Effect of the addition of ZnO seeds on the electrical proprieties of ZnO-based varistors

ZnO has the characteristic of presenting an intermediate value for the effective 3 eV barrier at room temperature. ZnO ceramics are applied in high-voltage systems or circuits. Attempts were made to reduce the number of effective barriers in the system by adding large particles of ZnO to the varistor composition. This procedure reduced the breakdown field of the varistors by values up to 90% lower than those initially obtained, and produced nonlinear coefficients as low as 20. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Importance of oxygen atmosphere to recover the ZnO-based varistors properties

A methodology to recover the non-ohmic properties of ZnO based varistors after degradation with long and short duration pulses was proposed in this work. The basic idea consists in submitt the degraded ceramics at different temperatures and oxygen flows. Thermal treatment at 900 degrees C for 2 h with oxygen flow of 15 l/h allowed to obtain better non-linear coefficient (alpha= 52.5) compared to the standard sample. Rietveld refinement showed that with the thermal treatment, the oxygen species and the beta-Bi2O3 phase, lost in the degradation process, are recovered in the grain boundary.

Influence of Ta2O5 on the electrical properties of ZnO- and CoO-doped SnO2 varistors

SnO2-based varistors doped with 0.5% cobalt, 0.5% zinc and various tantalum amounts were prepared by the solid-state route. Experimental evidence shows that small quantities of Ta2O5 improve the nonlinear properties of the samples significantly. It was found that samples doped with 0.05 mol% Ta2O5 exhibit the highest density (98.5%), the lowest electric breakdown field (E-b = 1050 V/cm) and the highest coefficient of nonlinearity (alpha = 11.5). The effect of Ta2O5 dopant could be explained by the substitution of Ta5+ by Sn4+. (C) 2004 Elsevier Ltd and Techna S.r.l. All rights reserved.

Analysis of secondary phases segregated and precipitated in SnO2-based varistors

Transmission and scanning electron microscopy techniques were used to study the heterogeneities found in the microstructure of (SnO2Co3O4Nb2O5Fe2O3)-Co-.-Nb-.-Fe-. and (SnO2ZnONb2O5FC2O3)-Zn-.-Nb-.-F-. varistors. Second phases encountered both inside the grains and ingrain boundary regions were identified using energy dispersive spectrometry and electron diffraction patterns. Through the electrical characterisation, the presence of iron oxide among the additives was determined to highlight the non-linear properties of the specimens. A discussion on the influence of second phases on the non-linear features of these systems is also addressed. (C) 2004 Elsevier Ltd. All rights reserved.

Nonlinear characteristics of Cr2O3, WO3, ZnO and CoO doped SnO2 varistors

SnO2 based ceramics doped with 1.0 mol% ZnO, 1.0 mol% CoO, 0.1 mol% WO3 and 0.05 mol% Cr2O3 show varistor behavior with nonlinear coefficient alpha = 33, breakdown electric field E-B = 12.5 kV/cm, leakage current I = 0.63 mA/cm(2) and average grain size of 1.52 mu m. Experimental evidence shows that the addition of Cr2O3 improves the nonlinear properties of the samples significantly, the impedance data, represented by means of Nyquist diagrams, show a dramatic increase in the resistivity for the samples doped with Cr2O3. (C) 2005 Elsevier B.V. All rights reserved.

Influence of La2O3, Pr2O3 and CeO2 on the nonlinear properties of SnO2 multicomponent varistors

The influence of La2O3, Pr2O3 and CeO2 on a new class of polycrystalline ceramics with nonlinear properties based on SnO2, was investigated. La2O3 and Pr2O3 were found to precipitate at the grain boundary region, causing a considerable increase in the nonlinear behavior. It was found that CeO2 forms a solid solution in the bulk but. unlike La2O3 and Pr2O3, it does not increase the nonlinear behavior. A higher nonlinear coefficient of similar to80 was obtained for La2O3-doped SnO2-based systems. (C) 2002 Elsevier B.V. B.V. All rights reserved.

The failure analyses on ZnO varistors used in high tension devices

The main purpose of this work is to evaluate the failure caused by electrical discharge on commercial ZnO varistor doped with oxide of Bi, Sb, Si, Cr, Co utilized in electric transmission systems. In order to observe the effect of electrical discharge over the microstructure and electrical properties of the varistors, two kinds of pulses were applied: long pulse (2000 ms) and short pulse (8/20 mu s). In both cases, a decrease in grain size and increase in micropores and leakage current were observed. The degraded samples present oxygen defficiency mainly in the grain boundary and phase tranformation from the bismuth oxide phase. (c) 2005 Springer Science+ Business Media, Inc.

Recent research developments in SnO2-based varistors

This paper discusses some advances in research conducted on SnO2-based electroceramics. The addition of different dopants, as well as several thermal treatments in oxidizing and inert atmospheres, were found to influence the microstructure and electrical properties of SnO2-based varistor ceramics. Measurements taken by impedance spectroscopy revealed variations in the height and width of the potential barrier resulting from the atmosphere in which thermal treatments were performed. High nonlinear coefficient values, which are characteristic of high-voltage and commercial ZnO varistors, were obtained for these SnO2-based systems. All the systems developed here have potentially promising varistor applications. (C) 2004 Elsevier B.V. All rights reserved.

The influence of the synthesis route on the final properties of SnO2-based varistors

A comparative study of two customary routes of ceramics processing applied to the synthesis of SnO2-based varistors is reported in this paper. Devices of equivalent composition were prepared through the Pechini method and through directly mixing the oxides without the addition of anti-agglomerants or binders. The microstructures of the sintered samples were characterised with X-ray diffraction and scanning and transmission electron microscopies. The electrical behaviour of the devices was studied on the basis of the current density versus electric field (J-E) characteristics and impedance spectroscopy measurements. The Pechini method ensures the homogeneity in the distribution of the additives in the tin oxide matrix but the formation of secondary phases seems to be independent of the synthesis route. Devices with similar non-linear coefficients of 18 and 21 were obtained through the mixed oxides route and the Pechini method, respectively. (C) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

A new interpretation for the degradation phenomenon of ZnO varistors

The electrical degradation phenomena of zinc oxide-based varistors were studied using a high-energy current pulse and a.c. polarization at different temperatures. Activation energy measurements during the degradation process showed that these phenomena are associated with diffusion and that the diffusion-controlling species are slower than Zn., For degradation promoted by current pulses of 8×20 μs, the Schottky potential barrier deformation was measured. A decrease in height and width of the potential barrier due to the reduction of surface states density, N s, without a significant change in donor density, N d, was observed. To explain these results, a modification of the unstable components model is proposed for the potential barrier in which the degradation is due to oxi-reduction reactions between atomic defects. These reactions promote the elimination of zinc vacancies and/or adsorbed oxygen on the grain boundaries. © 1992 Chapman & Hall.

Effect of seed addition on SnO2-based varistors for low voltage application

The effect of seed addition on the microstructure and non-ohmic properties of the SnO2 + 1%CoO + 0.05%Nb2O5 ceramic-based system was analyzed. Two classes of seeds were prepared: 99% SnO2 + 1%CuO and 99% SnO2 + 1%CoO (mol%); both classes were added to the ceramic-based system in the amount of 1%, 5%, and 10%. The two systems containing 1% of seeds resulted in a larger grain size and a lower breakdown voltage. The addition of 1% copper seeds produces a breakdown voltage (V b) of ∼ 37 V and a leakage current (fic) of 29 μA. On the other hand, the addition of 1% cobalt seeds produced a breakdown voltage of 57 V and a leakage current of 70 μA. Both systems are of great technological interest for low voltage varistor applications, by means of appropriate strategies to reduce the leakage current. Using larger amounts of seeds was not effective since the values of breakdown voltage in both cases are close to a system without seeds. To our knowledge, there are no reports in the literature regarding the use of seeds in the SnO2 system for low voltage applications. A potential barrier model which illustrates the formation of oxygen species (O′2(ads), O′ads, and O″ads) at the expense of clusters near the interface between grains is proposed. © 2012 The American Ceramic Society.

Degradation analysis of the SnO2 and ZnO-based varistors using electrostatic force microscopy

The degradation phenomena of ZnO and SnO2-based varistors were investigated for two different degradation methods: DC voltage at increased temperature and degradation with 8/20 μs pulsed currents (lightning type). Electrostatic force microscopy (EFM) was used to analyze the surface charge accumulated at grain-boundary regions before and after degradation. Before the degradation process, 85% of the barriers are active in the SnO2 system, while the ZnO system presents only 30% effective barriers. Both systems showed changes in the electrical behavior when degraded with pulses. In the case of the ZnO system, the behavior after pulse degradation was essentially ohmic due to the destruction of barriers (about 99% of the interfaces are conductive). After the degradation with 8/20 μs pulsed currents, the SnO2 system still presents nonohmic behavior with a significant decrease in the quantity of effective barriers (from 85% to 5%). However, when the degradation is accomplished with continuous current, the SnO2 system exhibits minimum variation, while the ZnO system degrades from 30% to 5%. This result indicates the existence of metastable defects of low concentration and/or low diffusion in the SnO2 system. High energy is necessary to degrade the barriers due to defect annihilation in the SnO2 system. © 2013 The American Ceramic Society.

Influence of the concentration of Sb2O3 on the electrical properties of SnO2 varistors

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Comparative electrical behavior at low and high current of SnO(2)- and ZnO-based varistors

The complete I-V characteristics of SnO(2)-based varistors, particularly of the Pianaro system SCNCr consisting in 98.9%SnO(2)+1%CoO+0.05%Nb(2)O(5)+0.05%Cr(2)O(3), all in mol%, have been seldom reported in the literature. A comparative study at low and high currents of the nonohmic behavior of SCNCr- and ZnO-based varistors (modified Matsuoka system) is proposed in this work. The SCNCr system showed higher nonlinearity coefficients in the whole range of measured current. The electrical breakdown field (E(b)) was twice as high for the SCNCr system (5400 V/cm) than for the ZnO varistor (2600 V/cm) due to a smaller average grain size of the former (4.5 mu m) with respect to the latter (8.5 mu m). Nevertheless, we consider that another important factor responsible for the high E(b) in the SCNCr system is the great number of electrically active interfaces (85%) as determined with electrostatic force microscopy (EFM). It was also established that the SCNCr system might be produced in disks of smaller dimensions than that of commercial ZnO-based product, with a 5.0 cm(-1) minimal area-volume (A/V) ratio. The SCNCr reached the saturation current in a short time because of the high resistivity of the grains, which is five times higher than that of the grains in ZnO-based varistors.

Field-dependent changeover from current-to voltage-limiting characteristics by non-linear n-type BaTiO3 ceramics

Non-linear resistors having current-limiting capabilities at lower field strengths, and voltage-limiting characteristics (varistors) at higher field strengths, were prepared from sintered polycrystalline ceramics of (Ba0.6Sr0.4)(Ti0.97Zr0.03)O3+0.3 at % La, and reannealed after painting with low-melting mixtures of Bi2O3 + PbO +B2O3. These types of non-linear characteristics were found to depend upon the non-uniform diffusion of lead and the consequent distribution of Curie points (T c) in these perovskites, resulting in diffuse phase transitions. Tunnelling of electrons across the asymmetric barrier at tetragonak-cubic interfaces changes to tunnelling across the symmetric barrier as the cubic phase is fully stabilized through Joule heating at high field strengths. Therefore the current-limiting characteristics switch over to voltage-limiting behaviour because tunnelling to acceptor-type mid-bandgap states gives way to band-to-band tunnelling.