Effects of Additive Nd_2O_3 on Varistor Voltage and Microstructure of ZnO Varistor

The influence of additive Nd_2O_3 on varistor voltage and microstructure of ZnO varistor was studied,and its mechanism was proposed from theoretical analysis. The results show that the varistor voltage of ZnO varistor increases with the content of Nd_2O_3 in the range of 0～0.04 (%,mol fraction). However when the content of Nd_2O_3 is more than 0.04 (%,mol fraction),the varistor voltage of ZnO varistor decreases with the content increase. The microstructure analysis indicates that a small amount of new compound with Nd exists at ZnO grain boundary and hinders the movement of grain boundary,which decreases the size of ZnO grain and makes the grain size and distribution homogeneous,as a result,additive (Nd_2O_3) raises the varistor voltage of the varistor greatly.

Inhomogeneity of Grain Boundaries of ZnO Varistor

The zinc oxide varistor with a low threshold voltage and large grain size was derived with ZnO crystalline seeds from a molten salt process The chemical composition and I-V characteristics of single grains and single grain boundaries were determined by means of energy dispersive spectrum (EDS) and microcontact measurement respectively. Temperatu re dependence of dielectric loss at various frequencies and voltage dependence of capacitance were carefully measured. Based on these experimental data. the barrier heights of giain boundaries are estimated to be 0.2. 0.5 and 0.6 eV respectively corresponding to thick, th in and direct contact grain boundaries. In addition. a computerized electrical circuit simufation is employed in simulating I-V characteristics of single grain boundary within ZnO varistor. By adjustjng parameters of resistor and diode, a general agreement between the measured data and simulated curves is achieved

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.

Power loss transition of stable ZnO varistor ceramics: Role of oxygen adsorption on the stability of interface states at the grain boundary

Highly stable ZnO varistor ceramics with steadily decreasing power loss have been put into applications in electrical and electronic systems for overvoltage protections, even with the absence of general understandings on their aging behaviors. In this paper, we investigated their aging nature via conducting comparative direct current (DC) aging experiments both in air and in nitrogen, during which variations of electrical properties and interface properties were measured and analyzed. Notably, continuously increasing power loss with severe electrical degradation was observed for the sample aged in nitrogen. The power loss transition was discovered to be closely related to the consumption of oxygen adsorption at the grain boundary (GB), which could, however, remain constant for the sample aged in air. The interface density of states (DOS) Ni, which is crucial for pinning the potential barrier, was proved to decrease in nitrogen, but keep stable in air. Therefore, it is concluded that the oxygen adsorption at the GB is significant for the stability of interface states, which further correlates to the long-term stability of modern stable ZnO varistor ceramics.

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。

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。

Cr_(2)O_(3)对ZnO-Bi_(2)O_(3)基高压压敏陶瓷性能的影响

采用固相烧结法制备ZnO-Bi_(2)O_(3)-Co_(2)O_(3)-NiO-Mn_(3)O_(4)-SiO_(2)-Cr_(2)O_(3)压敏陶瓷,研究不同掺杂量的Cr_(2)O_(3)对ZnO压敏陶瓷的微观结构和电气性能的影响。通过X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)及电化学工作站分别对样品的物相、微观形貌及电性能进行表征。结果表明:Cr_(2)O_(3)的加入不仅具有抑制ZnO晶粒异常生长和提升晶粒均匀分布的作用,而且能显著降低ZnO晶粒电阻,增加晶界电阻。在Cr_(2)O_(3)添加量为0%~0.21%(摩尔分数,下同)范围内,随着添加量的增大,压敏陶瓷的非线性系数表现为先增加后减小。当Cr_(2)O_(3)掺杂量为0.14%时,ZnO压敏陶瓷具有优异的电气性能:电位梯度E_(1 mA)=216 V·mm^(-1)、泄漏电流J_L=0.36μA·cm^(-2)、非线性系数α=25、残压比K=1.815、老化系数K_(ct)=0.647。此外,该压敏陶瓷在4/10μs波形下100 kA脉冲电流冲击2次后U_(1 mA)仍保持为初始的96.75%,表现出良好的冲击稳定性,在配电系统避雷器中具有巨大的应用潜力。

施主掺杂提高ZnO压敏电阻的冲击稳定性

研究了铝铟共掺杂对ZnO压敏电阻的微观结构和电学性能的影响,特别是浪涌冲击稳定行为。采用X射线衍射、扫描电子显微镜对ZnO压敏电阻的微观结构进行了表征,通过电流—电压测试、脉冲电流冲击测试和电容—电压测试对电性能进行了评估。结果表明:当Al^(3+)和In^(3+)掺杂量分别为0.0008 mol%和0.0033 mol%时,ZnO压敏电阻表现出了最佳的电性能;此时的电位梯度为95.3 V·mm^(-1)、非线性系数为74、残压比为2.43。另外,ZnO压敏电阻在8/20μs 10 k A电流下冲击20次后,正反压敏电压变化率分别为+3.30%和-6.67%。

ZnO压敏电阻微观结构调控与性能提升研究综述

金属氧化物避雷器是电力系统重要的过电压保护设备,ZnO压敏电阻是其核心部件。提高ZnO压敏电阻性能,不仅有利于优化现有系统的绝缘配合设计,在面对未来新能源广泛应用的新型电力系统时,也有利于提高对系统的保护能力,并促进设备小型化、紧凑化、轻量化。一直以来,人们主要按照机械混粉烧结的工艺路线,通过改进材料配方、改善烧结工艺、优化粉体制备等来提升ZnO压敏电阻的性能。这些工作对提高ZnO压敏电阻性能发挥了重要作用,但进一步提升的潜力有限。表面包覆形成的核壳结构能使ZnO压敏电阻的微观结构更加均匀,并可能在烧结过程中对ZnO压敏电阻的微观结构进行定制化的有效调控,在提升ZnO压敏电阻的性能方面有一定的潜力。因此,基于表面包覆的ZnO压敏电阻有望成为研究高性能ZnO避雷器的新途径。该文从传统机械混粉和表面包覆两种技术路线的角度对ZnO压敏电阻的微观结构调控与性能提升研究做了归纳整理,并对包覆路线下需要开展的研究工作进行了思考,希望能为相关领域的研究提供一定的参考。

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.

Preparation and characterization of layered low-voltage ZnO varistors

Double-layered, low-voltage ZnO varistors have been fabricated by feeding two kinds of ZnO powders into a die using dry extrusion molding. Compared with ZnO varistors fabricated by the conventional route, the layered ZnO varistors have larger non-linear coefficients, lower breakdown electric fields, and lower leakage current densities. The improvement in electrical performance of the layered low-voltage ZnO varistors is attributed to the asymmetric band structure at grain boundary between the two layers.

Percolation effects in dc degradation of ZnO varistors

For quantitative estimation of the degree of electrical disorder(electrical inhomogeneity)in ZnO varistor ceramics caused by a variation in the barrier height at different grain boundaries in a sample,the comparison of threshold electric fields(onsets of highly nonlinear current-voltage characteristics)in ceramics and single grain boundary(GB)is suggested and approved.At dc degradation similar behavior of the current-voltage characteristics of ZnO varistor ceramics and single GB is observed.The percolation model of Shklovskii-De Gennes is applicable for the description of a disorder in ZnO varistor ceramics.The degree of the disorder in ZnO varistor ceramics is not dependent on the duration of dc degradation at least at degradation time below 60 h.At voltages close to the onset of a highly nonlinear region of current-voltage characteristic the correlation radius of infinite cluster is~5 times greater than the average grain size.

Effect of sintering temperature on microstructure and nonlinear electrical characteristics of ZnO varistor

The nonlinear properties of ZBMCCS-based varistors,which are composed of ZnO-Bi_(2)O_(3)-MnO_(2)-Cr_(2)O_(3)-Sb_(2)O_(3)-Co_(3)O_(4) and SiO_(2) are studied inrelation to sintering temperature,in the range of 1280–1350℃.The samples are investigated for grain morphology by using scanning electron microscope(SEM).These samples were examined by using X-ray diffraction patterns(XRD)and DC electrical measurements.X-ray diffraction analysis of the samples show the presence of ZnO,Zn_(2)SiO_(4) willemite phase and Co_(2.33)Sb_(0.67)O_(4) spinel phases.The average grain size of ZnO increased as the sintering temperature increased from 2.57 to 6.84
m.In the examined temperature range,the breakdown field decreased from 2992 to 127 V/cm with the increase of sintering temperature.This system gives a relatively high nonlinearity coefficientα=33.61(at a sintering temperature of 1280℃)with a low leakage current of 0.21 mA/cm^(2).

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.

ZnO varistors with high voltage gradient and low leakage current by doping rare-earth oxide

The surge arrester of 1000 kV gas-insulated substation (GIS) needs ZnO varistor with high voltage gradient to effectively improve the potential distribution along ZnO varistor column inside the metal-oxide surge arresters. In this paper, the elec-trical and structural parameters of ZnO varistors are changed by doping with some rare-earth oxides, and the mechanism which leads these changes is discussed. When rare-earth oxide additives are added into ZnO varistors, the growing speed is slowed down due to the stabilization of the new spinel phases formed in the grain-boundary by rare-earth oxide additives, then the size of ZnO grains is smaller, and the voltage gradient of varistor increases obviously. By adding suitable amount of oxides of metal Co and Mn, the leakage current can be effectively decreased and the nonlinearity coefficient increased. The novel ZnO varistor samples sintered with the optimal additives have a voltage gradient of 492 V/mm, and the nonlinearity coefficient of 76, but their leakage currents are only 1 μA.

采用Ga掺杂的具有低泄漏电流和高稳定性避雷器ZnO压敏电阻

为了获得性能更为稳定的ZnO压敏电阻,研究了含有Ga掺杂的ZnO压敏电阻的稳定特性,对所获得的实验样品的微观结构和电气特性进行了电子显微镜扫描测试、电压-电流非线性特性测试、电容-电压特性测试、X-射线衍射谱测试、能谱扫描测试、介质损耗测试及交流加速老化测试.实验结果表明,随着Ga掺杂量的进一步增加,Ga离子占据了ZnO晶格上的空位,增加了界面态密度,提高了肖特基势垒高度,一方面降低了ZnO压敏电阻的泄漏电流密度,另一方面抑制了耗尽层中自由电子的迁移,提高了ZnO压敏电阻在高荷电率环境下的稳定特性.Al离子固溶到ZnO晶格当中,产生大量的自由电子,降低了ZnO晶粒的电阻率,从而有效降低了ZnO压敏电阻在通过大电流时的残压比.当Ga的掺杂摩尔分数达到0.6%时,泄漏电流密度为0.84μA/cm^(2),残压比为1.97,非线性系数为66,其肖特基势垒高度为1.81 eV.在115℃环境下,对试验样品施加87%E1 mA,89%E1 mA和91%E1 mA的交流加速老化电压,老化时间为1000 h,老化系数分别为0.394,0.437和0.550.此研究将有助于进一步提高ZnO避雷器的保护水平,实现深度限制电网过电压,提高电力系统的安全稳定性.

Influence of grain size on distribution of temperature and thermal stress in ZnO varistor ceramics

The nonuniformity of temperature distribution within ZnO varistor ceramics would decrease its energy absorption capability. In this paper, the distributions of current, temperature and thermal stress within the microstructures of ZnO varistor ceramics are simulated using Voronoi diagram models. The results show that the current concentrates through a few paths in ZnO varistor due to the nonuniformity of ZnO grain size and the variety of electrical characteristics of grain boundaries, which induces local high temperature and great thermal stress when injecting impulse current into ZnO varistor, and leads to melting puncture or cracking failure. The influence of the ZnO grain size on the distributions of temperature and thermal stress within ZnO varistor ceramics is analyzed in detail. The energy absorption capability of ZnO varistor ceramics can be greatly improved by increasing the uniformity of ZnO grain size or decreasing the average size of ZnO grains.

Microstructures and characteristics of deep trap levels in ZnO varistors doped with Y_2O_3

In this paper discussions on ZnO based varistor ceramics doped with different ratios of Y2O3 are presented.Analysis on the phase and microstructures of the samples indicates that an additional phase is detected in the samples doped with Y2O3,and the average grain size of the specimens decreases from about 9.2μm to 4.5μm,with an increase in the addition of Y2O3 from 0 mol%to 3 mol%.The corresponding varistor’s voltage gradient markedly increases from 462 V/mm to 2340 V/mm,while the nonlinear coefficient decreases from 22.3 to 11.5,respectively.Furthermore,the characteristics of deep trap levels in these ZnO samples are investigated by measuring their dielectric spectroscopies.The trap energy level and capture cross section evaluated by relaxation peak of the Cole-Cole plot vary slightly as the addition of Y2O3 increases.These traps may be ascribed to the intrinsic defects of ZnO lattice.

包覆形成的核壳结构对ZnO压敏电阻的改性机制

ZnO压敏电阻的性能,直接决定了避雷器的保护水平和电力系统的绝缘水平。为实现ZnO压敏电阻综合性能的优化,通过溶胶凝胶法将SiO_(2)均匀包覆在ZnO颗粒表面,获得了具备明显核壳结构的粉体颗粒。当Si^(4+)/Zn^(2+)包覆摩尔比为0.075时,在1050℃下所烧结制备的ZnO压敏电阻,电位梯度可达651.37 V/mm,相较于未包覆样品提升115.6%;非线性系数可达73.02,提升104.5%;泄漏电流密度为0.73μA/cm^(2),降低77.5%。基于不同样品晶相测试结果中的区别,结合宏观电学性能、微观晶界势垒特性、介电响应特性等方面的差异,研究了包覆所形成的ZnO@SiO_(2)核壳结构对ZnO压敏电阻性能改善的晶粒生长控制机制、固溶反应机制和氧输运机制。