature dielectric constant was 2 290 and the lowest dielectric loss was 0.004 when the Mn concentration was 0.5mol%.     

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%。     

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.     

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).     

Bi4(Ti1/3Sn2/3)3O12掺杂BaTiO3基X8R陶瓷微观结构与介电性能

研究了Bi4(Ti1/3Sn2/3)3O12掺杂对钛酸钡基陶瓷微观结构和介电性能影响。结果表明,掺杂Bi4(Ti1/3Sn2/3)3O12后钛酸钡基陶瓷晶粒明显长大,同时烧结温度可由1 280℃降低至1 180℃。系统的介电性能和Bi4(Ti1/3Sn2/3)3O12的掺杂量有密切关系。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,体系的居里峰被明显压低和展宽,当掺杂量为2mol%时居里峰变得不明显。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,系统的居里温度由131℃升高至139℃。当Bi4(Ti1/3Sn2/3)3O12的掺杂量为1mol%时,钛酸钡基陶瓷介电常数为1 930,介电常数温度变化率为5%(-55℃),13%(134℃),-8%(150℃),满足X8R标准。     

喷雾热分解法制备的钛酸钡颗粒内钡钛元素分布

基于氯化钡和二氧化钛具有不同的溶解特性,采用溶剂萃取法分别对喷雾热分解法和喷雾水解反应法制备的钛酸钡前驱体干燥产物颗粒内钡和钛分布进行定性分析,从而间接钛酸钡颗粒内的钡和钛分布情况。实验结果表明,该法可快速而准确地分析组合分析组分偏析情况。     

溶胶-凝胶法制备功能陶瓷超微粉末

陶瓷超微粉末的研究是目前高技术领域中的一项重要课题。溶胶-凝胶法是近几年来才开发的一种制备陶瓷超微粉末的新技术。应用该方法所合成的粉末纯度高、化学成份均匀、颗粒度小且分布范围窄,易烧结成致密的陶瓷体,尤其对于多元陶瓷粉末的制备这些优点更为突出。因而对该方法的研究及应用已引起人们的普遍重视。PbTiO_3、BaTiO_3和Pb(Zr,Ti)O_3作为陶瓷压电材料广泛应用于电子信息技术和光电技术领域;有关它们的研究报道甚多。     

熔盐法制备Ca0.9La0.2/3Cu3Ti4O12陶瓷粉体及其介电性能研究

以CaCO3,CuO,TiO2,La2O3为反应物,NaCl,KCl为熔盐,通过熔盐法分别在700、750、800、850℃条件下合成Ca0.9La0.2/3Cu3Ti4O12陶瓷粉体。利用XRD和SEM分别对陶瓷粉体的物相结构和微观形貌进行了分析,并对其介电性能进行了测试。实验结果表明,随着合成温度的升高,陶瓷粉体的钙钛矿相含量逐渐增大,与传统固相法相比,熔盐法制备的粉体无团聚现象,耗时少。Ca0.9La0.2/3Cu3Ti4O12粉体制备的陶瓷在1 000℃烧结、测试频率在100 Hz~10 kHz时,获得优良的介电性能:介电常数大大超过104,介电损耗在0.1~0.47之间。     

聚苯胺颗粒材料的表面改性

用改性的溶胶-凝胶法制备了表面包覆有一定厚度的钛酸钡薄膜的聚苯胺,通过TEM和FT-IR分析方法研究了其形貌及微结构,并探讨了改性聚苯胺材料的电流变性能.FT-IR研究结果表明,在聚苯胺与钛酸钡之间存在着N－O间的氢键作用.TEM研究结果表明,改性聚苯胺粒子的直径在1.0～1.5 μm之间.此外,包覆工艺显著改善了材料的介电性能和电流变性能,为制备出高性能的电流变材料提供了一条可行的途径,值得进一步研究.     

钐掺杂对钛酸钡锶陶瓷结构和介电性能的影响

采用溶胶-凝胶法制备了系列Sm掺杂的Ba(0.8-3x/2)SmxSr0.2TiO3(x=0,0.001,0.003,0.006,0.008 and 0.010)粉体及陶瓷。利用X射线粉末衍射、扫描电子显微镜和精密阻抗分析表征了样品的结构和性质。X射线衍射结果表明Ba(0.8-3x/2)SmxSr0.2TiO3粉体在800℃预烧2 h后为单一的钙钛矿结构;通过对陶瓷微观形貌研究发现,Sm掺杂可以明显地抑制陶瓷晶粒生长,随着Sm掺杂量的增加,晶粒尺寸由40μm减小到2μm;居里温度随着Sm掺杂量的增加而线性降低,移动速率为10℃/mol%,室温下介电常数呈现先增加后减小的趋势,并在x=0.006时达到最大值7800。     

锶、铈和镧共掺杂铈钛酸锶钡陶瓷的固溶性和介电性能的研究

采用冷压陶瓷技术,制备了(Ba1-x-0.02SrxLa0.02)(Ti1-yCey)O3(x=0.05,0.10,0.15;y=0.03,0.04,0.05)(BSLTC)陶瓷,通过X射线衍射(XRD)和介电温谱测试对BSLTC陶瓷的固溶性和介电性能进行调查。XRD结果表明,所有样品均为立方钙钛矿结构,La掺杂量为2%时,能够将(Sr,Ce)组合的固溶提高到(x=0.10,y=0.04)或(x=0.15,y=0.03)。介电结果表明,各样品的居里温度都在室温附近,介电峰明显宽化。其中,(x=0.05,y=0.03)组合的样品显示出最高的室温介电常数(ε’RT≈6000)和低介电损耗(tanδ<0.02),满足美国EIA"Y5V"高介电陶瓷材料指标。     

Study of Ba3M(II)M(IV)WO9 (M(II) = Ca, Zn; M(IV) = Ti, Zr) perovskite oxides: competition between 3C and 6H perovskite structures

We describe an investigation of Ba3MIIMIVWO9 oxides for MII = Ca, Zn, and other divalent metals and MIV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P63/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the Ba3MIITiWO9 oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba2(Zn2/3Ti1/3)(W2/3Ti1/3)O6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fmm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d0-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the Ba3MIIMIVWO9 series.     

锰掺杂Ba0.6Sr0．4TiO3-MgTiO3复相陶瓷的制备和介电性能

以分析纯的Ba(NO3)2、Sr(NO3)2、草酸和钛酸丁酯为原料,采用草酸盐共沉淀法制备了钛酸锶钡(Ba0.6Sr0.4tiO3,BST)纳米粉体.XRD和SEM分析结果表明,该方法制备出立方相的Ba0.6Sr0.4TiO3粉体,平均粒径小于100 nm,具有较高的烧结活性.用传统固相法制备了锰掺杂钛酸锶钡.钛酸镁(Ba0.6Sr0.4TiO3-MgTiO3,BST-MT)复相陶瓷,系统研究了掺杂0.1%-2.0%(x,摩尔分数,下同)锰对钛酸锶钡-钛酸镁复相陶瓷微观形貌和介电性能的影响机理.结果表明,当锰的掺杂量小于1.5%时,Mn作为受主掺杂取代占据钙钛矿ABO3的B位,因此导致居里点略微向高温偏移和相变扩散的发生,锰的掺杂导致晶格畸变,促进了晶粒生长,使晶界相比例下降,因此介电损耗随着锰掺杂量的增大而减小;当锰的掺杂量为1.5%时,介电损耗达到最小值,继续增大掺杂量,介电常数下降,介电损耗上升.     

锰掺杂Ba0.6Sr0.4TiO3-MgTiO3复相陶瓷的制备和介电性能

以分析纯的Ba(NO3)2、Sr(NO3)2、草酸和钛酸丁酯为原料, 采用草酸盐共沉淀法制备了钛酸锶钡（Ba0.6Sr0.4TiO3, BST）纳米粉体. XRD和SEM分析结果表明, 该方法制备出立方相的Ba0.6Sr0.4TiO3粉体, 平均粒径小于100 nm, 具有较高的烧结活性. 用传统固相法制备了锰掺杂钛酸锶钡-钛酸镁(Ba0.6Sr0.4TiO3-MgTiO3, BST-MT)复相陶瓷, 系统研究了掺杂0.1%-2.0%(x, 摩尔分数, 下同)锰对钛酸锶钡-钛酸镁复相陶瓷微观形貌和介电性能的影响机理. 结果表明, 当锰的掺杂量小于1.5%时, Mn作为受主掺杂取代占据钙钛矿ABO3的B位, 因此导致居里点略微向高温偏移和相变扩散的发生, 锰的掺杂导致晶格畸变, 促进了晶粒生长, 使晶界相比例下降, 因此介电损耗随着锰掺杂量的增大而减小; 当锰的掺杂量为1.5%时, 介电损耗达到最小值, 继续增大掺杂量, 介电常数下降, 介电损耗上升.     

The Solgel Preparation and Electric Properties of MnO2-doped PbTiO3 Ceramics

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聚吡咯/Ba_(0.9)Nd_(0.1)Fe_(11.5)Cr_(0.5)O_(19)复合物的可控合成及电磁性能

用溶胶凝胶法制备了一系列Nd掺杂Ba-铁氧体粉末(Ba1-xNdxFe11.5Cr0.5O19,x=0.00,0.05,0.10,0.15,0.20),选取磁性能相对较好的Ba0.9Nd0.1Fe11.5Cr0.5O19作为磁核,通过原位聚合法制备了不同铁氧体含量的聚吡咯/Ba0.9Nd0.1Fe11.5Cr0.5O19(PPy/BNFCO)复合物.用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(FTIR)、振动样品磁强计(VSM)、四探针测试仪和矢量网络分析仪等表征了铁氧体粉末和复合物微粒的结构、形貌以及电磁性能.结果表明,Nd的掺杂明显改变了Ba-铁氧体的饱和磁化强度和矫顽力;PPy/BNFCO复合物具有比较明显的核壳结构;复合物的饱和磁化强度随BNFCO含量的增加而增大;电导率则与PPy含量成正比,mpy/mBNFCO=5/1为复合体系渗流阈值;复合物对电磁波的反射损耗和有效带宽是PPy和ZCGFO协同作用的结果,当mpy/mBNFCO为5/1时,PPy/ZCGFO复合物中组分间的协同作用达到最大,其反射峰值和有效带宽分别达到-27.68dB和9.04GHz.PPy/ZCGFO复合物由于良好的微波吸收性能,有望成为电磁波吸收与屏蔽领域的候选材料.     

Synthesis, structure and dielectric properties of Ba1-xSrx My Ti1-yO3 (M = Zr, Sn)

A series of Ba1-xSrxMyTi1-yO3 (M = Zr, Sn, 0≤x≤0.4, 0≤y≤0.3) solid solutions were synthesized with the soft chemical method below 100 ℃. XRD pattern and cell parameters-composition figures of the prepared powder demonstrate that they are completely miscible solid solutions based on BaTiO3. Furthermore, TEM shows that they have a shape of uniform, substantially spherical particles with an average particle size of 70 nm in diameter. The sintered ceramics of the powder doped with Sr2 and Zr4 or Sn4 have dielectric constant eight times higher and dielectric loss thirty per cent lower than those of pure BaTiO3 phase at room temperature.     

Graded PZT ceramics for piezoelectric transformers

In the present study two types of the synthesized Pb(Zr_1−xTi_x)O₃ (PZT) powders differing in Zr/Ti ratio were used to prepare the spatially inhomogeneous (i.e., graded) structure. A position-dependent chemical composition was expected to cause the property gradient. Disk-shaped compacts were prepared in a way such that two different orientations of the radial gradients were formed. The solid state sintering under pressure was utilized to prepare ceramics. Simultaneous thermal analysis was used to study thermal behavior of the ceramic powders. Graded PZT ceramics were characterized using X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. It was also characterized in terms of its dielectric properties by both bridge technique and the impedance spectroscopy. On the basis of graded PZT ceramics the disk-shaped radial mode piezoelectric transformer was developed and fabricated.     

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。