Phase development in ZnO varistors

Based on a typical ZnO varistor composition (97·0 mol.-% ZnO, 1·0 mol.-% Bi₂O₃, 1·0 mol.-% Sb₂O₃, 0·5 mol.-% MnO and 0·5 mol.-% Co₃O₄), phase development of the ZnO varistor during sintering has been investigated using in situ high temperature X-ray diffraction up to 900°C, and conventional ambient X-ray diffraction for samples sintered at 900°C to 1250°C. The results indicate that α-Bi₂O₃ can be detected until 700°C; the pyrochlore phase can be detected in the samples heat treated at 700°C and up to 1250°C; the spinel phase is present at and >900°C. However, the main phases in the varistor are established by 950°C. By this temperature, the essential microstructure features are formed, and the varistors exhibit non-linear electrical properties, with a non-linear coefficient α of 35 and breakdown field of 8000 V cm^?1. With increasing sintering temperature, both the α value and breakdown field decrease.     

Influence of sintering on microstructure and electrical properties of ZnO-based multilayer varistor (MLV)

The effect of sintering on microstructure, dielectric property and varistor property of ZnO-based multilayer varistor (MLV) were investigated. The results show that an optimum microstructure of ZnO-based MLV can be obtained when sintering at 950 °C/1.5 h. The reaction between ZnO and Sb₂O₃ is noted. Also, the segregation of Bi₂O₃ to the inner electrode and thus the reaction of Bi₂O₃ with Pd are observed. The V_B and α value of ZnO-based MLV can be controlled in a straightforward manner through the control of grain size. The decrease in V_B directly relates to the grain growth of ZnO grains when increasing the sintering temperatures from 900 to 1050 °C. Moreover, the increase of capacitance with sintering temperature may mainly result from the coalescence of ZnO matrix grains. The energy absorption capabilities in terms of electro-static discharge (ESD) and peak current (PC) measurements of ZnO-based MLV are reported. The optimum varistor properties of ZnO-based MLV can be obtained when sintering at 950 °C.     

High temperature stable dielectric properties and enhanced energy-storage performance of (1− x)(0.85Na0.5Bi0.5TiO3 − 0.15Ba0.8Ca0.2Ti0.8Zr0.2O3)− xK0.5Na0.5NbO3 lead-free ceramics

Novel high temperature ceramic capacitors (1??x)(Na_0.5Bi_0.5TiO₃ ??0.15Ba_0.8Ca_0.2Ti_0.8Zr_0.2O₃)??xK_0.5Na_0.5NbO₃ were synthesized in the solid-state reaction route. The influence of K_0.5Na_0.5NbO₃ modification on dielectric behavior, energy-storage properties, ac impedance and temperature stable dielectric performance were systematically investigated. The reduced grain size and enhanced relaxor properties are obtained with the addition of KNN. The content of x?=?0.1 exhibits a stable permittivity (~ 1630) and dielectric loss (<?0.05) over a relatively broad temperature range (66–230?°C). A variation in permittivity within ±?15% can be observed over a pretty wide temperature range of 66–450?°C. Beyond that, this ceramic shows enhanced energy-storage properties with the density (W_rec) of 0.52?J/cm³ and efficiency (η) of 80.3% at 110?kV/cm. The possible contributions of the grain and the grain boundary to the ceramic capacitance are discussed by the ac impedance spectroscopy.     

Cold sintering ZnO based varistor ceramics with controlled grain growth to realize superior breakdown electric field

Controlling the grain growth and grain boundary morphology is of great importance in the manipulation of electrical properties of electro-ceramics. However, it has been a challenge to achieve dense varistor ceramics with grain sizes in submicrons and nanometers using conventional thermal sintering at high temperatures. Here we present a strategy to fabricate dense ZnO based ceramics with controlled grain growth and thin grain boundaries using cold sintering process (CSP). With CSP, the sintering temperature of ZnO based ceramics dramatically drops from 1100 °C to 300 °C. The Bi₂O₃, Mn₂O₃, and CoO dopants suppress the grain growth of ZnO under CSP conditions, and Bi-rich intergranular films (2?5 nm) can be observed along grain boundaries. The cold sintered ZnO-Bi₂O₃-Mn₂O₃-CoO ceramic shows a non-linear coefficient of 33.5, and a superior breakdown electric field of 3550 V/mm. This work thus demonstrates that CSP is a promising technique for designing new submicron-/nano-ceramics with superior performances.     

Microstructure and electrical properties of ZnO–ZrO2–Bi2O3–M3O4 (MCo,Mn) varistors

Phase evolution, microstructure and the electrical properties of ZrO₂-added pyrochlore-free ZnO–Bi₂O₃–M₃O₄ (MCo, Mn) varistors have been studied as functions of ZrO₂ content up to 10 vol% and the sintering temperature between 900 and 1300 °C. Zirconia remained as intergranular second phase particles up to 1100 °C, which retarded densification and inhibited the grain growth of ZnO. At higher temperatures, on the contrary, ZrO₂ particles began to be entrapped in ZnO grains and irreversibly transform from monoclinic to stable cubic phase dissolving transition metal ions. The grain size of ZnO decreased with increasing ZrO₂ content, and increased with the increase of the sintering temperature. Accordingly breakdown voltage changed with both ZrO₂ content and the sintering temperature as was expected. Nonlinear coefficient (α) depended primarily on the sintering temperature: it increased to >40 up to 1000 °C, and significantly decreased to <30 at higher temperatures probably due to the volatilization of Bi₂O₃. While the specimens sintered at 1200 °C or above had relatively high leakage current (I_L) and large clamping ratio (C_R), those with ZrO₂ content of 0.5–5.0 vol% and sintered below 1200 °C revealed low I_L of ⩽20 μA/cm² and C_R well below 2.0. In spite that varistor characteristics of ZrO₂-added system could not match those of commercial ZnO varistors, its low temperature sinterability and ease of breakdown voltage control via ZrO₂ content without a serious loss of its figures of merit are worth noticing, particularly for multi-layered chip varistor (MLV) application.     

Effects of Sb2O3 on the microstructure and electrical properties of ZnO–Bi2O3-based varistor ceramics fabricated by two-step solid-state reaction route

In this work, the ZnO–Bi₂O₃–Cr₂O₃–Co₂O₃–MnO₂ varistors doped with different content of Sb₂O₃ were prepared by two-step solid-state reaction route, including a pre-calcining of the mixtures of nanosized ZnO and the other additives at an optimized temperature, followed by a consequent sintering process at different temperatures. Meanwhile, the effects of Sb₂O₃ on the sintering temperature, microstructure and electrical properties of the objective varistors were investigated. It was found the densification temperature went up in a proper range and the content of pyrochlore phase, spinel phase and β-Bi₂O₃ phase increased with the increasing content of Sb₂O₃, while the grain size of ZnO–Bi₂O₃-based varistor reduced. The results demonstrated that at the same sintering temperature, the second particles increased with the increasing amount of Sb₂O₃, which was helpful to control the grain growth, leading to a higher breakdown voltage. However, the decrease of α-Bi₂O₃ phase (melting point of α-Bi₂O₃ phase is 825 °C), which is the main component of the liquid Bi₂O₃ phase in the sample during sintering process, leads to the increase of the sintering temperature of the green pallet. As a result, the ZnO varistor doped with 3.0 mol% Sb₂O₃ sintered at 1000 °C exhibited the highest breakdown voltage of 1863.3 V/mm. By contrast, the ZnO varistor without Sb₂O₃ doping sintered at 900 °C had the optimum nonlinear coefficient of 59.8.     

Effect of Nb2O5 on ZnBiMnO varistor ceramic prepared by solid-state sintering at 850°C

Nb₂O₅ is a commonly used donor dopant for ZnO-based varistor ceramics, but its effect, especially on the low-temperature sintered ZnO varistor ceramics, is not fully understood. To provide a possible answer to this problem, ZnO–Bi₂O₃–MnCO₃ (ZnBiMnO) based varistor ceramics with 0.05%–0.3% (in mole ratio) Nb₂O₅ were fabricated by solid-state sintering at 850 °C for 3 h. Their microstructure and nonlinear electrical properties were studied by XRD, SEM and the standard current-voltage (I–V) tests to reveal the effect of Nb₂O₅. With the increase of Nb₂O₅ from 0.05 mol% to 0.3 mol%, more solid Bi₅Nb₃O₁₅ inter-granular particles form within the ceramic during sintering, thereby decreasing the Bi-rich liquid phase. As a result, the average size of ZnO grain decreases from 4.35 μm to 1.67 μm. This microstructural change leads to the increase of the breakdown voltage in the range of 821 V/mm to 1851 V/mm. The ZnBiMnO varistor ceramic with 0.1 mol% Nb₂O₅ shows the best nonlinear properties. The optimum nonlinear coefficient is 35.81, the breakdown voltage is 907.51 V/mm, and the leakage current is 7.72 μA/cm². The result of this study provides a promising candidate material for manufacturing the multilayered low-voltage varistor that may use Ag, Ni or even Cu as the inner electrodes.     

Bi2O3 vaporization from ZnO-based varistors

Bi₂O₃-doped ZnO ceramic varistors are usually sintered at temperatures near to 1200 °C in the presence of a Bi-rich liquid phase, which is partially vaporized during the sintering process. Volatilization of bismuth oxide depends on the total surface area in direct contact to the reaction atmosphere and this in turn is related to the area/volume ratio of the ceramic compact. This loss of Bi₂O₃ has a significant role on the development of the varistor microstructure and more specifically ZnO grain growth, which is strongly enhanced by the presence of the liquid phase, should be particularly affected. In the present paper, X-ray fluorescence analysis is performed to describe the Bi₂O₃ vaporization profile as a function of distance to the outer surface, taking into account its influence on microstructural evolution.     

Gibbs free energy of formation of Bi2O3 from EMF cells with δ-Bi2O3 solid electrolyte

Determination of thermodynamic data on the formation of Bi₂O₃ was established by emf measurements as a function of temperature in the range 660–820°C on the system Metal, Bi(1)|Bi₂O₃|Pt, O₂. From the results using a tungsten electrode the following relation was found: ΔG⁰ = ?(134.7 ± 1.2) + (64.0 ± 1.2) × 10^?3 T kcal mole^?1 (validity range: 940–1080 K). Standard thermodynamic data at 298 K were calculated as ΔG⁰ = ?119.2 ± 2.1 kcal mole^?, ΔH⁰ = ?139.0 ± 1.2 kcal mole^?1, and ΔS⁰ = ?66.3 ± 1.2 eu.     

The characteristics of ZnO–Bi2O3-based varistor ceramics doped with Y2O3 and varying amounts of Sb2O3

ZnO–Bi₂O₃-based varistor samples doped with 0.45 mol% of Y₂O₃ and varying amounts of Sb₂O₃ in the range from 1.8 to 0.0 mol% were fired at 1230 °C. Only in the samples co-doped with Sb₂O₃ did doping with Y₂O₃ resulted in the formation of a fine-grained Bi–Zn–Sb–Y–O phase (the Y₂O₃-containing phase) at the grain boundaries, which very effectively hinders the grain growth. Despite of a decrease in the amount of added Sb₂O₃ from 1.8 to 0.45 mol% and a significant decrease in the amount of spinel phase the samples had a similar ZnO grain size and a threshold voltage of 200 V/mm. The results confirmed that doping with Y₂O₃ is a very promising route for the production of fine-grained high-voltage ZnO–Bi₂O₃-based varistor ceramics, and determining the proper amounts of added Sb₂O₃ and Y₂O₃ is of great importance.     

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.     

A highly conductive Ce0.8Nd0.2O1.9 electrolyte with double sintering aids for intermediate-temperature solid oxide fuel cells

In this paper, the influence of Bi/Zn mass ratio on the phase composition, microstructure, sintering properties, and electrical properties of Bi/Zn co-added Nd_0.2Ce_0.8O_1.9 (NDC) used for intermediate-temperature solid oxide fuel cells (SOFCs) was investigated. At 700 °C, the total conductivity of the NDC-based electrolyte (3Bi/1Zn-NDC) with the mass ratio 3:1 for Bi₂O₃ and ZnO was as high as 5.89 × 10^?2 S cm^?1, 4.60 and 4.51 times higher than the single addition of 4 wt% Bi₂O₃ and 4 wt% ZnO, respectively. In addition, the 3Bi/1Zn-NDC electrolyte exhibited a good physical and chemical compatibility with the electrode materials. The open circuit voltage (OCV) of the cell supported by the 3Bi/1Zn-NDC electrolyte was 0.67 V, and the output power density could reach 402.25 mW cm^?2 at 700 °C. It showed stable power output and OCV in the long-term stability test within 50 h. Overall, the combination of 3 wt% Bi₂O₃ and 1 wt% ZnO was a very effective dual sintering aid for NDC electrolyte.     

Temperature-stable dielectric ceramics based on Na0.5Bi0.5TiO3

Multiple ion substitutions to Na_0.5Bi_0.5TiO₃ give rise to favourable dielectric properties over the technologically important temperature range ?55?°C to 300?°C. A relative permittivity, ε_r,?=?1300?±?15% was recorded, with low loss tangent, tanδ?≤?0.025, for temperatures from 310?°C to 0?°C, tanδ increasing to 0.05 at ?55?°C (1?kHz) in the targeted solid solution (1–x)[0.85Na_0.5Bi_0.5TiO₃–0.15Ba_0.8Ca_0.2Ti_1-yZr_yO₃]–xNaNbO₃: x?=?0.3, y?=?0.2. The ε_r-T plots for NaNbO₃ contents x?<?0.2 exhibited a frequency-dependent inflection below the temperature of a broad dielectric peak. Higher levels of niobate substitution resulted in a single peak with frequency dispersion, typical of a normal relaxor ferroelectric. Experimental trends in properties suggest that the dielectric inflection is the true relaxor dielectric peak and appears as an inflection due to overlap with an independent broad dielectric peak. Process-related cation and oxygen vacancies and their possible contributions to dielectric properties are discussed.     

Varistor and Magnetic Properties of Nickel Copper Zinc Niobium Ferrite Doped with Bi2O3

Bi₂O₃ was added into nickel copper zinc niobium ferrite and treated with different thermal processes to change the grain‐boundary chemical composition. The relationship between the grain‐boundary composition and varistor properties were investigated using scanning electron microscopy, transmission electron microscopy, energy dispersion spectroscopy, and X‐ray photoelectric spectroscopy. The experimental results show that Bi₂O₃ reacts and diffuses into the spinel ferrite grain, forming bismuth iron compounds, causing the spinel ferrite chemical composition near grain boundary becomes iron deficient. The Fe deficiency spinel ferrite near the grain boundary then changes into p‐type conduction. The annealing process after sintering improves the bismuth oxide diffusion and chemical reaction near the grain boundary, which can increase the grain‐boundary resistivity. The n‐type semiconductive grain interior and p‐type spinel ferrite near the grain‐boundary combination can form a double Schottky barrier, leading the specimen to exhibit varistor properties. A multifunctional varistor‐magnetic material with a nonlinear coefficient of 10 and initial permeability of about 225 at 10 MHz can be successfully fabricated by sinteringNi_0.2881Cu_0.1825Zn_0.4802Nb_0.0096Fe_2.0168O₄ ferrites added with 5 mol% Bi₂O₃ sintered at 950°C, then annealed at 650°C for 1 h.     

Effect of ZnBi2O4 and Bi2O3 addition on the densification,microstructure, and varistor properties of ZnO varistors

In this study, 1 wt% Bi₂O₃ (1B), 1 wt% ZnBi₂O₄ (1BZ), and a composite (a mixture of 1 wt% Bi₂O₃ and various amounts (1-4 wt%) of ZnBi₂O₄ ,1B1BZ-1B4BZ) were added to ZnO varistors to investigate the effects of additives on the densification, microstructure, and varistor performance. The results showed that the addition of ZnBi₂O₄ can lower the densification temperature to about 850^oC. When the additive was changed from 1 wt% Bi₂O₃ to 1 wt% ZnBi₂O₄, the α value increased from 42 to 54, the breakdown voltage increased from 775 V/mm to 1011 V/mm, and the leakage current decreased to 0.11 μA. Additions of ZnBi₂O₄ and transition metal cations as donor dopants for the ZnO varistors promote oxygen chemisorption at grain boundaries, resulting in greater α value and lower leakage currents. This suggests the addition of ZnBi₂O₄ can effectively promote densification and improve the varistor properties of ZnO varistors.     

Electrical impedance spectroscopy and structural characterization of liquid-phase sintered ZnO–V2O5–Nb2O5 varistor ceramics doped with MnO

The influence of the MnO content on the microstructure and the electrical response of liquid-phase sintered ZnO–V₂O₅ varistor ceramics wereanalysed using A.C. impedance spectroscopy on samples prepared via the conventional solid state route.The impedance spectra were analysed with the help of one model equivalent circuit at high frequencies and another at low frequencies, involving both resistor and non-Debye constant phase elements (CPEs). The results indicate a significant contribution of grain boundary resistance to the total resistance and non-ohmic characteristic of the studied materials. The Arrhenius plots show two slopes with a turnover at 150 °C/200 °C for both the higher- and lower-frequency time constants. These behaviours can be related to the decrease of the minor charge carrier density. These activation energies were associated with the adsorption and reaction of O₂ (as well as V) species at the grain boundary interface. Consequently, better varistor performance is achieved for 96.9 mol% ZnO+0.5 mol% V₂O₅+0.10 mol% Nb₂O₅+2.5 mol% MnCO₃ with nonlinear coefficient α=21.6, breakdown field E_1mA=191.47 V/mm, leakage current density J_L=36.46 µA/cm² and activation energies of 0.639 eV and 0.644 eV. X-ray diffraction shows that in addition to the major ZnO phases, Zn₃(VO₄)₂ and ZnV₂O₄, were detected as minor secondary phases. SEM analysis of the morphology shows that the grain growth increases with increases in the MnO doping level.     

High‐pressure synthesis of a 12CaO·7Al2O3–12SrO·7Al2O3 solid solution

Solid solutions of 12CaO·7Al₂O₃ (C12A7) and 12SrO·7Al₂O₃ (S12A7) crystals were synthesized under high pressure. X‐ray diffraction patterns revealed that the lattice constants of the synthesized samples depend linearly on the compositional ratio of C12A7 and S12A7. Electron‐probe X‐ray microanalyses show that the chemical compositions of the crystals are represented by xC12A7·(1?x)S12A7 (0<x<1). These results indicate that the variation in the lattice constants is originated from a difference in the ionic radii of Ca²⁺ and Sr²⁺ ions. From impedance measurements, it was found that S12A7 has the highest conductivity (~1 × 10^?3 Scm^?1 at 550°C) among the solid solutions in the C12A7–S12A7 system.     

Effects of spark plasma sintering on ferroelectricity of 0.8Bi3.15Nd0.85Ti3O12-0.2CoFe2O4 composite ceramic

The 0.8Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT)-0.2CoFe₂O₄ (CFO) composite multiferroic ceramics have been fabricated by spark plasma sintering (SPS) at 850?°C. The relative density of as-sintered SPS ceramic reaches 97.4 (±0.3)%. The composites are composed of pure BNdT and CFO phases without any preferred c-orientation. The a-orientation preference is more obvious perpendicular to the pressure direction. The average grain-sizes of BNdT and CFO are 163 and 146?nm, respectively. The BNdT phase has more grains below 100?nm (～20%). The super energy-dispersive X-ray analyses suggest no serious reaction between BNdT and CFO. The Raman spectrum verifies the nano-structure of the SPS ceramic via the broadening bands and peak shifts. The Curie temperature of the SPS ceramic declines to 560?°C with stabilized dielectric loss. The grain boundary resistance plays a dominant role on impedance above 700?°C. The remanent polarization approaches to 15.2?μC/cm² (300?kV/cm) with lower coercive fields (?89/+95?kV/cm).     

High performance multi-layer varistor (MLV) from doped ZnO nanopowders by water based tape casting: Rheology,sintering, microstructure and properties

In this work, we report the fabrication of a high performance multi-layer varistor (MLV) via water based tape casting method using novel compositions of nanomaterials. Bi₂O₃, CaO and Co₃O₄ doped ZnO nanopowders were prepared by solution combustion synthesis (SCS) route, calcined at different temperatures (550, 650, 750 and 850?°C) and characterized by TEM, XRD, SEM and AFM. The nanopowder (crystallite size ~30?nm) calcined at 650?°C for 1?h was used as the starting material for MLV fabrication. Compositions of the slurry containing doped ZnO nanopowders, binder and plasticizer in water solvent were optimized for the fabrication of thick film. The rheological properties of the slurries having different solid loadings were analysed and thick films of various thicknesses (50–500?µm) were prepared by varying the feeding rate of tape casting. The film roughness of 38.3?nm for the thick film made from 40?wt% solid slurry was found to be superior compared to other samples due to the presence of reduced crack and shrinkage. MLV fired at 950?°C for 1.5?h exhibited a coefficient of nonlinearity of 18 and breakdown voltage of 291.5?V that yields superior properties compared to commercial MLVs.     

Intermediate temperature electrical properties in 4 mol% ZnO-doped Zr0.92Y0.08O2-α/NaCl-KCl composite electrolyte

In this paper, 4?mol% ZnO-doped Zr_0.92Y_0.08O_2-α (8YSZ) and its 8YSZ+4ZnO/NaCl-KCl composite electrolyte were synthesized by a solid-state reaction. The X–ray diffraction (XRD) analysis indicates that 8YSZ+4ZnO and inorganic chlorides phases can coexist. The inorganic chlorides decrease the synthesis temperature of 8YSZ+4ZnO. The highest conductivities of 8YSZ+4ZnO and 8YSZ+4ZnO-NK are 7.0?×?10^?3 S?cm^?1 and 7.7?×?10^?2 S?cm^?1 at 700?°C, respectively. The oxygen concentration discharge cell shows that 8YSZ+4ZnO and 8YSZ+4ZnO-NK are good oxide ionic conductors under an oxygen-containing atmosphere. Finally, an H₂/O₂ fuel cell based on the 8YSZ+4ZnO-NK electrolyte reached the maximum power density (P_max) of 315.5?mW?cm^?2 at 700?°C.