High-current measurement of the grain resistivity in zinc oxide varistor ceramics

A new pulse technique for grain resistivity measurement in varistor ceramics is suggested. Such technique allows obtaining more precise value of the grain resistivity due to the use of the concept of differential electrical resistance. This technique can be used in the current density range where the overheating of varistor sample is insignificant. The technique was verified using commercial ZnO varistors. Grain resistivities of 0.60±0.02 Ω cm at 293 K and of 3.40±0.13 Ω cm at 77 K were obtained. This result indicates the negative temperature coefficient of grain resistance in ZnO varistor in the range (77–293) K. The contribution of the grain boundaries to the current–voltage characteristic of ZnO varistor is estimated on the basis of the measured grain resistivity and the current–voltage data. It is shown that the electrical conduction in ZnO varistor is controlled by grains if the current density exceeds approximately 1000 А сm⁻².     

Effects of MgO doping in ZnO–0.5 mol% V2O5 varistors

The effects of MgO (0–40 mol%) on the microstructure and the electrical properties have been studied in a binary ZnO–0.5 mol% V₂O₅ system. The microstructure of the samples consists mainly of ZnO grains with MgO and γ-Zn₃(VO₄)₂ as the minority secondary phases. MgO is found to be effective as a grain growth inhibitor in controlling the ZnO grain growth, and a more uniform microstructure can be obtained. The non-linear coefficient α value is found to increase with the amount of MgO, and a highest value of 8.7 is obtained for the sample doped with 10 mol% MgO. Further addition of ≥20 mol% MgO decreases the α value.     

Cr2O3 doping in ZnO–0.5 mol% V2O5 varistor ceramics

The effects of the amount of Cr₂O₃ (0.5–4 mol%) on the microstructure and the electrical properties have been studied in a binary ZnO–0.5 mol% V₂O₅ system. The microstructure of the samples consists mainly of ZnO grains with ZnCr₂O₄ and α-Zn₃(VO₄)₂ as the minority secondary phases. The addition of Cr₂O₃ is found to be effective in controlling the abnormal ZnO grain growth often found in V₂O₅-doped ZnO ceramic system, and a more uniform microstructure can be obtained. The varistor performance is also improved as observed from the increase in the non-linear coefficient α of the Cr₂O₃-doped ZnO–V₂O₅ samples. The α value is found to increase with the amount of Cr₂O₃ for up to 3 mol% Cr₂O₃ content. Further increase in Cr₂O₃ is found to cause a decrease in the α value. The highest α value of 28.9 is obtained for the ZnO–0.5 mol% V₂O₅–3 mol% Cr₂O₃ sample.     

Microstructure and electrical properties of rare earth doped ZnO-based varistor ceramics

ZnO-based varistor ceramics doped with Nd₂O₃ and Y₂O₃ have been prepared by the conventional ceramics method. The phase composition, microstructure and electrical properties of the ceramics have been investigated by XRD, SEM and a V–I source/measure unit. The XRD and EDS analyses show the presence of ZnO, Bi₂O₃, Zn₇Sb₂O₁₂, Y₂O₃, Nd-rich phase and Y-containing Bi-rich phase. The electrical properties analyzed show that the nonlinear coefficient of the varistor ceramics is in the range of 4.4–70.2, the threshold voltage is in the range of 247.1–1288.8 V/mm, and the leakage current is in the range of 1.51–214.6 μA/cm². The 0.25 mol% Nd₂O₃ added varistor ceramics with 0.10 mol%Y₂O₃ sintered at 1050 °C exhibits excellent electrical properties with the high threshold voltage of 556.4 V/mm, the nonlinear coefficient of 61 and the leakage current of 1.55 μA/cm². The results illustrate that doping Nd₂O₃ and Y₂O₃ in ZnO-based varistor ceramics may be a very promising route for the production of the higher threshold voltage and the nonlinear coefficient of ZnO-based varistor ceramics.     

High Nonlinearity and High Voltage Gradient ZnO Varistor Ceramics Tailored by Combining Ga2O3, Al2O3, and Y2O3 Dopants

This paper deals with the electrical characteristics of rare‐earth‐doped ZnO varistor ceramics. Multiple donor dopants (Al³⁺, Ga³⁺, and Y³⁺) were employed to improve the comprehensive performance of ZnO varistor ceramics. The leakage current of rare‐earth‐doped ZnO varistor ceramics decreased noticeably with Ga₂O₃ dopants. The Ga³⁺ dopant occupies the defect sites of grain boundaries and increases the barrier potential of ZnO varistor ceramics, so the leakage current is effectively inhibited. Y₂O₃ is primarily located around the grains, which restrains ZnO grain growth, increasing the voltage gradient. The Al³⁺ goes into the lattices of ZnO grains, decreasing the grain resistance; thus, the residual voltage ratio can be controlled at low levels under a high impulse current. With the combined incorporation of Al³⁺, Ga³⁺, and Y³, excellent electrical properties of ZnO varistor ceramics can be acquired with a nonlinearity coefficient of 87, voltage gradient of 517 V/mm, leakage current of 0.96 μA/cm², and residual voltage ratio of 1.60. These rare multiple donor dopants can aid in engineering high‐quality ZnO varistors.     

Sintering of surfactant modified ZnO–Bi2O3 based varistor nanopowders

Surfactant modified nano-origin ZnO–Bi₂O₃ varistor powder was prepared in presence of cetyltrimethyl ammonium bromide (CTAB) surfactant through an aqueous reflux reaction at 100 °C. The compacted varistor discs made from the nano-origin powders were subjected to step-sintering, microwave sintering and solid-state sintering. The influences of CTAB in different sintering methods were analyzed from the densification characteristics, evolution of sintered microstructures and associated varistor properties (I–V). The conventional solid-state sintering produced 96% theoretical sintered dense samples at 1100 °C. The step and microwave sintered samples showed 93% and 99% sintered densities, respectively, with controlled microstructures having grain sizes in the range of 2–6 μm at the given conditions. The CTAB advantages were clearly seen in grain structuring and grain boundary properties, in addition to the enhanced densification and homogenous microstructures for obtaining high breakdown voltage and non-linearity coefficient.     

Two-step method fabricating high nonlinearity ZnVSb based varistors

A two-step method was introduced to fabricate ZnO–V₂O₅–Sb₂O₃ (ZnVSb) based varistor at low temperatures, such as 900–950 °C. Sb₂O₃/V₂O₅ (V/Sb) precursor was first synthesized and then used to replace Sb₂O₃ as one of the main dopants. The effect of its concentration on the microstructure and electrical properties of the ZnVSb based ceramic was investigated at doping levels up to 1.5 mol%. The microstructural homogeneity of the ceramic was greatly improved by the addition of the precursor. With increasing V/Sb precursor, the average grain size decreased, while the nonlinearity of the as sintered ceramic was enhanced (α_Max = 89). The ZnVSb ceramic is a promising material in the fabrication of multi-layered varistor, in which it could be co-sintered with pure Ag inner electrode.     

Microstructure and dielectric properties of Dy/Mn doped BaTiO3 ceramics

Dy/Mn doped BaTiO₃ with different Dy₂O₃ contents, ranging from 0.1 to 5.0 at% Dy, were investigated regarding their microstructural and dielectric characteristics. The content of 0.05 at% Mn was constant in all the investigated samples. The samples were prepared by the conventional solid state reaction and sintered at 1290°, and 1350 °C in air atmosphere for 2 h. The low doped samples (0.1 and 0.5 at% Dy) exhibit mainly fairly uniform and homogeneous microstructure with average grain sizes ranged from 0.3 μm to 3.0 μm. At 1350 °C, the appearance of secondary, abnormal, grains in the fine grain matrix and core–shell structure were observed in highly doped Dy/BaTiO₃. Dielectric measurements were carried out as a function of temperature up to 180 °C. The low doped samples sintered at 1350 °C, display the high value of dielectric permittivity at room temperature, 5600 for 0.1Dy/BaTiO₃. A nearly flat permittivity–temperature response was obtained in specimens with 2.0 and 5.0 at% additive content. Using a Curie–Weiss and modified Curie–Weiss low, the Curie constant (C), Curie like constant (C′), Curie temperature (T_C) and a critical exponent (γ) were calculated. The obtained values of γ pointed out the diffuse phase transformation in highly doped BaTiO₃ samples.     

Low-voltage ZnO varistor fabricated by the solution-coating method

A novel solution nano-coating technique, by coating ZnO powder with a mixed solution of dopants, has been developed to produce high performance low-voltage ZnO varistors. The sintering temperature in the present route is about 50 °C lower than that in the conventional oxide mixing route. The microstructure and electrical characteristics were examined by XRD, SEM and dc power supply and the results showed that the specimens prepared by the solution-coating route have bigger grain sizes, more evenly distributed intergranular phases, higher densities and nonlinearity coefficients, lower breakdown fields and leakage currents than those from the conventional oxide mixing route. The improved current–voltage properties are attributed to the excellent performance of the nano-composite ZnO powder and the advantages of the solution nano-coating technique.     

Microstructure, electrical properties, and aging behavior of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-Er2O3 varistor ceramics

The microstructure, electrical properties, and aging behavior of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-Er₂O₃ varistor ceramics were investigated for different contents of Er₂O₃. The microstructure consisted of ZnO grain and an intergranular layer (Pr, Y, and Er-rich phases) as a secondary phase. The increase of Er₂O₃ content decreased the average grain size and increased the sintered density. As the Er₂O₃ content increased, the breakdown field increased from 4206 V/cm to 5857 V/cm and the nonlinear coefficient increased from 32.6 to 48.6. The varistor ceramics added with 1.0 mol% Er₂O₃ exhibited excellent stability by exhibiting −0.2% in the variation rate of the breakdown field and −2.7% in the variation rate of the nonlinear coefficient for aging stress of 0.95 E_1 mA/150 °C/24 h.     

Microstructural, crystal structure and electrical characteristics of shock-consolidated Ga2O3 doped ZnO bulk

Ga₂O₃ (5 wt.%) doped zinc oxide (ZnO, 95 wt.%) bulk was fabricated by underwater shock compaction technique. The microstructural, crystal structure and electrical properties of shock-consolidated samples were investigated and compared to a commercially available sintered Ga₂O₃ (5 wt.%) doped ZnO (95 wt.%). The relative density of shock-consolidated sample was about 97% of the theoretical density, and no grain growth and lattice defects were confirmed. The grain boundary resistance was remarkably higher than that of commercial sintered Ga₂O₃ doped ZnO and nonlinear current-voltage (I-V) characteristics of shock-consolidated ZnO and Ga₂O₃ doped ZnO were very lower than that of commercial ZnO varistor.     

Sintering behavior and electromagnetic properties of Fe-deficient NiZn ferrites

Sintering behavior and electromagnetic properties of Ni_0.5Zn_0.5Fe_2−xO_4−3/2x ferrite (x = 0, 0.4, 0.8) by the sol–gel method are investigated. Fe deficiency in the composition enhances sintering and retards grain growth. The near fully dense Fe-deficient samples could be obtained at a sintering temperature as low as 1120 °C and the highest relative density appears in the x = 0.8 sample sintered at 1150 °C. Second phase zincite ZnO resulting from Fe deficiency plays an important role in spinel NiZn ferrites by acting as a grain growth inhibitor and the grain growth of NiZn ferrite is effectively suppressed. When the sintering temperature is above 1200 °C, extensive grain growth occurs due to the probability of serious volatilization of zinc at high temperatures. The ratio of Ni to Zn of NiZn ferrites increases with increasing Fe deficiency due to the separation of zinc from spinel lattice, which results in the decrease in initial permeability and the increase in Curie temperature and resonant frequency.     

Shock-sintering of low-voltage ZnO-based varistor ceramics with Bi4Ti3O12 additions

Microstructure development in ZnO ceramics with Bi₄Ti₃O₁₂ (BIT) additions was studied in dependence of sintering temperature, inversion boundary (IBs) nucleation, heating rate and doping with transition metal oxides (NiO, MnO₂ and Co₃O₄). We demonstrated that one of the essential conditions for homogeneous microstructure development in this system is rapid release and efficient distribution of TiO₂, necessary for the formation of Ti-rich (tail-to-tail) IBs in ZnO grains. This can be achieved via the so-called shock-sintering procedure described in this article. Immediate decomposition of BIT to TiO₂-rich Bi₂O₃ liquid phase above 1200 °C leads to nucleation of ZnO grains with IBs. Exploiting the growth of ZnO grains with IBs, microstructure development can be easily controlled via the IB-induced grain growth mechanism, previously described in SnO₂-doped and Sb₂O₃-doped ZnO. In contrast to conventional sintering, where erratic nucleation of IBs leads to bimodal grain size distribution, shock-sintering sintering regime produces microstructures with uniform coarse-grain sizes, required for low-voltage varistor ceramics.     

Investigation on the origin of the giant dielectric constant in CaCu3Ti4O12 ceramics through analyzing CaCu3Ti4O12-HfO2 composites

A full range of CaCu₃Ti₄O₁₂-HfO₂ (CCTO-HfO₂) composites were prepared by sintering mixtures of the two components at 1000 °C for 10 h. X-ray diffraction studies confirmed the two-phase nature of the composites. The evolution of the microstructure in the composites, in particular, the size distribution of CCTO grains, was examined by scanning electron microscopy. The studies showed that, as more HfO₂ was added, the abnormal grain growth of CCTO and coarsening of the microstructure were gradually suppressed. As a result, the average CCTO grain size was reduced from 50 to 1 μm. The measured dielectric constants agree well with the values calculated from Lichtenecker's logarithmic law, using only the dielectric constants of pure CCTO and HfO₂ as two end points. The agreement suggests to us that the dielectric constant of CCTO is dominated by domain boundaries within the grains rather than by grain boundaries between the grains.     

Morphology investigation of mechanically activated ZnO–SnO2 system

Powder mixtures of zinc oxide and tin oxide in the molar ratio, ZnO:SnO₂ = 2:1, were mechanically activated in a planetary ball mill in the time intervals of 0–160 min. The adsorption–desorption isotherms, specific surface area, pore volume and pore size distribution spectra of mechanically activated powder mixtures were established by N₂ adsorption at 77 K. Microstructure analysis was performed using scanning electron microscopy (SEM) and digital pattern recognition (DPR) microstructure quantity analysis. The phase composition of the mixed powders was determined by X-ray analysis. Mechanochemical activation of the ZnO–SnO₂ system resulted in fine grinding of the starting particles and generation of contacts between them, mass transfer at contacts zones and formation of Zn₂SnO₄ spinel, which was observed after 40 min of activation.     

Electrical properties and AC degradation characteristics of low voltage ZnO varistors doped with Nd2O3

The electrical properties and degradation characteristics of low voltage ZnO varistors were investigated as a function of Nd₂O₃ content. The varistor ceramics with 0.03 mol% Nd₂O₃ sintered at 1250 °C were far more densified than those with 0.06, 0.09 and 0.12 mol% Nd₂O₃. The addition of Nd₂O₃ to the low voltage ZnO varistors greatly improved the current–voltage characteristics; the nonlinear coefficient of varistors increase from 12.2 to 34.6 with increasing Nd₂O₃ content. The samples with 0.03 mol% Nd₂O₃ showed excellent stability due to high density and relatively good V–I characteristics, with the nonlinear coefficient of 22.5 and the leakage current of 9.6 μA. Their variation rate of varistor voltage and nonlinear coefficient and leakage current were −4.7%, −5.4%, 18.3%, respectively, under AC degradation stress (1.0 V_1 mA/125 °C/24 h).     

Formation of rod-like Si3N4 grains in porous SRBSN bodies using 6Y2O3–2MgO sintering additives

The porous reaction-bonded silicon nitride (RBSN) bodies using (6 wt.% Y₂O₃–2 wt.% MgO) 6Y2M were fabricated by nitridation process at 1350 °C for 8 h. The porous gas pressure sintered (GPSed)-RBSN bodies post-sintered at 1550–1850 °C for 6 h show a microstructure with low aspect ratios having high porosity. The compressive strength of samples sintered at 1650 °C, 1750 °C and 1850 °C were about 146 MPa, 251 MPa and 285 MPa, respectively. The duration time for sintering had a significant effect on the microstructure and grain morphology of the GPSed-RBSN bodies. Even though the GPSed-RBSN was carried out at the comparatively low temperature (1550 °C) for 9 h, high aspect ratio of rod-like Si₃N₄ grains with about 9 was observed. The material properties of samples such as porosity, phase ratio (β/(α + β)) and compressive strength of sample sintered at 9 h were about 43.2%, 99% and 141 MPa, respectively.     

Inversion boundary induced grain growth in TiO2 or Sb2O3 doped ZnO-based varistor ceramics

In low-voltage varistor ceramics, the phase equilibrium and the temperature of liquid-phase formation are defined by the TiO₂/Bi₂O₃ ratio. The selection of a composition with an appropriate TiO₂/Bi₂O₃ ratio and the correct heating rate is important for the processing of low-voltage varistor ceramics. The total amount of added Bi₂O₃ is important as the grain growth is slowed down by a larger amount of Bi₂O₃-rich liquid phase at the grain boundaries. Exaggerated grain growth in low-voltage varistor ceramics is related to the occurrence of the liquid phase and the presence of TiO₂ which triggers the formation of inversion boundaries (IBs) in only a limited number of grains, and as a result the final microstructure is coarse grained. The Zn₂TiO₄ spinel phase only affects grain growth in compositions with a TiO₂/Bi₂O₃ ratio higher than 1.5. In high-voltage varistor ceramics, just a small amounts of Sb₂O₃ trigger the formation of IBs in practically every ZnO grain, and in compositions with a Sb₂O₃/Bi₂O₃ ratio lower than 1, grain growth that is controlled entirely by an IBs-induced grain growth mechanism results in a fine-grained microstructure. The spinel phase interferes with the grain growth only at higher Sb₂O₃/Bi₂O₃ ratios.     

Structural,dielectric properties and electrical conduction behaviour of Dy substituted CaCu3Ti4O12 ceramics

Dy substituted CCTO ceramics were synthesized using solid state reaction method. Effect of Dy on structural, microstructural, dielectric and electrical properties has been studied over a wide temperature (300–500 K) and frequency range (100 Hz–1 MHz). Rietveld refinement, carried out on the samples, confirmed single phase formation and indicated overall decrease in lattice constant. Microstructure showed bimodal distribution of grains in CCTO with bigger grains surrounded by smaller grains. Dy substitution reduced grain size. Dy substitution in CCTO reduces the dielectric constant which may be attributed to increase of the Schottky potential barrier. The dielectric constant remains nearly constant in temperature range 300–400 K. The AC conductivity obeys a power law, σ_ac=A fⁿ, where n is the temperature dependent frequency exponent. The AC conductivity behaviour can be divided into three regions, over entire temperature range, depending on conduction processes. The relevant charge transport mechanisms have been discussed.     

Nucleation and growth of basal-plane inversion boundaries in ZnO

Grain growth studies of zinc oxide ceramics have indicated that inversion boundaries (IBs) are growth faults that control the growth of the zinc oxide (ZnO) grains. To substantiate this observation, we designed experiments to study the nucleation of IBs. Low-temperature experiments showed that in the ZnO–SnO₂ system, IBs form before the Zn₂SnO₄ spinel phase and grains with IBs grow exaggeratedly at the expense of the normal ZnO grains until they completely dominate the microstructure. Experiments using ZnO single crystals embedded into ZnO powder with the addition of SnO₂, Sb₂O₃ and In₂O₃ showed that depending on the oxidation state of the IB-forming dopant ions, there are two competing mechanisms of IB nucleation: (i) internal diffusion, and (ii) surface nucleation and growth. The first mechanism is typical for III+ dopants and is controlled by Zn-vacancy diffusion, whereas the second mechanism holds for all IB-forming dopants and is controlled by chemisorption of the dopants on Zn-deficient (0 0 0 1) surfaces. In both cases, the driving force for the inversion is the preservation of the local charge balance.