Effects of high-energy ball milling oxide-doped and varistor ceramic powder on ZnO varistor

ZnO varistor ceramics doped with Bi2O3, Sb2O3, CO2O3, Cr2O3, and MnO2 were prepared separately by two high-energy ball milling processes： oxide-doped and varistor ceramic powder. A comparison in the electrical and microstructural properties of the samples obtained by both methods was made. The best results on these characteristics were achieved through the high-energy ball milling varistor ceramic powder route, obtaining a nonlinear coefficient of 57 and a breakdown field of 617 V/mm at a sintering temperature of 1000 ℃ for 3 h. The samples synthesized by this technique show not only high density value, 95% of the theoretical density, but also a homogeneous microstructure, which compete with those obtained by the high-energy ball milling oxide-doped powder route. With the advantage that the high-energy ball milling varistor ceramic powder route can refine grain, increase the driving force of sintering, accelerate the sintering process, and reduce the sintering temperature.

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.

INFLUENCE OF Li_2CO_3-SiO_2 ADDITIVE ON THE PROPERTIES AND PROCESSING OF DOUBLE-FUNCTION SrTiO_3-BASED LOW VOLTAGE VARISTOR CERAMICS

Semiconducting SrTiO 3 based voltage sensing and dielectric ceramics were prepared by single step sintering with Li 2CO 3 SiO 2 as liquid phase additives.The effects of the content of liquid phase,the ratio of Li/Si and the sintering temperatures on properties were discussed in terms of electrical properties and microstructures of materials.The results showed thatSrTiO 3 based varistor ceramics,with 0.6 mol% Li 2CO 3 SiO 2(Li/Si=3/2) and sintered at 1 380 ℃ in graphite and N 2 reducing atomosphere,had excellent current volatage sensing and dielectric characteristics.

Effect of sintering temperature on microstructure and varistor properties of Zn-V-O-based ceramics incorporated with Mn-Nb-Tb

The effect of sintering temperature on microstructure and varistor properties of Zn-V-O-based ceramics incorporated with Mn-Nb-Tb was investigated. The results showed that the increase of sintering temperature in the range from 875 to 950 °C decreased the densities of sintered pellets in the range of 5.55 to 5.45 g/cm3 and increased the average grain size in the range of 4.1 to 8.8 ？m. The breakdown field decreased noticeably from 7443 to 1064 V/cm with increasing sintering temperature from 875 to 950 °C. The varistor ceramics sintered at 900 ？C exhibited nonlinear properties, with 49.4 in the nonlinear coefficient and 0.21 m A/cm2 in the leakage current density. The dielectric constant increased greatly from 440.1 to 2197.2 with increasing sintering temperature from 875 to 950 °C; however, the dissipation factor exhibited a fluctuation between 0.237 and 0.5. These ceramic compositions and sintering conditions can be applied to the development of advanced multiplayer varistors with silver as an inner electrode.

INFLUENCE OF Li2CO3-SiO2 ADDITIVE ON THE PROPERTIES AND PROCESSING OF DOUBLE-FUNCTION SrTiO3-BASED LOW VOLTAGE VARISTOR CERAMICS

Semiconducting SrTiO 3 based voltage sensing and dielectric ceramics were prepared by single step sintering with Li 2CO 3 SiO 2 as liquid phase additives.The effects of the content of liquid phase,the ratio of Li/Si and the sintering temperatures on properties were discussed in terms of electrical properties and microstructures of materials.The results showed thatSrTiO 3 based varistor ceramics,with 0.6 mol% Li 2CO 3 SiO 2(Li/Si=3/2) and sintered at 1 380 ℃ in graphite and N 2 reducing atomosphere,had excellent current volatage sensing and dielectric characteristics.

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%.

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 Rare-Earth La_2O_3 Addition on Microstructures and Electrical Properties of SrTiO_3 Varistor-Capacitor Dual Functional Ceramics

The effects of rare-earth La_2O_3 addition on microstructures and electrical properties of SrTiO_3 ceramics were investigated. Semiconductor SrTiO_3-based voltage-sensing and dielectric dual functional ceramics was prepared by a single step sintering technology in this study, and the effects of the content of La_2O_3 on characteristics of the product were discussed in terms of microstructures and electrical properties of materials. The results show that SrTiO_3-based ceramics doped with La_2O_3 exhibits more homogeneous grain distribution, greater grain size, and excellent voltage sensing and dielectric characteristics than those without La_2O_3 doping. The samples doped with 1 1% La_2O_3 were sintered at 1420 ℃ in N_2+C weak reducing atmosphere. The average grain size of the samples doped with La_2O_3 is 40 μm, the breakdown voltage of 19.7 V·mm^(-1), the nonlinear exponent of 7.2, and dielectric constant of 22500. The results reveal that final products are suitable to use in low operating voltage.

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 Lu_2O_3-doped ZnO-Bi_2O_3-based varistor ceramics

Lu2O3-doped ZnO-Bi2O3-based varistor ceramics samples were prepared by a conventional mixed oxide route and sintered at temperatures in the range of 900-1 000°C,and the microstructures of the varistor ceramics samples were characterized by X-ray diffractometry(XRD)and scanning electron microscopy(SEM);at the same time,the electrical properties and V-I characteristics of the varistor ceramics samples were investigated by a DC parameter instrument for varistors.The results show that the ZnO-Bi2O3-based varistor ceramics with 0.3%Lu2O3(molar fraction)sintered at 950°C exhibit comparatively ideal comprehensive electrical properties.The XRD analysis of the samples shows the presence of ZnO,Bi-rich,spinel Zn7Sb2O12 and Lu2O3-based phases.

Influence of Yb_2O_3 doping on microstructural and electrical properties of ZnO-Bi_2O_3-based varistor ceramics

ZnO-Bi2O3-based varistor ceramics doped with Yb2O3 in the range from 0 to 0.4% （molar fraction） were obtained by a solid reaction route. The X-ray diffractometry （XRD） and scanning electron microscopy （SEM） were applied to characterize the phases and microstructure of the varistor ceramics, and a DC parameter instrument for varistor ceramics was applied to investigate their electrical properties and V-I characteristics. The XRD analysis of the samples shows that the ZnO phase, Bi2O3 phase, ZnTSbaOl2-type spinel phase and Zn2Bi3Sb3O14-type pyrochlore are present, and the Yb2O3 phases and Sb2O4 phases are found in varistor ceramics with increasing amounts of Yb2O3. The average size of ZnO grain firstly increases and then decreases with the increase of Yb2O3 content. The result also shows that the threshold voltage is between 656 V/nun and 1 232 V/mm, the nonlinear coefficient is in the range of 14.1-22.3, and the leakage current is between 0.60 μA and 19.6 μA. The 0.20% Yb2O3-added ZnO-Bi2O3-based varistor ceramics sintered at 900 ℃ have the best electrical characteristics.

Comparative characteristics of yttrium oxide and yttrium nitric acid doping in ZnO varistor ceramics

The effect of different molar ratios of Y2O3 and Y（NO3）3 on the microstructure and electrical response of ZnO-Bi203-based varistor ceramics sintered at 1 000 ℃ was investigated, and the mechanism by which this doping improves the electrical characteristics of ZnO-Bi203-based varistor ceramics was discussed. With increasing amounts of Y（NO3）3 or Y2O3 in the starting composition, Y2O3, Sb204 and Y-containing Bi-rich phase form, and the average grain size significantly decreases. The average grain size significantly decreases as the contents of rare earth compounds of Y（NO3）3 or Y2O3 increase. The maximum value of the nonlinear coefficient is found at 0.16% Y（NO3）3 or 0.02% YaO3 （molar fraction） doped varistor ceramics, and there is an increase of 122% or 35% compared with the varistor ceramics without Y（NO3）3 or Y2O3. The threshold voltage VT of Y（NO3）3 and Y2O3 reaches at 1 460 V/mm and 1 035 V/ram, respectively. The results also show that varistor sample doped with Y（NO3）3 has a remarkably more homogeneous and denser microstructure in comparison to the sample doped with Y2O3.

Influence of soaking time on nonlinear electrical behavior and dielectric properties of TiO_2-based varistor ceramics

The influence of soaking time on the nonlinear electrical behavior and dielectric properties of TiO2-based varistor ceramics was investigated. Based on single sintering process, six disk samples of （Sr, Bi, Si, Ta）-doped TiO2-based varistor ceramics were fabricated by sintering at 1 250 ℃ for 0.5-5.0 h. The samples were characterized by X-ray diffraction, voltage-current characteristics, energy spectra, metallographs, breakdown voltages, and apparent dielectric constant. It is found that the breakdown electrical field intensity at a current density of 10 mA/cma decreases from 5.5 to 4.1 V/mm first and then increases to 7.0 V/mm, the nonlinear coefficient increases from 2.39 to 2.62 first and then decreases to 2.42, and the apparent dielectric constant increases from 98 200 to 1l5 049 first and then decreases to 73 865 with the soaking time increasing from 0.5 to 5.0 h. These indicate that the optimal soaking time is 2.0-3.0 h considering both nonlinear electrical behavior and dielectric properties.

Influence of soaking time on semi-conductivity and nonlinear electrical properties of TiO_2-based varistor ceramics

We investigated the influence of soaking time on the semi-conductivity and nonlinear electrical properties of TiO2- based varistor ceramic samples. We used a single sintering process and fabricated six disk samples of （Sr, Bi, Si, Ta）-doped TiO2- based varistor ceramics sintered at 1 250℃ for 0.5 h, 1.0 h, 2.0 h, 3.0 h, 4.0 h, and 5.0 h, respectively. The samples were characterized by X-ray diffraction, breakdown voltage, and complex impedance. The results show that as the soaking time increases from 0.5 h to 5.0 h, the breakdown voltage drops before rising while the nonlinear coefficient increases and then decreases. We suggest that, considering both grain semi-conductivity and nonlinear electrical properties of the TiO2-based varistor ceramics, the optimal soaking time is between 2.0 h and 3.0 h.

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.

Effect of capacitance on ZnO-Bi_2O_3-Yb_2O_3 based varistor for nanosecond transients

The microstructure and electrical properties of ZnO-Bi2O3-Yb2O3 based varistor ceramics were investigated with various temperature effects from 900°C to 1050°C.From the results,it was observed that the increase of sintering temperature offers a reduced capacitive effect from 0.460 nF to 0.321 nF.Furthermore,the grain sizes of varistors were varied from 6.8μm to 9.8μm.The consequence of such smaller grain sizes provided a better voltage gradient of about 895 V/mm for the disc sintered at 900°C and fallen drastically to 410 V/mm for the sample sintered at 1050°C.In addition,there was an increase of non-linearity index to a maximum value of 36.0 and reduced leakage current of 0.026 mA/cm2.However,the density of the varistor decreased with an increase of temperature from 5.41 g/cm3 to 5.24 g/cm3.With this base,the influence of varistor capacitance and high voltage gradient were scrutinized and it led an improved transition speed of the varistor assembly from non-conduction to conduction mode during intruding nanosecond transients.

Influence of Ag doping on the microstructure and electrical properties of ZnO-Bi_2O_3-based varistor ceramics

Silver in the form of AgNO3 was added to ZnO-based varistor ceramics prepared by the solid-state reaction method.The effects of AgNO3 on both the microstructure and electrical properties of the varistors were studied in detail.The optimum addition amount of AgNO3 in ZnO-based varistors was also determined.The mechanism for grain growth inhibition by silver doping was also proposed.The results indicate that the varistor threshold voltage increases substantially along with the AgNO3 content increasing from 0 to 1.5mol%.Also,the introduction of AgNO3 can depress the mean grain size of ZnO,which is mainly responsible for the threshold voltage.Furthermore,the addition of AgNO3 results in a slight decrease of donor density and a more severe fall in the density of interface states,which cause a decline in barrier height and an increase in the depletion layer.

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.

Nonlinear Electrical Properties of SnO_2-Li_2O-Nb_2O_5 Varistor System

The electrical properties of (Nb, Li)-doped SnO2 ceramics as a new varistor material were investigated. The sample 97.95%SnO2·0.50%Li2O·0.05%Nb2O5 (mol fraction) sintered at 1450= possess the highest density (ρ=6.77 g/cm3) and nonlinear electrical coefficient (α=11.6). The substitution of Sn4+ with Li+ increases the concentration of oxygen vacancies, together with the formation of solid solution, which will increase the sintering rate greatly and decrease the optimized sintering temperature. The substitution of Sn4+ with Li+ and the variation of temperature play very important effects on the densities, dielectric constant, nonlinear electrical properties and other characteristics of the samples. The properties of the grain boundary barrier and the microstructural characteristics were investigated to ensure the effect of the dopants and the temperature. A grain boundary defect barrier model was used to illustrate the grain boundary barriers formation in SnO2-Li2O-Nb2O5 varistors.