Nonlinear electrical behaviour of the Cr2O3, ZnO, CoO and Ta2O5-doped SnO2 varistors

The effects of Cr2O3 on the properties of (Zn, Co, Ta)-doped SnO2 varistors were investigated in this study. The samples with different Cr2O3 concentrations were sintered at 1400 degrees C for 2 h. The properties of (Zn, Co, Ta, Cr)-doped SnO2 varistors were evaluated by XRD. dilatornetry, SEM, I-V and impedance spectroscopy. DC electrical characterization showed a dramatic increase ill the breakdown electrical field and in the nonlinear coefficient with the increase in Cr2O3 concentration. The grain size was found to decrease from 13 to 5 mu m with increasing the Cr2O3 content. The impedance data, represented by means of Nyquist diagrams, show two time constants, one at low frequencies and the other at high frequencies. (c) 2005 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

ZnO varistors from intensively milled powders

Two ways of application of intensive milling in ZnO varistors processing were compared. First was intensive milling of mixture of previously prepared constituent phases. In this case, intensive milling was applied only to obtain highly activated nanocrystalline varistor powder mixtures. Second application is intensive milling of simple mixture of oxides that could result not only in activation and formation of nanocrystal line powders, but also in mechanochernical reaction and synthesis of constituent phases. Powders and ceramics samples were characterized by XRD and SEM analysis. as well as by de electrical measurements (nonlinearity coefficients, leakage current and breakdown field). Differences in microstructural and electrical properties of obtained varistors were discussed and optimal milling and processing conditions were recommended. The best electrical characteristics were found in sample ZI -DMCP-m, which exhibited leakage current of 2.5 mu A/cm(2), nonlinear coefficient reaching 58 and breakdown field of 8950 V/cm. (c) 2007 Elsevier Ltd. All rights reserved.

Grain-boundary segregation and precipitates in La2O3 and Pr2O3 doped SnO2 center dot CoO-based varistors

Structural heterogeneities in SnO2.CoO-based varistors were analyzed by transmission electron microscopy. In SnO2.CoO-based system doped with La2O3 and Pr2O3 two kinds of precipitate phases at grain boundary region were found. Using energy dispersive spectrometry they were found to be Co2SnO4 and Pr2Sn2O7, presenting a defined crystalline structure. It was also identified that such precipitate phases are mainly located in triple-junctions of the microstructure. HRTEM analysis revealed the existence of other two types of junctions, one as being homo-junctions of SnO2 grains and other due to twin grain boundaries inside the SnO2.CoO grain. The role of these types of junction in the overall nonlinear electrical features is also discussed. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

BARRIER VOLTAGE DEFORMATION OF ZNO VARISTORS BY CURRENT PULSE

The phenomenon of electrical degradation in ZnO varistors was studied by application of high-intensity current pulses. A wave shape of 8 X 20-mu-s and rectangular waves of 1 and 2 ms were used. The degradation was estimated by reference electric-field variation and by Schottky voltage barrier deformation. The results showed that current pulses reduce both the height and the width of the barrier voltage. It was also observed that the donor density N(d) did not change but the surface states density N(s) decreased with degradation.

Dependence of La2O3 content on the nonlinear electrical behaviour of ZnO, CoO and Ta2O5 doped SnO2 varistors

The effects of La2O3 on the properties of (Zn, Co, Ta) doped SnO2 varistors were investigated in this study. The samples with different La2O3 concentrations were sintered at 1400 degrees C for 2 h and their properties were characterized by XRD, SEM, I-V and impedance spectroscopy. The grain size was found to decrease from 13 pm to 9 gm with increasing La2O3 content. The addition of rare earth element leads to increase the nonlinear coefficient and the breakdown voltage. The enhancement was expected to arise from the possible segregation of lanthanide ion due to its larger ionic radius to the grain boundaries, thereby modifying its electrical characteristics. Furthermore, the dopants such as La may help in the adsorption of O' to O '' at the grain boundaries characteristics. (c) 2006 Elsevier B.V. All rights reserved.

Effect of oxidizing and reducing atmospheres on the electrical properties of dense SnO2-based varistors

The SnO2 based varistor systems recently presented in the literature appear to have a promising potential in commercial applications. Experimental evidence shows that there is a dependence of nonlinear constant values with thermal treatment under different atmospheres. Thermal treatments in oxygen and nitrogen rich atmospheres at 900 degreesC prove this dependence, indicating that the nonlinear constant values are significantly lower when the material is submitted to a nitrogen atmosphere. Moreover, electrical properties can be restored when the varistor is subjected to thermal treatment at the same temperature in an oxygen atmosphere, indicating that the mechanism seems to be reversible. This paper discusses this behavior focusing in the grain boundary region. Ta2O5 mol% concentrations are also analyzed and the results indicate an optimum Ta2O5 concentration of 0.05 mol% for the electrical properties (alpha = 44 and E-B = 6150 V cm(-1)). (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Structural and electrical properties of ZnO varistors containing different spinel phases

Structural and electrical properties of ZnO varistors were investigated as a function of spinel composition. Six varistor mixtures differing only in chemical composition of spinel, were prepared by mixing separately synthesized constituent phases (DSCP method). Compositions of constituent phases in sintered samples were investigated by changes of lattice parameters of the phases, as well as by EDS analysis of the constituent phases. It was found that compositions of ZnO, intergranular and spinel phases were partially changed during sintering due to redistribution of additives, that was controlled by starting spinel composition and its stability. Electrical characterization showed significant difference in electrical properties of investigated varistors: nonlinearity coefficients ranging from 22 to 55 and leakage currents differing by the order of magnitude. Activation energies of conduction were obtained from ac impedance spectroscopy measurements. Calculated values of activation energies were in the range 0.61-1.0 eV confirming difference in defect structure of ZnO grain boundaries in varistors containing different spinel phases. (C) 2001 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Nonlinear properties and stability of SnO2 varistors prepared by evaporation and decomposition of suspensions

SnO2 varistors doped with CoO, Cr2O3 and Nb2O5 were prepared by evaporation and decomposition of suspensions. The composition of the varistors was optimized to improve electrical properties, such as nonlinearity, leakage current and electrical stability. The best results were achieved with the following composition: 99.15% SnO2 +0.75% CoO+0.05% Cr2O3 +0.05% Nb2O5. Samples showed high density, reaching 99.5% of the theoretical density, as well as an homogeneous microstructure. The nonlinear coefficient was higher than 30 in the current range from 10(-7) to 10(-2) A/cm(2). The leakage current was 0.86 mu A/cm(2). These samples showed high stability of electrical parameters when they were exposed to high current of 27 mA/cm(2) for different time periods up to 30 min. (c) 2005 Elsevier Ltd. All rights reserved.

Characterization of ZnO-degraded varistors used in high-tension devices

The effects of the degradation process on the structural, microstructural and electrical properties of ZnO-based varistors were analyzed. Rietveld refinement showed that the BiO2-x phase is affected by the degradation process. Besides the changes in the spinel phase, the degradation process also affects the lattice microstrain in the ZnO phase. Scanning electron microscopy analysis showed electrode-melting failure, while wavelength dispersive X-ray spectroscopy qualitative analysis showed deficiency of oxygen species at the grain boundaries in the degraded samples. Atomic force microscopy using electrostatic mode force illustrated a decrease in the charge density at the grain boundaries of the degraded sample. Transmission electron microscopy showed submicrometric spinel grains embedded in a ZnO matrix, but their average grain size is smaller in the degraded sample than in the standard one. Long pulses appeared to be more harmful for the varistors' properties than short ones, causing higher leakage current values. The electrical characteristics of the degraded sample are partially restored after heat treatment in an oxygen-rich atmosphere. (C) 2006 Elsevier Ltd. All rights reserved.

Synthesis of SnO2 by chemical routes and its use in varistors production

Tin oxide, SnO2. is a very used compound in industry and one of its uses is as varistor. For the current requirements of the technology is necessary a strict control of the chemical purity and the particle size of the raw material; for that reason the great interest that exists at the moment to develop synthesis methods that allow to get these requirements. In this work, ceramic powders of the Sn-Co-Nb-Ti-Al system using the controlled precipitation and polymeric precursor (Pechini) methods were synthesized. The raw material obtained was characterized using X-ray diffraction (XRD), thermal analysis (DTA/FG) and scanning electron microscopy (SEM). The sintering samples shown a good varistor behavior with non-linear coefficient (alpha) values similar to 22, and Er 2083 V/cm(2). (c) 2007 Elsevier Ltd. All rights reserved.

The influence of aluminium on the overall properties of SnO2-based varistors

The influence of aluminium on the development of the microstructure and on the electrical behaviour of the SnO2 center dot Co3O4 center dot Nb2O5 typical varistor system was studied. Two sources of Al were used, alumina (Al2O3) and boehmite (AlO(OH)). The microstructural features were characterised with scanning (SEM) and transmission (TEM) electron microscopies. The different phases present in the studied samples were also studied with XRD, EDS and electron diffraction patterns of selected areas (SAED). Particles containing Sri, Co, Al, and O were unveiled with TEM. Impedance spectroscopy measurements and current density versus electric field characteristics revealed superior electrical properties for samples with AlO(OH). The higher non-linearity (alpha = 19) was achieved with the addition of 0.1% mol of boehmite. The influence of the secondary phases on the electrical properties is also addressed in this work.

PROCESSING AND CHARACTERIZATION OF LOW-VOLTAGE VARISTORS

ZnO seed particles and Cr2O3 were used in this study to control the microstructure of ZnO varistors. The seed particles were prepared by adding 1.0 mol % BaO to ZnO. The powder was then calcined at 800-degrees-C for 2 h, pressed into pellets and sintered at 1400-degrees-C for 8 h. The sintered ZnO was ground and the BaO eliminated by washing in water. The remaining ZnO powder was classified into a size fraction ranging from 38 to 149 mum. The addition of a small amount (1 weight %) ZnO seed grains produces varistors with low breakdown voltages (7.6 V/mm) and an alpha coefficient of approximately 10. The addition of Cr2O3 stabilizes the spinel phase yielding a more homogeneous microstructure, but degraded electrical behaviour of the ZnO varistor.

Thermal conductivity features of ZnO-based varistors using the laser-pulse method

The thermal conductivity of several commercial ZnO-based varistor systems was determined based on the laser-pulse method, a technique that proved extremely useful and easy to apply. Using this technique, the thermal conductivity was found to be dependent on the microstructural features of the devices, involving the mean grain size and phase composition. Among the phases existing in commercial ZnO-based varistors, ZniSb2O12 and Bi2O3 were found to contribute strongly to the thermal conductivity of the devices. (C) 2003 Elsevier B.V. All rights reserved.

The role of oxygen vacancies on the microstructure development and on the electrical properties of SnO2-based varistors

Variations on the microstructure development and on the electrical properties of SnO2-based varistors are discussed on the basis of the oxygen vacancies created or annihilated by the presence of different additives. Electron paramagnetic resonance (EPR) analysis of sintered samples evidenced a substantial increase in the paramagnetic oxygen vacancies concentration when Nb2O5 is added to the SnO2 center dot Co3O4 system. on the other hand, the observed diminution in the concentration of such species after the addition of Fe2O3 indicates solid solution formation. The quantification of paramagnetic oxygen vacancies allowed to confirm the proposed substitutions taking place in the lattice during sintering. These findings are supported by scanning electron microscopy, by density measurements and by current density versus electric field curves. The characterization of secondary phases through EDS assisted SEM and TEM is also reported in this work.

Influence of the oxygen adsorbed on tin varistors doped with Co, Mn and Cr oxides

The non-ohmic properties of the 98.90% SnO2+(1-x)%CoO+0.05% Cr2O3+0.05% Nb2O5+x% MnO2 varistor system (all of them in mol %), as well as the influence of the oxidizing and reducing atmosphere on this system were studied in this work. Experimental evidence indicates that the electrical properties of the varistor depend on the defects that occur at the grain boundary and on the adsorbed oxygen species such as O''(2), O'(2), O in this region. Thermal treatments at 900 degreesC in oxygen and nitrogen atmospheres indicated such a dependence with the values of the non-linearity coefficient (alpha) increasing under oxygen atmosphere, being reduced in nitrogen atmosphere and restored after a new treatment in oxygen atmosphere, presenting a reversibility in the process. EDS analysis accomplished by SEM showed the distribution of the oxides in the varistor matrix. (C) 2002 Kluwer Academic Publishers.