Effect of sintering temperature on the properties of modified mechanical alloyed CaCu3Ti4O12

This paper presents the effects of calcination time and sintering temperature on the properties of CaCu(3)Ti(4)O(12). Electroceramic material of CaCu(3)Ti(4)O(12) was prepared using a modified mechanical alloying technique that covers several processes, which are preparation of raw material, mixing and ball milling for 5 hours, calcination, pellet forming and, sintering. The objective of this modified technique is to enable the calcination and sintering processes to be carried out at a shorter time and lower temperature. The x-ray diffraction (XRD) analysis result shows that a single-phase of CaCu(3)Ti(4)O(12) was completely formed by calcination at 750 degrees C for 12 hours. Meanwhile, the grain size of a sample sintered at 1050 degrees C for 24 hours is extremely large, in the range of 20-50 mum obtained from field emission scanning electron microscopy (FESEM) images. The dielectric constant value of 14,635 was obtained at 10 kHz by impedance (LCR) meter in the sintered sample at 1050 degrees C. However, the dielectric constant value of samples sintered at 900 and 950 degrees C is quite low, in the range of 52-119.     

溶胶-凝胶法制备CaCu_3Ti_4O_(12)粉体及其电性能

利用溶胶-凝胶法制备CaCu3Ti4O12粉体,采用差热分析、X射线衍射、扫描电子显微镜等技术进行表征,并探讨CaCu3Ti4O12粉体的烧结特性及电性能。结果表明,干凝胶经750℃低温煅烧可获得粒径分布较窄、平均粒径为80～100 nm的CaCu3Ti4O12粉体。CaCu3Ti4O12陶瓷在1 000℃时实现致密烧结,比固相反应法制备的粉体烧结温度降低100～200℃,具有较宽的烧结温区。溶胶-凝胶法制备的陶瓷经1 050℃烧结2 h,获得优良的电性能,相对介电常数为20 190,介电损耗为0.022,非线性系数为4.530。     

SrTiO_3/CaCu_3Ti_4O_(12)复合陶瓷材料的介电性能

本文采用固相反应法制备了xSrTiO_3/(1-x)CaCu_3Ti_4O_(12)(x=0,0.2,0.4,0.6,0.8,1)复合陶瓷,研究了复合材料的物相、微观结构和宽温度宽频率范围内的介电性能。结果表明:在1348~1600K的温度范围内烧结能够得到致密性良好的xSrTiO_3/(1-x)CaCu_3Ti_4O_(12)(x=0,0.2,0.4,0.6,0.8,1)复合陶瓷。频率为100kHz时,样品的室温介电常数随SrTiO_3含量的增加而减少,从71358(x=0)单调减少至270(x=1),其变化规律遵循Lichtenecker法则。介电损耗随SrTiO_3含量的增加先增大后减少。当x=0.2时,样品与CaCu_3Ti_4O_(12)陶瓷的介电性能相似,存在低温的介电弛豫和巨介电常数平台。随着SrTiO_3含量的增加,复合陶瓷的低温介电弛豫激活能增大,介电响应被抑制,而高温介电响应由于高温电导的影响而增强,使得CaCu_3Ti_4O_(12)特有的巨介电常数平台随着SrTiO_3的增加逐渐消失,xSrTiO_3/(1-x)CaCu_3Ti_4O_(12)复合材料的温度依赖性增强。     

CaCu3Ti4O12中的晶界弛豫

研究了CaCu3Ti4O12在低温低频下的内耗曲线特征,发现金属中来源于晶界的内耗规律也适合CaCu3Ti4O12材料.测量了晶界弛豫激活能的大小和不同温度下该材料的特征弛豫时间.与常温的情况相比,低温下CaCu3Ti4O12的特征弛豫时间明显增加.分析表明:这种弛豫时间的增加来源于在畴区上极化弛豫的动态慢化效应.     

Sintering Behavior and Microwave Dielectric Properties of MgTiO3 Ceramics Doped with B2O3 by Sol-Gel Method

The B2O3-doped MgTiO3 powders and ceramics have been prepared by sol-gel method using Mg(NO3)2·6H2O, Ti(C4H9O)4 and H3BO3 as the starting materials. The sintering behavior and microwave dielectric properties of ceramics prepared from powders with different particle sizes were investigated. The gels were calcined at 650, 700, 750, 800, 850 and 900 C and the derived particle sizes of powders were 20-30 nm, 30-40 nm, 40-60 nm, 60-90 nm, 90-120 nm and 120-150 nm, respectively. The nanoparticles with the size of 30-60 nm benefited the sintering process with high surface energy whereas nanoparticles with the size of 20-30 nm damaged the microwave dielectric properties due to the pores in the ceramics. The addition of B2O3 used as a liquid sintering aid reduced the sintering temperature of MgTiO3 ceramic, which was supposed to enter the MgTiO3 lattice and resulted in the formation of (MgTi)2(BO3)O phase. The B2O3-doped MgTiO3 ceramic sintered at 1100 C and prepared from the nanoparticles of 40-60 nm had compact structure and exhibited good microwave dielectric properties: εr=17.63, Q × f=33,768 GHz and τ f= 48×10 6 C 1.     

Strong nonlinear current-voltage behaviour in perovskite-derivative calcium copper titanate

The discovery of a giant dielectric constant of 10(5) in CaCu(3)Ti(4)O(12) has increased interest in this perovskite-type oxide. Here we demonstrate that, in addition to high permittivity, CaCu(3)Ti(4)O(12) has remarkably strong nonlinear current-voltage characteristics without the addition of any dopants. An intrinsic electrostatic barrier at the grain boundaries is responsible for the unusual nonlinear behaviour. The nonlinear coefficient of CaCu(3)Ti(4)O(12) reaches a value of 900, which is even greater than that of the varistor material ZnO. As a result, CaCu(3)Ti(4)O(12) may lead to efficient switching and gas-sensing devices.     

CaCu3Ti4-3/4zFezO12/偏聚氟乙烯和Ca1-3/2xLaxCu3-yMgyTi4O12/偏聚氟乙烯复合材料的制备及介电性能研究

以CaCu3Ti4O12为原料,采用溶胶-凝胶法制备CaCu3Ti4-3/4zFezO12 (CCTFO)和Ca1-3/2xLaxCu3-y MgyTi4O12(CLCMTO)前驱粉体,以聚偏氟乙烯(PVDF)为基体采用球磨共混法热压制备CaCu3Ti4-3/4zFezO12(CCTFO)/PVDF和Ca1-3/2xLaxCu3-yMgyTi4O12(CLCMTO)/PVDF复合材料,考察掺杂量和前驱粉体填充质量对复合材料微观结构和介电性能的影响。结果表明:当前驱粉体填充质量增加到50%时,复合材料出现团聚现象。复合材料的介电常数和介电损耗均随填料含量的增加而升高,Fe掺杂后虽然不能提高复合材料的介电常数,但能降低中到高频段的介电损耗,La、Mg双掺杂不仅可以提高介电常数还可以降低介电损耗。     

Phase formation and high dielectric constant of calcium copper titanate using sol–gel route

Nano-sized calcium copper titanate (CCTO) powder was synthesized from a quick and innovative sol–gel process. Calcium nitrate, copper nitrate and titanium isopropoxide were used as the raw materials to synthesize the precursor product. The dried precursor powder was then milled and calcined at 450, 550, 650, 800, 850 and 950 °C for 3 h. The XRD results of the powder calcined at 800 °C indicates the formation of CCTO single phase. AFM studies shows that the average particle size of CCTO powder ranges around 80 nm. From the FTIR spectra the modes observed at 606, 525 and 463 cm⁻¹ was assigned to vibration modes of Ca–O, Cu–O and Ti–O–Ti, respectively. The samples sintered at 1,040 °C shows high density (96%) as compared to the theoretical value. The grain sizes of sintered pellets were determined by FE-SEM and the dielectric properties were studied by LCR meter.     

Synthesis and microwave dielectric properties of CaO-MgO-SiO2 submicron powders doped with Li2O-Bi2O3 by sol-gel method

Using Ca(NO₃)₂·4H₂O, Mg(NO₃)₂·6H₂O, Si(OC₂H₅)₄, LiNO₃ and Bi(NO₃)₃·5H₂O as raw materials, CaO-MgO-SiO₂ submicron powders were prepared at low temperature by sol-gel method. The crystallization temperature was decreased enormously by the introduction of Li-Bi liquid phase sintering aids into Ca-Mg-Si sol, and the powders with average particle sizes of 80-100 nm and 200-400 nm were obtained at the calcining temperature of 750 °C and 800 °C, respectively. The sintering characteristic and dielectric properties of powders calcined at 750 °C with different content of powders calcined at 800 °C were studied. When the content of powders calcined at 800 °C was 10 wt%, the dielectric ceramic sintered at 890 °C had compact structure, and possessed excellent microwave dielectric properties: ?_r = 7.16, Q × f = 25630 GHz, τ_f = −69.26 ppm/°C.     

巨介电常数陶瓷CaCu3Ti4O12的研究进展

CaCu_3Ti_4O_(12)(CCTO)陶瓷具有高介电常数和高热稳定性,这使得CCTO可能在高密度信息储存、高介电电容器、大规模集成电路等领域获得广泛使用。系统地介绍了CCTO高介电常数起源的内禀机制和外禀机制,详细归纳了元素掺杂对CCTO介电特性的影响,阐述了巨介电常数与本征点缺陷的内在关联,肯定了晶粒电导赝极化理论,指出了CCTO巨介电常数陶瓷研究的重点在于:基于外禀机制的IBLC模型,通过晶胞掺杂或晶界掺杂改变晶粒或者晶界的电导,进而调控CCTO的介电损耗,使CCTO保持较高介电常数的前提下,在很宽的频率范围内使介电损耗正切值降低到0.1以下。     

Dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> prepared by sol–gel self combustion technique

The preparation of Calcium copper titanate (CCTO) nanopowder was carried out by a sol–gel self combustion method. The X-ray diffraction analysis indicated that the samples calcined at 800 °C were fully crystallized in the CCTO phase. The results of atomic force microscope showed the particles size of CCTO was in the range of 60–80 nm. The absorption bands corresponding to vibrations of Cu–O, Ti–O–Ti and νCa–O were observed at 512, 450 and 562 cm⁻¹ using FTIR. The samples sintered at 950 °C showed the densities as high as 97% of theoretical density. The grain sizes of sintered pellets were determined by HRSEM. The dielectric properties of prepared samples were studied by LCR meter.     

Electrical properties of nanocrystalline Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta) (0.1 < or = x < or = 0.3) ceramics for IT-SOFC

Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta) (0.1 < or = x < or = 0.3) nano-sized powders were successfully synthesized by the solution combustion synthesis process. The calcined nanopowders showed a ceria-based single phase with a cubic fluorite structure. In this study, we discussed the structural and electrical characteristics of the sintered Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta). We obtained high-quality Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta) ceramics with a high density, ultra-fine grain size, and high electrical conductivity even at low sintering temperature using the nanosized powders. The electrical conductivities at 800 degrees C for the Ce(0.8)Sm(0.2)O(2-delta) sintered at 1400 degrees C and the Ce(0.8)Gd(0.2)O(2-delta) sintered at 1350 degrees C were 0.110 and 0.104 Scm(-1), respectively.     

Resistive-switching behavior in polycrystalline CaCu(3)Ti(4)O(12) nanorods

Highly aligned CaCu(3)Ti(4)O(12) nanorod arrays were grown on Si/SiO(2)/Ti/Pt substrates by radio-frequency sputtering at a low deposition temperature of 300 °C and room temperature. Structural and morphological studies have shown that the nanostructures have a polycrystalline nature and are oriented perpendicular to the substrate. The high density of grain boundaries in the nanorods is responsible for the nonlinear current behavior observed in these arrays. The current-voltage (I-V) characteristics observed in nanorods were attributed to the resistive memory phenomenon. The electrical resistance of microcapacitors composed of CaCu(3)Ti(4)O(12) nanorods could be reversibly switched between two stable resistance states by varying the applied electric field. In order to explain this switching mechanism, a model based on the increase/decrease of electrical conduction controlled by grain boundary polarization has been proposed.     

Sintering conditions of cordierite for microwave/millimeterwave dielectrics

With the advent of ubiquitous age, the high-quality, dielectric materials have been required for the applications of wireless communications available to millimeterwave as well as microwave frequencies such as ultra-high speed local area network (LAN), electronic toll collection (ETS), and car anticollision systems on the intelligent transport system (ITS), and so on. Cordierite (Mg(2)Al(4)Si(5)O(18)), which is one of the silicates, is a good candidate for microwave/ millimeterwave dielectrics due to low dielectric constant epsilon(r) and low loss. This study is focused on optimization of the sintering condition of cordierite. A single phase of cordierite could be obtained from the powders calcined from 1355 degrees C to 1375 degrees C for 3 hours, and the samples sintered from 1375 degrees C to 1440 degrees C for 2 hours. The highest relative density of 98.7% was obtained for the samples sintered at 1440 degrees C for 2 hours. The dielectric constant and the quality factor of cordierite depend on the sintering temperatures. The density also was improved to 2.51 g/cm(3) by a slower heating and cooling rate of 3 degrees C/minute. The microwave dielectric properties are as follows: epsilon(r) = 6.14, Q . f = 59682 GHz, and tau(f) = -26.1 ppm/ degrees C.     

(Sr,Pb)TiO3超微粉体的制备和性质

应用草酸盐共沉淀法制备（Ｓｒ，Ｐｂ）ＴｉＯ３超细粉体，分析了共学淀产物的热分解过程，确定了昌化温度和煅烧条件，同时，测量了粉示的晶粒尺寸，标定了材料的晶体结构，试验了粉体的烧结条件。     

CaCu3Ti4O12高介电材料的研究进展

在介绍CaCu3Ti4O12材料体心立方类钙钛矿结构的基础上总结了CaCu3Ti4O12块材和薄膜的制备方法,综述了CaCu3Ti4O12材料在高介电性能、晶界阻挡层效应引起的非线性特性以及金属离子掺杂改性等方面的最新研究进展.     

Synthesis of nanocrystalline Ce(0.8)Gd(0.2)O(2-delta) electrolyte materials for IT-SOFC

We successfully synthesized nano-sized Ce(0.8)Gd(0.2)O(2-delta) powders by combustion method, using gelatin as fuel. The calcined powders showed high-quality characteristics, i.e., nano-scale size (14-35 nm) and narrow size distribution. The structural, morphological, and electrical characteristics of the sintered Ce(0.8)Gd(0.2)O(2-delta) were studied systematically, depending on sintering temperature. The crystal structure of the Ce(0.8)Gd(0.2)O(2-delta) belonged to the cubic fluorite structure. The gelatin-assisted combustion synthesized Ce(0.8)Gd(0.2)O(2-delta) powders allowed to sinter well at low temperature for dense and ultra-fine Ce(0.8)Gd(0.2)O(2-delta) electrolyte with good electrical conductivity. The sintering temperature of the Ce(0.8)Gd(0.2)O2 powder was approximately 300 degrees C lower than that of conventional solid-state synthesized powder. The nanopowder produced was sintered into pellets with relative densities over 99.1% of the theoretical value even at 1400 degrees C. The Ce(0.8)Gd(0.2)O(2-delta) sintered at 1400 degrees C exhibited a conductivity of 0.101 S/cm at 800 degrees C in air.     

Mesoporous Co3O4 for low temperature CO oxidation: effect of calcination temperatures on their catalytic performance

Mesoporous Co3O4 particles are prepared by using mesoporous silica KIT-6 (with double gyroid Ia-3d symmetry) as a hard-template and Co(No3)2 x 6H2O as an inorganic precursor. In the former section, we investigate the effect of the calcination temperatures at which the Co salts are converted into Co3O4 inside the mesopores on the textural parameters of the products. The results of N2 adsorption-desorption analysis indicates that the calcination temperatures do not obviously affect the textural parameters such as the surface areas and pore volumes. However, when the calcination temperature reaches 800 degrees C, the mesostructural ordering is dramatically decreased, resulting in the reduction of the surface areas and pore volumes. After 800 degrees C calcination, the formation of large Co3O4 grains is partially confirmed on the particle surface by SEM observation. The grain size is much larger than the mesopore size of the original KIT-6, meaning the crystal growth is continuously occurred by breaking the rigid silica frameworks. In the latter section, we discuss the effect of the calcination temperatures and textural parameters on the catalytic activity for CO oxidation by both steady state and kinetic measurements. All mesoporous Co3O4 particles show a high catalytic activity, for example, -72 degrees C for sample calcined at 450 degrees C. Only 10 degrees C difference in T50 (the temperature of 50% conversion of CO) is found between the samples with the highest and lowest catalytic activity. The values of activation energy (Ea) and pre-exponential factor (A) per unit area are almost the same between two samples calcined at 450 degrees C and 800 degrees C. It is demonstrated that calcination process can not alter the essential catalytic property of mesoporous Co3O4 particles.     

Effect of CeO<Subscript>2</Subscript> on dielectric,ferroelectric and piezoelectric properties of PMN–PT (67/33) compositions

Lead magnesium niobate–lead titanate [Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃] powders doped with different mole % of CeO₂ were prepared by a modified columbite route with compositions corresponding to morphotropic phase boundary (MPB) region. These powders were calcined at 800 °C for 4 h and circular test specimens were prepared by uniaxial pressing. The specimens were sintered at 1150 °C/2 h, poled at 2 kV/mm d.c. voltage and were characterized for dielectric, ferroelectric and piezoelectric properties. It was observed that the piezoelectric and ferroelectric properties initially increase up to 2 mol% of ceria addition and then decrease with increase in ceria concentration. The diffusivity of the dielectric curves increases with increase in ceria concentration. The decrease in Curie temperature was observed from 173 °C corresponding to pure PMN–PT to a temperature of 138 °C for 10 mol% of ceria addition.     

Synthesis of CaCu3Ti4O12 ceramic via a sol-gel method

The novel nano-ultrafine powders for the preparation of CaCu₃Ti₄O₁₂ ceramic were prepared by the sol-gel method and citrate auto-ignition method. The obtained precursor powders were pressed, sintered at 1000 °C to fabricate microcrystal CaCu₃Ti₄O₁₂ ceramic. The microcrystalline phase of CaCu₃Ti₄O₁₂ was confirmed by X-ray powder diffraction (XRD). The morphology and size of the grains of the powders and ceramics under different heat treatments were observed using scanning electron microscopy (SEM). The relative dielectric constant of the ceramic sintered at 1000 °C was measured with a magnitude of more than 10⁴ at room temperature, which was approaching to those of Pb-containing complex perovskite ceramics, and the loss tangent was less than 0.20 in a broad frequency region. The relative dielectric constant and loss tangent were also compared with that of CaCu₃Ti₄O₁₂ ceramic prepared by other reported methods.