Effect of SiO_2 addition on the microstructure and electrical properties of ZnO-based varistors

The microstructure and electrical properties of ZnO-based varistors with the SiO2 content in the range of 0-1.00mol% were prepared by a solid reaction route. The varistors were characterized by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectrometry, inductively coupled plasma-atomic emission spectrometry, and X-ray photoelectron spectroscopy. The results indicate that the average grain size of ZnO decreases with the SiO2 content increasing. A new second phase （Zn2SiO4） and a glass phase （Bi2SiO5） are found. Element Si mainly exists in the grain boundary and plays an important role in controlling the Bi2O3 vaporization. The electric measurement shows that the incorporation of SiO2 can significantly improve the nonlinear properties of ZnO-based varistors, and the nonlinear coefficients of the varistors with SiO2 are in the range of 36.8-69.5. The varistor voltage reaches the maximum value of 463 V/mm and the leakage current reaches the minimum value of 0.11 μA at the SiO2 content of 0.75mol%.

Improvement of sintering,nonlinear electrical,and dielectric properties of ZnO-based varistors doped with TiO2

The effects of TiO2 on sintering and nonlinear electrical properties of（98.5-x）ZnO–0.5MnO2–0.5Co2O3-0.5Bi2O3–xTiO2（x = 0.3,0.5,0.7,0.9 mol%） ceramic varistors prepared by the ceramic technique are investigated in this work.The optimum sintering temperature of the prepared samples is deduced by determining the firing shrinkage and water absorption percentages.The optimum sintering temperature is found to be 1200℃,at which each of the samples shows a maximum firing shrinkage and minimum water absorption.Also minimum water absorption appears in a sample of x = 0.9 mol%.Higher sintering temperature and longer sintering time give rise to a reduction in bulk density due to the increased amount of porosity between the large grains of ZnO resulting from the rapid grain growth induced by the liquid phase sintering.The crystal size of ZnO decreases with increasing TiO2 doping.The addition of TiO2 improves the nonlinear coefficient and attains its maximum value at x = 0.7 mol% of TiO2,further addition negatively affects it.A decrease in capacitance consequently in the dielectric constant is recorded with increasing the frequency in a range of 30 kHz–200 kHz.The temperature and composition dependences of the dielectric constant and AC conductivity are also studied.The increase of temperature raises the dielectric constant because it increases ionic response to the field at any particular frequency.

Fabrication of ZnO-based thick film varistors with high potential gradient

ZnO-based thick film varistors have been fabricated by Y203 doping and low-temperature sintering, of which the sample with the best electrical properties has a high potential gradient value of 3159.4 V/mm. The effects of Y2O3 doping concentration and sintering temperature on the potential gradient of the samples were systematically investigated. The results show that the sample with the best electrical properties can be obtained by doping 0.08 mol% Y2O3 and sintering at 725℃. Under these optimum preparation conditions, the leakage current and the nonlinear coefficient are found to be 36.4 gA and 13.1. The sample with the best electrical properties has a grain size of 1.290um, a single grain boundary voltage of 4.08 V, a barrier height of 0.81 eV, and a depletion layer width of 10.2 nm, which are determined by thermionic emission. Small grain size with good grain boundary characteristics is beneficial to improve the electrical properties of varistors and promote the potential gradient.

Microstructure and electrical properties of Y_2O_3-doped ZnO-based varistor ceramics prepared by high-energy ball milling

Y2O3-doped ZnO-based varistor ceramics were prepared using high-energy ball milling （HEBM） and low-temperature sin- tering technique, with voltage-gradient of 1934-2197 V/mm, non-linear coefficients of 20.8-21.8, leakage currents of 0.59-1.04 μA, and densities of 5.46-5.57 g/cm3. With increasing Y2O3 content, the voltage-gradient increases because of the decrease of ZnO grain size; the non-linear coefficient and the leakage current improve but the density decreases because of more porosity; the donor con- centration and density of interface states decrease, whereas the barrier height and width increase because of the acceptor effect of Y2O3 in varistor ceramics.

Microstructure and Electrical Properties of Er_2O_3-Doped ZnO-Based Varistor Ceramics Prepared by High-Energy Ball Milling

The microstructure, electrical properties and density of ZnO-based varistor ceramics with different Er2O3 content prepared by high-energy ball milling （HEBM） and sintered at 800℃ were investigated. With increasing Er2O3 content, the ZnO grain size decreases due to the Er-rich phases inhibiting grain growth ; and nonlinear coefficient （ α ） decreases because of the decrease of barrier height （φB） The breakdown voltage （Eb） and density increase, whereas leakage current （IL） decreases with increasing Er2O3 content. The barrier height （φB）, donor concentration （Nd）, density of interface states （Ns） decrease and barrier width （ω） increases with increasing Er2O3 content due to acceptor effect of Er2O3 in varistor ceramics.

Effects of cooling rate on the microstructure and electrical properties of Dy_2O_3-doped ZnO-based varistor ceramics

The microstructure, electrical properties, and density of Dy2O3-doped ZnO-based varistor ceramics, prepared using high-energy ball milling （HEBM） and sintered at 800℃, were investigated by increasing the cooling rate in the order of H （slow cooling in furnace） → L （cooling in furnace） → K （cooling in air）. With the increase in cooling rate, the grain size and density decreased, the breakdown voltage （VImA/mm） increased, and the nonlinear coefficient （α） and leakage current （IL） exhibited extremum. The sample with the cooling type L showed the best properties with the breakdown voltage of 2650 V/ram, o：of 20.3, IL of 5.2 laA, and density of 5.42 g/cm^3. The barrier height （ФB）, donor concentration （Nd）, density of the interface states （Nd）, and barrier width （ω） all exhibited extremum during the alteration in cooling rate. The different relative amount of Bi-rich phase and its distribution as well as the characteristic parameters of grain boundary, resulting from the alteration of cooling rate, led to the changes in the properties of varistor ceramics.

Microstructure and electrical properties of La_2 O_3-doped ZnO-based varistor thin films by sol-gel process

Microstructure and electrical properties of La2 O3-doped ZnO-Bi2 O3 thin films prepared by sol–gel process have been investigated.X-ray diffraction shows that most diffraction peaks of ZnO are equal,and the crystals of ZnO grow well.Scanning electron microscopy and atomic force microscopy results indicate that the samples have a good structure and lower surface roughness.The nonlinear V–I characteristics of the films show that La2 O3 develops the electrical properties largely and the best doped content is 0.3% lanthanum ion,with the leakage current of 0.25 mA,the threshold field of 150 V/mm and the nonlinear coefficient of 4.0 in detail.

EFFECTS OF In_2O_3 DOPING AND SINTERING TEMPERATURE ON THE ELECTRICAL PROPERTIES OF ZnO VARISTORS

ZnO varistors are prepared using the 0.1-0.3mm ZnO powders. The effects of the sintering temperature, contents of In2O3 doping on the non-linear properties of ZnO varistors have been investigated. Theresults show that this kind of ZnO powder has a high sintering activity. It is suitable for making the low voltage varistors. The Vc decreases with the increase of sintered temperature, when the In2O3 content is fixed(0. 98 %, mass fraction), and increases with the increase of In2O3 contents when the temperature is steady.

DEGRADATION DUE TO ENERGY PULSE IN HIGH-ENERGY ZnO VARISTORS

The degradation phenomena due to the energy pulse in the high-energy ZnO varistors used for deexitation and overvoltage protection of hydroelectric generator are investigated. The energy pulse, obtained by releasing the energy stored in an inductor, can be equivalent to the combination of the DC field components and the energy component. The variations of the characterized voltages, nonlinear coefficients and pre-breakdown V-A characteristics, increase with the number of the applied energy pulse. The asymmetrical variations of the electric properties of the high-energy ZnO varistors after the energy pulse arise from the deformation of the double Schottky barriers due to the ion migration occuring in the depletion layer and in the grain boundary.

Effects of Rare Earth Oxide on Microstructure of Zinc Varistors

The influence of Pr6O11 on the microstructure of ZnO varistors was researched. The results of experiment indicate that addition of Pr6O11 leads to the change of the formation process of the spinel phase. A lot of pyrochlore phases （ Bi3Zn2Sb3O14 ） produce at about 700℃, and decompose to fine spinel phase （Zn7Sb2O12） when the temperature reaches to 900℃.This type of spinel phase makes ZnO crystal size minor. Also, the phase contained the Pr and different Pr oxides, which makes the whole material crystal size more uniform and compact. The fine structure improves the threshold voltage by about 60%, and modifies nonlinear coefficient of the ZnO material.

Nanojunctions Contributing to High Performance Thermoelectric ZnO-Based Inorganic-Organic Hybrids

Organic-inorganic nanojunctions can result in a selective scattering of charge carrier depending on their energy, which leads to a simultaneous increase in the Seebeck coefficient S and the power factor. In this work, the nanojunction is successfully employed at the organic-inorganic semiconductor interface of polyparaphenylene （PPP） and Zn1-xAgxO nanoparticles through the sol-gel method. The presence of nanoinclusions PPP in Zno.gAgoa 0 matrix is found to be effective in improving the figure of merit （ZT） by the dual effects of an increase in the power factor consistent with the heterojunetion effect and a reduction in thermal conductivity. Zno.gAgo.10/0.1 wt% PPP exhibits a maximum figure of merit, i.e., ZT= 0.22.

Mechanism and Development of TiO_2-Doped ZnO-Bi_2O_3-Based Varistors

This paper reviews the history of ZnO varistor,discribes its properties and recenttechnological status and forecasts its evolution.The future development trend is to produce the low-voltage high-energy multi-layer ZnO varistors.After the two additives are classified by their functions,the effect mechanism of Bi_2O_3 and TiO_2 additives are researched theoretically.TiO_2 will make ZnO graingrow bigger and V_ImA/mm be depressed down.Especially the colloid TiO_2 additive in the scale ofnanometer brings about a new method to realize the low voltage of ZnO varistor,which resolves theproblem of how to disturb nanometer powder evenly.Moreover the sintering temperature has prominenteffect on the electrical properties of ZnO varistors.Generally,the appropriate sintering temperature forlow-voltage ZnO varistor ceramics should not be more than 1 250℃.These provide an effective methodand rationale for studying low-voltage ZnO varistors.

Effect of Cr doping on secondary phases and electrical properties of zinc oxide ceramic thick film varistors

In order to get high-performance low voltage varistors,Cr2O3 doped ZnO ceramic thick films were fabricated by modified sol-gel process. The precursors were fabricated by dispersing doped-ZnO ceramic nano-powders in the sols,which were prepared by dissolving zinc acetate dihydrate into 2-methoxyethanol and stabilized by diethanolamine and glacial acetic acid and doped with a concentrated solution of bismuth nitrate,phenylstibonic acid,cobalt nitrate,manganese acetate and chromium nitrate. The results show that ZnCr2O4 phase can form in ZnO based ceramic films doped 1.0%(mole fraction) Cr2O3. Three secondary phases,such as Bi2O3,Zn7Sb2O12,and ZnCr2O4 phases,are detected in the thick films. The Raman spectra show that the intensity and the position of Raman bands of Zn7Sb2O12 and ZnCr2O4 phases change obviously with increasing Cr2O3 doping. The nonlinearity coefficient α of ZnO thick films is 7.0,the nonlinear voltage is 6 V,and the leakage current density is 0.7 μA/mm2.

A Grain Boundary Defect Model for ZnO Ceramic Varistors by Deep Heat Treatment

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现代稳定型氧化锌压敏陶瓷的直流老化研究进展

现代稳定型氧化锌压敏陶瓷的直流老化功耗随时间持续降低,完全不同于功耗不断上升的传统老化现象,给基础老化理论和工程应用均带来了巨大挑战。这种反常的老化现象已经超出了经典离子迁移老化理论的范畴,其非阿雷尼乌斯特征也使实际状态评估和寿命预测难以开展。文中详述了现代稳定型氧化锌压敏陶瓷的直流老化及恢复特征:正向伏安特性在直流老化后存在“交叉”现象;老化过程可逆,试样充分恢复后能达到其未老化状态。离子重排(donorionredistribution,DIR)老化模型可合理解释氧化锌压敏陶瓷的直流老化现象。氧化锌压敏陶瓷的老化功耗取决于界面态消耗与耗尽层离子“U”型分布之间的竞争,前者导致功耗上升而后者有利于功耗降低。稳定型氧化锌压敏陶瓷的势垒界面态在高温、缺氧气氛等条件下不能保持稳定,其原本下降的功耗也能转变为不断上升。此外,广为应用的功耗(泄漏电流)具有显著的电压依赖特性,并不能反映氧化锌压敏陶瓷真实的老化状态,反向老化系数则有望成为一种有效的老化状态表征参数。通过深化现代稳定型氧化锌压敏陶瓷的老化现象、老化机制及状态评估的认识,本文旨在推进我国高性能氧化锌压敏陶瓷生产制造和高端避雷器发展。

ZnO压敏电阻微观结构参数与宏观电气性能的关联机制

ZnO压敏电阻是金属氧化物避雷器的核心部件,在抑制电力系统过电压方面发挥了重要的作用。随着特高压输电技术的发展,对ZnO压敏电阻的残压、通流容量等电气特性提出了更高的要求。该文从材料计算的角度出发,以基于Voronoi模型的ZnO压敏电阻优化计算模型为基础,计算研究了晶粒尺寸、尺寸不均匀度、晶粒电阻率等微观结构参数与多种宏观电气性能之间的关联机制,将多变量、多目标的最优化问题,极大地简化为仅包含三类优化变量、两类优化目标的最优化问题,并制定出具有针对性的优化策略和步骤,为ZnO压敏电阻性能的改进提供了重要理论依据,对高性能避雷器的设计制造具有重要意义。

SiO_(2)掺杂量对SnO_(2)压敏电阻电气性能的影响

采用传统方法制备了掺杂不同物质的量分数(0.01%,0.05%,0.10%,0.15%,0.20%)SiO_(2)的SnO_(2)压敏电阻,研究了SiO_(2)掺杂量对SnO_(2)压敏电阻电气性能的影响。结果表明:随着SiO_(2)掺杂量的增加,SnO_(2)压敏电阻的电压梯度、非线性系数、势垒高度、施主密度和界面态密度均先增大后减小,泄漏电流密度先减小后增大,晶界电阻增大;当SiO_(2)物质的量分数为0.10%时,SnO_(2)压敏电阻的综合电气性能最佳,其电压梯度、非线性系数、施主密度、界面态密度、势垒高度最大,泄漏电流密度最小,分别为582 V·mm^(-1),33,1.7×10^(23)m-3,6.7×10^(16)m^(-2),2.03 eV,7.06μA·cm^(-2)。

基于Si纳米膜的差分结构矢量水听器工艺研究

通过关键工艺步骤,将硅(Si)纳米膜制备在差分结构水听器上作为压敏电阻,利用Si纳米膜的巨压阻效应来提高水听器的灵敏度;利用深Si刻蚀,将Si柱与芯片一体化,减少了差分结构的对准误差,同时抑制海洋洋流带来的振动干扰。设计了相对应的光刻掩模版和整套工艺流程,通过MEMS工艺,成功加工出Si纳米膜作为压敏电阻,实现矢量水听器芯片与Si柱集成化。对制备好的芯片进行观测与测试,使用激光共聚焦显微镜和扫描电子显微镜(SEM)设备观察芯片形貌良好,尺寸与设计基本一致;通过半导体分析仪测量得到压敏电阻器的阻值为15.3×10^(4)Ω,线性度良好,符合矢量水听器功能需求。

不同类型冲击电流对ZnO压敏电阻老化的影响研究

为了比较不同类型冲击电流对氧化锌(ZnO)压敏电阻直流老化的影响,将相同类型的ZnO压敏电阻样品分别开展2 ms方波(峰值为2 kA)耐受试验和4/10μs冲击电流(峰值为100 kA)试验。实验结果表明,在1~3轮(3~9次)的冲击耐受下,2 ms方波对ZnO压敏电阻的老化特性能起到一定优化作用,而4/10μs大电流冲击则使得ZnO压敏电阻老化特性持续劣化。利用扫描电子显微镜(SEM)、光谱仪、数字源表研究其微观结构以及电气性能参数变化。结合实验结果分析原因,4/10μs冲击电流对ZnO压敏电阻的损伤程度大于2 ms方波冲击电流的损伤程度,更容易引起ZnO压敏电阻的老化,在1~3轮(3~9次)2 ms方波耐受下,可以改善压敏电阻老化特性,其原因在于冲击电流产生热效应使构成晶界势垒亚稳定成分填隙锌离子在晶界发生反应而降低其浓度,得到比冲击前更稳定的晶界结,从而提高了其老化特性。

基于经验傅里叶分解的混合式高压直流断路器耗能支路故障检测方法研究

为实现更强的能量耗散能力,混合式高压直流断路器的耗能支路需串并联大量金属氧化物压敏电阻(metal oxidevaristor,MOV),耗能支路的可靠性将直接影响混合式高压直流断路器的可靠性。但是,现有的耗能支路故障检测方法并不能适应整个能量耗散阶段。为此,提出一种基于经验傅里叶分解的混合式高压直流断路器耗能支路故障检测方法,具体为:首先是信号预处理,对耗能支路每个子模块的分支电流进行归一化和一阶差分计算来获取分析电流;然后是故障特征提取,利用经验傅里叶分解(empirical Fourier decomposition,EFD)对分析电流进行分解,提取最高频时频分量作为故障特征分量;最后是检测判据,通过故障特征分量构造突变峰值量化指标,进而通过突变峰值实现耗能支路故障检测。大量实验表明,该检测方法可在能量耗散阶段末期实现可靠地故障检测,且具备一定的抗干扰能力。