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.
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.
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.
ZnO-Bi2O3-based varistor ceramics doped with EU2O3 in a range from 0 to 0.4% were obtained by high-energy ball milling and fired at 900-1000 ℃ for 2 h. XRD and SEM were applied to determine the phases and microstructure of the varistor ceramics. A DC parameter instrument was applied to investigate the electronic properties and V-I characteristics. The XRD analysis of Eu2O3-doped ZnO-Bi2O3-based varistor ceramics shows that the ZnO, Eu-containing Bi-rich, Zn7Sb2O12-type spinel and Zn2Bi3Sb3O14-type which is the pyrochlore phase are present. With increasing Eu2O3 content, the average size of ZnO grain firstly decreases and then increases. The grain boundary defect model was particularly used to explain the excellent nonlinearity of ZnO-Bi2O3-based varistor ceramics with the addition of0.1% Eu2O3 and sintered at 950 ℃.
A series of ZnO-Bi2O3-based varistor ceramics doped with 0-0.4 mol.% Sc2O3 were prepared by high-energy ball milling and sintered at temperatures between 1000 and 1150oC. X-ray diffractometry （XRD） and scanning electron microscopy （SEM） were applied to characterize the phases and microstructure of the varistor ceramics. A DC parameter instrument for varistor ceramics was applied to investigate the electronic properties and V-I characteristics. The results showed that there were no changes in crystal structure with Sc2O3-doped varistor ceramics and that the average size of ZnO grain increased first and then decreased. The best electronic characteristics of the varistor ceramics prepared by high-energy ball milling were found in 0.3 mol.% Sc2O3-doped ZnO-Bi2O3 -based ceramics sintered at 1000 oC, which exhibited a threshold voltage of 821 V/mm, nonlinear coefficient of 62.1 and leakage current of 0.16 μA.
