Sintering of Zinc Oxide Doped with Antimony Oxide and Bismuth Oxide

The phase change, densification, and microstructure development of ZnO doped with both Bi₂O₃ and Sb₂O₃ are studied to better understand the sintering behavior of ZnO varistors. The densification behavior is related to the formation of pyrochlore and liquid phases; the densification is retarded by the former and promoted by the latter. The pyrochlore phase, whose composition is Bi_3/2ZnSb_3/2O₇, appears below 700°C. The formation temperature of the liquid phase depends on the Sb/Bi ratio: about 750°C for Sb/Bi < 1 by the eutectic melting in the system ZnO—Bi₂O₃, and about 1000°C for Sb/Bi > 1 by the reaction of the pyrochlore phase with ZnO. Hence, the densification rate is determined virtually by the Sb/Bi ratio and not by the total amount of additives. The microstructure depends on the sintering temperature. Sintering at 1000°C forms intragrain pyrochlore particles in ZnO grains as well as intergranular layers, but the intragrain particles disappear at 1200°C by the increased amount of liquid phase, which enhances the mobility of the solid second phase.     

Microstructure of Varistors Prepared with Zinc Oxide Nanoparticles Coated with Bi2O3

Zinc oxide (ZnO) nanoparticles coated with 1–5 wt% Bi₂O₃ were prepared by precipitating a Bi(NO₃)₃ solution onto a ZnO precursor. Transmission electron microscopy showed that a homogeneous Bi₂O₃ layer coated the surface of the ZnO nanoparticles and that the ZnO particle size was ∼30–50 nm. Scanning electron microscopy showed that ZnO grains sintered at 1150°C were homogeneous in size and surrounded by a uniform Bi₂O₃ layer. When the ZnO grains were surrounded fully by Bi₂O₃ liquid phases, further increases in the ZnO grain size were not affected by the Bi₂O₃ content. This predesigned ZnO nanoparticle structure was shown to promote homogeneous ZnO grains with perfect crystal growth.     

Admittance—Frequency Response in Zinc Oxide Varistor Ceramics

The lumped parameter/complex plane analysis technique revealed several contributions to the terminal admittance of the ZnO—Bi₂O₃ based varistor grain-boundary ac response. The terminal capacitance has been elucidated via the multiple trapping phenomena, a barrier layer polarization, and a resonance effect in the frequency range 10⁻²≤ f ≤ 10⁹ Hz. The characterization of the trapping relaxation behavior near ∼ 10⁵ Hz (∼ 10⁻⁶ s) provided a better understanding of a previously reported loss-peak. The possible nonuniformity in this trapping activity associated with its conductance term observed via the depression angle of a semicircular relaxation in the complex capacitance ( C *) plane has been postulated.     

Sintering and Characterization of Nanophase Zinc Oxide

Nanocrystalline, single-phase undoped ZnO was sintered to 95%–98% of theoretical density at 650°–700°C, using pressureless isothermal sintering. The density increased very rapidly at 500°–600°C, remained constant with sintering temperature until ∼900°C, and then decreased slightly. The estimated activation energy for densification at 600°–700°C (275 kJ/mol) was comparable to grain-growth activation energies previously reported for microcrystalline ZnO but much greater than the grain-growth activation energy measured in the present work. A bimodal microstructure, consisting of nanocrystalline grains within larger ensembles ("supergrains"), was observed, and both modes grew as the sintering temperature increased. The grain-growth activation energy for the nanocrystalline grains was extremely low, ∼20 kJ/mol. The activation energy for the growth of the supergrains depended strongly on temperature but was ∼54 kJ/mol at >500°C. The important mechanisms probably are rearrangement of the nanoparticle grains, with simultaneous surface and boundary diffusion, and vapor transport above 900°C.     

Grain Growth of Zinc Oxide During the Sintering of Zinc Oxide—Antimony Oxide Ceramics

Grain growth in a high-purity ZnO with systematic additions of Sb₂O₃ from 0.29 to 2.38 wt% was studied for sintering in air from 1106° to 1400°C. The results are discussed and compared with previous studies of pure ZnO and ZnO with Bi₂O₃ additions in terms of the kinetic grain growth expression: Gⁿ – Gⁿ ₀= K ₀ t exp(— Q/RT ). Additions of Sb₂O₃ inhibited the grain growth of ZnO and increased the grain growth exponent ( n -value) to 6 from 3 for pure ZnO and 5 for the ZnO—Bi₂O₃ ceramic. The apparent activation energy for the grain growth of ZnO also increased to about 600 kJ/mol from 220 kJ/mol for pure ZnO and 150 kJ/mol for the ZnO—Bi₂O₃ ceramics. Both the grain growth exponent and the activation energy were independent of the Sb₂O₃ content. Particles of the Zn₇Sb₂O₁₂ spinel were observed on the grain boundaries and at the grain triple point junctions. It was also observed that the Sb₂O₃ additions caused twin formation in each ZnO grain. It is concluded that both the Zn₇Sb₂O₁₂ particles and the twins are responsible for the ZnO grain growth inhibition by Sb₂O₃.     

Direct-Write Fabrication of Zinc Oxide Varistors

Zinc oxide (ZnO)-based pastes with tailored rheological properties have been developed for direct-write fabrication of thick-film varistor elements in highly integrated, multifunctional electroceramic devices. Such pastes exhibited pseudoplastic behavior with a low shear apparent viscosity of roughly 1 × 10⁴ Pa·s. Upon aging, the pastes attained printable, steady-state viscosities of approximately 3 × 10² Pa·s at 10 s⁻¹. Square and rectangular elements were patterned on dense alumina substrates and sintered at varying temperatures between 800° and 1250°C. Varistor elements fired at 900°C exhibited nonlinearity coefficients (α= 30) that were equivalent to high-density (>95%) varistors formed by cold isostatic pressing at 100 MPa (15 ksi) of a similar chemically derived powder heat-treated under analogous conditions.     

Mechanical Strength and Microstructure of Zinc Oxide Varistor Ceramics

ZnO-based varistor ceramics were sintered under various conditions to optimize their mechanical strength. For highest strength, the optimum sintering temperature was 1070°C or below. At higher maximum temperature, the strength decreased because of grain coarsening and the increasingly inhomogeneous distribution of secondary phases thereby induced. Fracture typically started from holes associated with hollow or poorly compacted sprayed granules. All series contained the same type of critical flaws, but, depending on the sintering temperature, the fracture toughness changed, which led to different strengths. At sintering temperatures above 1050°C, the density started to decrease slightly because of swelling attributed to the pressure of gas entrapped in closed pores.     

Zinc Vanadates in Vanadium Oxide-Doped Zinc Oxide Varistors

Convergent-beam electron diffraction has been used to determine the space groups of β- and γ-Zn₃(VO₄)₂ particles in vanadium oxide-doped zinc oxide varistors. The crystal structure of β-Zn₃(VO₄)₂ has been determined to be monoclinic with space group P 2₁ and lattice parameters of a = 9.80 Å, b = 8.34 Å, c = 10.27 Å, and β= 115.8°, whereas that of γ-Zn₃(VO₄)₂ is monoclinic with space group Cm and a = 10.40 Å, b = 8.59 Å, c = 9.44 Å, and β= 98.8°. Energy-dispersive X-ray microanalysis of these two phases shows significant deviations from their expected stoichiometry. It is apparent that the β-phase is, in fact, the metastable Zn₄V₂O₉ phase, whereas the γ-phase either is a new oxide that consists of zinc, vanadium, and manganese or, more likely, is a zinc vanadate phase with a Zn:V atomic ratio of 1:1 that has the ability to go into solid solution with manganese.     

Microstructure Development of Zinc Oxide in Hydrogen

Zinc oxide powder compacts with green densities of 60% of theoretical sintered in hydrogen do not densify but exhibit significant grain coarsening. The temperature dependence of the coarsening was greater than that expected from vapor-phase coarsening models and is close to that obtained for grain growth in dense ZnO. This suggests that the rate of particle coarsening is controlled by grain-boundary mobility. This possibility was reinforced by the reduction in coarsening with ZnAl₂O₄ present as a second phase. The results emphasize the importance of controlling grain growth throughout all stages of densification.     

Sintering of Platelike Bismuth Titanate Powder Compacts with Preferred Orientation

The sintering of platelike Bi₄Ti₃O₁₂ powder particles was investigated. Special emphasis was given to the role of particle orientation in the green sheet on densification and microstructure development. Compacts were made by tape-casting and dry-pressing. During the initial stage of sintering, the particles rearranged and formed colonies with the development of face-to-face contacts. Pores between particles in a colony disappeared during colony formation, and the volume of pores between colonies decreased on further heating. Grain growth started when the sintered density reached about 90% of theoretical density. The growth of well-oriented grains increased the degree of orientation. Thus, highly oriented sintered bodies with high densities were prepared by heating at 1150°C.     

Microstructure and Current–Voltage Characteristics of Multicomponent Vanadium-Doped Zinc Oxide Varistors

The effects of the oxide additives MnO₂, Co₃O₄, and Sb₂O₃, commonly incorporated in commercial Bi₂O₃-doped ZnO varistors, on the current–voltage characteristics and microstructure of 0.25 mol% V₂O₅-doped ZnO varistors have been studied. MnO₂ is the most significant additive in terms of its effects on varistor performance. Varistor performance can also be improved by increasing the V₂O₅ content to 0.5 mol% in a ZnO ceramic containing 1 mol% MnO₂. Further increases in the V₂O₅ content of 1 mol% MnO₂-doped material cause a deterioration in varistor behavior. The microstructure of the samples consists mainly of ZnO grains with zinc vanadates as the minority secondary phases. Additional spinel phase is formed when Sb₂O₃ is incorporated.     

Current–Voltage Characteristics of Cobalt-Doped Inversion Boundaries in Zinc Oxide Bicrystals

Undoped and cobalt-doped basal inversion boundaries were fabricated in ZnO bicrystals to investigate their current–voltage characteristics. High-resolution transmission electron microscopy observations and energy-dispersive X-ray spectroscopy analyses for a cobalt-doped bicrystal revealed that the boundary was highly coherent and free from intergranular phases and precipitates, but a certain amount of cobalt was present near the boundary. The cobalt-doped bicrystals exhibited nonlinear characteristics that depended on cooling rates from annealing temperature, in contrast to linear characteristics of the undoped bicrystals. It is suggested that the presence of cobalt impurities enhances the formation of acceptor-like native defects near the boundaries to generate electrostatic potential barriers.     

Aqueous Precipitation of Spherical Zinc Oxide Powders for Varistor Applications

Aqueous precipitation has been used to prepare spherical ZnO particles. These powders have been shown to be suitable for use in the preparation of varistors. The uniform size distribution and uniform coating of these powders with the appropriate dopants allowed fabrication of varistors with improved properties over those fabricated from conventionally ball-milled and calcined powders. The improved properties were a high coefficient of nonlinearity (∼44) in the nonohmic region, a sharp change in electrical behavior from ohmic to nonohmic, and a high resistivity (5×10¹² SOM°m) at low voltages.     

Structure and Chemistry of Basal-Plane Inversion Boundaries in Antimony Oxide-Doped Zinc Oxide

The atomic structure and the chemistry of basal - plane inversion boundaries in Sb₂O₃-doped ZnO were investigated using quantitative transmission electron microscopy techniques. Electron microdiffraction and high - resolution transmission electron microscopy were used to determine the orientation of the polar c -axis on both sides of the inversion boundary and the translation state between the inverted ZnO domains. Quantitative energy - dispersive X - ray spectroscopy combined with high - resolution transmission electron microscopy allowed us to determine the exact amount and the arrangement of antimony in the boundary layer. Inversion boundaries are head - to - head oriented with a displacement vector of the oxygen sublattice of R _IB=⅓[01[Onemacr]0] – 0.102[0001]. The boundary plane consists of a highly ordered SbZn₂ monolayer in which the cations occupy the octahedral interstices of the structure. In the octahedral boundary layer, zinc and antimony atoms constitute a honeycomb superstructure with a threefold (3 m ) in - plane symmetry.     

Differences in Wetting Characteristics of Bi2O3 Polymorphs in ZnO Varistor Materials

Detailed analysis of the microstructure of grain boundaries, especially triple-grain and multiple-grain junctions, in ZnO varistor materials has been performed using transmission electron microscopy. Different polymorphs of Bi₂O₃ are shown to exhibit different wetting properties on ZnO interfaces. Recent investigations suggest that the equilibrium configuration consists of crystalline Bi₂O₃ in the triple-grain and multiple-grain junctions and an amorphous bismuth-rich film in the ZnO/ZnO grain boundaries. The present investigation supports this suggestion for δ-Bi₂O₃ and also adds to the microstructural image and wetting properties of α-Bi₂O₃.     

Voltage-Current Characteristics of a Simple Zinc Oxide Varistor Containing Magnesia

This paper examines the effect of MgO addition on the structural and electrical characteristics of a ZnO varistor composition with few dopants. MgO acts as a grain-growth inhibitor. The electrical performances of the obtained varistors are improved.     

Fully Dense, Fine-Grained, Doped Zinc Oxide Varistors with Improved Nonlinear Properties by Thermal Processing Optimization

Fully dense, doped ZnO varistors were prepared using an easy two-stage pressureless-sintering method at temperatures as low as 825°C, with a grain size of ∼0.5 μm. After the highly nonohmic ZnO varistors were sintered, their fine microstructure consisted of uniformly sized grains, small spinel grains with partially dissolved manganese and cobalt oxides discontinuously distributed in the fairly wide grain boundaries, and an intergranular layer of bismuth-rich crystalline phase mainly detected at three or four ZnO grain junctions. There were twins near the middle of almost all the ZnO grains. The abnormally high nonlinear properties of the almost nanostructured varistors ( F _B≈ 6–8 kV/mm and α= 270) were attributed to a uniform and very fine microstructure, a high ZnO–ZnO grain direct contacts concentration, and a uniform hybrid layer substructure (grain boundaries and twin boundaries) with different (but probably accumulative) potential barriers.     

Effect of Heat Treatments on the Wetting Behavior of Bismuth-Rich Intergranular Phases in ZnO:Bi:Co Varistors

The effect of annealing on the wetting behavior of Bi-rich intergranular phases in ZnO:Bi:Co varistors was studied. The intergranular phase exhibits temperature-dependent grain-boundary wetting, with an average equilibrium dihedral angle of 0° at 1140°C and over 55° at 610°C. The temperature-dependent wetting may be related to the temperature dependence of the ZnO concentration in the Bi₂O₃ liquid phase. The effect of the intergranular phase distribation on the electrical properties of ZnO varistors is discussed.     

Pore–Boundary Separation Behavior during Sintering of Pure and Bi2O3-Doped ZnO Ceramics

Pore–boundary separation in ZnO and 99.95ZnO·0.05Bi₂O₃ (in mol%) specimens during sintering at 1200°C was investigated. In pure ZnO specimens, pores were attached to the grain boundaries and disappeared during the final stage of sintering. In the Bi₂O₃-doped specimens, on the other hand, many pores were separated from the boundaries and trapped inside the grains. Observation using transmission electron microscopy showed that a thin layer of Bi₂O₃-rich phase existed at the boundaries in the Bi₂O₃-doped specimens. The pore separation in 99.95ZnO·0.05Bi₂O₃ specimens was explained in terms of the dihedral angle change and the high mobility of a liquid film boundary.