Grain Growth of ZnO during Bi2O3 Liquid-Phase Sintering

Grain growth of ZnO during the liquid-phase sintering of binary ZnO–Bi₂O₃ ceramics has been studied for Bi₂O₃ contents from 3 to 12 wt% and sintering from 900° to 1400°C. The results are considered in combination with previously published studies of ZnO grain growth in the ZnO–Bi₂O₃ system. For the Bi₂O₃ contents of the present study, the rate of ZnO grain growth is found to decrease with increasing Bi₂O₃. Activation analysis, when combined with the results of similar analyses of the previous studies, reveals a change in the rate-controlling mechanism for ZnO grain growth. Following a low-Bi₂O₃-content region of nearly constant activation energy values of about 150 kJ/mol, further Bi₂O₃ additions cause an increase of the activation energy to about 270 kJ/mol. consistent with accepted models of liquid-phase sintering, it is concluded that the rate-controlling mechanism of ZnO grain growth during liquid-phase sintering in the presence of Bi₂O₃ changes from one of a phase-boundary reaction at low Bi₂O₃ levels to one of diffusion through the liquid phase at about the 5 to 6 wt% Bi₂O₃ level and above.     

Grain Growth in Sintered ZnO and ZnO-Bi2O3 Ceramics

Grain growth in a high-purity ZnO and for the same ZnO with Bi₂O₃ additions from 0.5 to 4 wt% was studied for sintering from 900° to 1400°C in air. The results are discussed and compared with previous studies in terms of the phenomenological kinetic grain growth expression: G ⁿ— G ⁿ₀= K ₀ t exp(— Q/RT ). For the pure ZnO, the grain growth exponent or n value was observed to be 3 while the apparent activation energy was 224 ± 16 kJ/mol. These parameters substantiate the Gupta and Coble conclusion of a Zn²⁺ lattice diffusion mechanism. Additions of Bi₂O₃ to promote liquidphase sintering increased the ZnO grain size and the grain growth exponent to about 5, but reduced the apparent activation energy to about 150 kJ/mol, independent of Bi₂O₃ content. The preexponential term K ₀ was also independent of Bi₂O₃ content. It is concluded that the grain growth of ZnO in liquid-phase-sintered ZnO-Bi₂O₃ ceramics is controlled by the phase boundary reaction of the solid ZnO grains and the Bi₂O₃-rich liquid phase.     

Influence of the Addition of Bi2O3 on the Grain Growth and Magnetic Permeability of MnZn Ferrites

Additions of Bi₂O₃ were used to promote grain growth and to increase magnetic permeability during sintering of MnZn ferrites. The results showed that small additions of Bi₂O₃ of <0.05 wt% remarkably increase the permeability of MnZn ferrites. On the other hand, addition of 0.05 wt% Bi₂O₃ induced the formation of a microstructure composed of giant grains with trapped pores embedded in a normal microstructure. The permeability of these samples showed a pronounced secondary maximum in permeability. At still higher Bi₂O₃ concentrations, above 0.2 wt%, the grain growth was retarded and a normal microstructure appeared; however, the magnetic permeability was strongly reduced.     

Grain Growth of ZnO in ZnO-Bl2O3 Ceramics with Ai2O3 Additions

Grain growth of ZnO during liquid-phase sintering of a ZnO-6 wt% Bi₂O₃ ceramic was investigated for A1₂O₃ additions from 0.10 to 0.80 wt%. Sintering in air for 0.5 to 4 h at 900° to 1400°C was studied. The AI₂O₃ reacted with the ZnO to form ZnAl₂O₄ spinel, which reduced the rate of ZnO grain growth. The ZnO grain-growth exponent was determined to be 4 and the activation energy for ZnO grain growth was estimated to be 400 kJ/mol. These values were compared with the activation parameters for ZnO grain growth in other ceramic systems. It was confirmed that the reduced ZnO grain growth was a result of ZnAl₂O₄ spinel particles pinning the ZnO grain boundaries and reducing their mobility, which explained the grain-growth exponent of 4. It was concluded that the 400 kJ/mol activation energy was related to the transport of the ZnAl₂O₄ spinel particles, most probably controlled by the diffusion of O^2- in the ZnAl₂O₄ spinel structure.     

Origin of Solid-State Activated Sintering in Bi2O3-Doped ZnO

Activated sintering in Bi₂O₃-doped ZnO has been studied with emphasis on the mechanistic role of intergranular amorphous films. The atomic-level microstructures and bismuth solute distributions in doped powders have been investigated using high-resolution electron microscopy and scanning transmission electron microscopy. Densification is observed to be significant below the bulk eutectic temperature in the presence of Bi₂O₃ concentrations as low as 0.58 mol%. Transmission electron microscopy of as-calcined and sintered powders shows that significant neck growth and particle coarsening occur in the solid state. Intergranular amorphous films of ∼1 nm thickness, terminating in wetting menisci at sinter-necks, are observed to form concurrently with the onset of activated sintering. In a few instances, amorphous films are also observed at surfaces of the ZnO particles. These films appear to be the free-surface counterpart to equilibrium-thickness intergranular films. Activated sintering in this binary system is attributed to rapid mass transport through subeutectic, equilibrium-thickness intergranular films, with the amorphous phase also providing capillary pressure.     

Effect of Bi2O3 on Impurity Ion Distribution and Electrical Resistivity of Li-Zn Ferrites

Preventing the incorporation of impurities in Li-Zn ferrite grains during sintering is essential for production of ceramics with reproducible magnetic and electrical properties. Li-Zn ferrites of composition Li_0.3Zn_0.4Mn_0.05Fe_2.25O₄ were prepared with Bi₂O₃ and borosilicate sintering additives. The distribution of impurity ions in the sintered ferrites was investigated using transmission electron microscopy (TEM) coupled with energy dispersive spectroscopy (EDS). Ceramics prepared with Bi₂O₃ contained Si, Ca, and S impurities, located at grain boundaries and triple point regions. The low viscosity and good wetting properties of the Bi₂O₃ and to a lesser extent the borosilicate liquid phase allowed impurities to be selectively removed from the growing ferrite phase during sintering, thus improving sample resistivities.     

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.     

Cubic-to-Tetragonal Displacive Transformation in Gd2O3–Bi2O3 Ceramics

Gd₂O₃-doped Bi₂O₃ polycrystalline ceramics containing between 2 and 7 mol% Gd₂O₃ were fabricated by pressureless sintering powder compacts. The as-sintered samples were tetragonal at room temperature. Hightemperature X-ray diffraction (XRD) traces showed that the samples were cubic at elevated temperatures and transformed into the tetragonal polymorph during cooling. On the basis of conductivity measurements as a function of temperature and differential scanning calorimetry (DSC), the cubic → tetragonal as well as tetragonal → cubic → teansition temperatures were determined as a function of Gd₂O₃ concentration. The cubic → tetragonal transformation appears to be a displacive transformation. It was observed that additions of ZrO₂ as a dopant, which is known to suppress cation interdiffusion in rare-earth oxide–Bi₂O₃ systems, did not suppress the transition, consistent with it being a displacive transition. Annealing of samples at temperatures 660°C for several hundred hours led to decomposition into a mixture of monoclinic and rhombohedral phases. This shows that the tetragonal polymorph is a metastable phase.     

Nature of Intergranular Phase in Nonohmic ZnO Ceramics Containing 0.5 Mol% Bi2O3

The intergranular phase obtained by sintering a binary mixture of ZnO + 0.5 mol% Bi₂O₃ was isolated by using a dilute solution of HCIO₄, which etches ZnO preferentially. The combined results of selected-area electron diffraction and microscopy, microprobe analysis, and X-ray diffraction strongly indicate that the intergranular material is a polycrystalline phase of tetragonal β-Bi₂O₃ ( P 42₁ c ), rather than the amorphous ZnO-Bi₂O₃ phase reported earlier. It appears that the nonohmic behavior in this prototype metal-oxide varistor must be an interfacial property associated with the semiconducting ZnO grains separated by thin layers of high-resistivity Bi₂O₃.     

Low Breakdown Voltage Varistors by Grain Boundary Diffusion of Molten Bi2O3 in ZnO

Diffusion of molten Bi₂O₃ into the grain boundaries of sintered, alumina-doped (0.23 and 0.7 mol%) ZnO pellets resulted in varistors with breakdown voltages in the 3–5 V range and nonlinearity coefficients of 10–24. The varistors were fabricated by spreading a thin layer of Bi₂O₃ powder on the surface of ZnO pellets and heating the combination to various temperatures (860–1155°C) and different times. The highest nonlinearity coefficients (20–24) and lowest breakdown voltages (3–5 V) were recorded in samples annealed at 860°C for 35 min. Longer annealing times and/or higher temperatures resulted in progressively higher breakdown voltages. Eventually the devices became insulating, which was attributed to the formation of an insulating Bi₂O₃ layer between the grains. Separate wetting experiments have shown that the penetration of Bi₂O₃ into ZnO grain boundaries was a strong function of alumina doping —the penetration rate was decreased by a factor of 5–7 as the ZnO was doped with as little as 0.2 mol% alumina. It is this slowing down of the penetration of the ZnO grain boundaries that is believed to be critical in the development of the low breakdown voltages observed.     

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.     

Microstructural Development in SnO2-Doped ZnO–Bi2O3 Ceramics

The effects of adding small quantities of SnO₂ to the basic ZnO–Bi₂O₃ varistor composition were studied in terms of phase reactions, microstructural development, and the formation of inversion boundaries. Scanning and transmission electron microscopy studies showed that the inversion boundaries, triggered by the addition of SnO₂, cause anisotropic grain growth in the early stages of sintering. ZnO grains that include inversion boundaries grow exaggeratedly, at the expense of normal grains, until they dominate the microstructure. Higher additions of SnO₂ lead to an increase in number of grains with inversion boundaries and to a more fine-grained microstructure. The increasing amount of secondary phases is also related to a higher level of SnO₂ addition; however, the influence of these phases on ZnO grain growth is subordinate to the role of inversion boundaries.     

Effect of Bi2O3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Bi₂O₃ was added to a nominal composition of Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature. When the Bi₂O₃ content was <8.0 mol%, a porous microstructure with Bi₄(SiO₄)₃ and SiO₂ second phases was developed in the specimen sintered at 885°C. However, when the Bi₂O₃ content exceeded 8.0 mol%, a liquid phase, which formed during sintering at temperatures below 900°C, assisted the densification of the ZS ceramics. Good microwave dielectric properties of Q × f =12,600 GHz, ɛ_r=7.6, and τ_f=−22 ppm/°C were obtained from the specimen with 8.0 mol% Bi₂O₃ sintered at 885°C for 2 h.     

Bi2O3 Vaporization in Microwave-Sintered ZnO Varistors

Vaporization of Bi₂O₃ in microwave-sintered ZnO varistors is discussed in this study. The Bi₂O₃ vaporization of ZnO varistors sintered by a conventional electric furnace is also studied for comparison. The results show that the Bi₂O₃ vaporization in microwave-sintered ZnO varistors is more homogenous from the surface to the inside of the sample, which results from the special thermal gradient inside the microwave-sintered samples, and we also find out that the Bi₂O₃ vaporization directly affects the electrical properties of ZnO varistors. Microwave-sintered samples exhibit more excellent electrical properties than the conventional ones because the homogenous Bi₂O₃ vaporization leads to more uniform microstructures.     

Low-Temperature Sintering, Densification, and Properties of Z-type Hexaferrite with Bi2O3 Additives

The effect of the addition of Bi₂O₃ on the densification, low-temperature sintering, and electromagnetic properties of Z-type planar hexaferrite was investigated. The results show that Bi₂O₃ additives can improve the densification and promote low-temperature sintering of Z-type hexaferrite prepared by a solid-state reaction method. The presence of Bi₂O₃ in the grain boundaries and the generation of Fe²⁺ degrade the initial permeability of the samples but make the quality factor and cut-off frequency increase. Various possible mechanisms involved in generating these effects were also discussed.     

Microstructure, Piezoelectric, and Ferroelectric Properties of Bi2O3-Added (K0.5Na0.5)NbO3 Lead-Free Ceramics

Lead-free piezoelectric (K_0.5Na_0.5)NbO₃– x wt% Bi₂O₃ ceramics have been synthesized by an ordinary sintering technique. The addition of Bi₂O₃ increases the melting point of the system and improves the sintering temperature of (K_0.5Na_0.5)NbO₃ ceramics. All samples show a pure perovskite phase with a typical orthorhombic symmetry when the Bi₂O₃ content <0.7 wt%. The phase transition temperature of orthorhombic–tetragonal ( T _{O − T} ) and tetragonal–cubic ( T _C) slightly decreased when a small amount of Bi₂O₃ was added. The remnant polarization P _r increased and the coercive field E _c decreased with increasing addition of Bi₂O₃. The piezoelectric properties of (K_0.5Na_0.5)NbO₃ ceramics increased when a small amount of Bi₂O₃ was added. The optimum piezoelectric properties are d ₃₃=140 pC/N, k _p=0.46, Q _m=167, and T _C=410°C for (K_0.5Na_0.5)NbO₃–0.5 wt% Bi₂O₃ ceramics.     

Effect of Bismuth of Oxide Content on the Sintering of Zinc Oxide

Densification and microstructure de velopment in Bi₂O₃-doped ZnO have been studied with a special emphasis on the effect of the Bi₂O₃ content. A small amount of Bi₂O₃ in ZnO (0.1 mol%) retarded densification, but the addition of Bi₂O₃ to more than 0.5 mol% promoted densification by the formation of a liquid phase above the eutectic temperature (∼740°C). The liquid phase increased grain-boundary mobility, which was responsible for the formation of intragrain pores and the decrease in the sintered density. The increase in the Bi₂O₃ content increased the probability of the formation of skeleton structure, which reduced the grain growth rate and the sintered density.     

Extended Defects in ZnO Ceramics Containing Bi4Ti3O12 Additive

Extended defects in ZnO ceramics containing, 6 wt% Bi₄Ti₃O₁₂ were studied by analytical electron microscopy. Apart from basal plane condensation stacking faults, which are also present in as-received ZnO, extended defects related to the presence of Bi₄Ti₃O₁₂ were observed. In samples sintered at 900°C they lie in the basal or in the prismatic     planes and they quite often form closed loops, whereas they form serpentine-shaped boundaries in samples sintered at 1200°C. Evidence is given that they are inversion boundaries. Their TEM image characteristics, as well as the unambiguous presence of Ti at the boundaries, suggest that they are formed due to the presence of 2-D coherent precipitates of Ti-rich (possibly Zn₂TiO₄-type spinel) phase.     

Microstructures of SrTiO3 Internal Boundary Layer Capacitors During and After Processing and Resultant Electrical Properties

The microstructure of strontium titanate internal boundary layer capacitors at various stages in their processing was studied by transmission electron microscopy of rapidly quenched and normally cooled samples. Compositions containing excess TiO₂, Al₂O₃, and SiO₂ have a completely wetting liquid phase at the sintering temperature; during cooling Ti_nO_{2 n −1}, Magneli phases precipitate at multiple grain junctions. Diffused metal oxides and flux (Bi₂O₃, PbO, CuO, and B₂O₃) rapidly penetrate as a liquid phase along boundaries in postsintering heat treatment. This liquid phase disappears during slow cooling.     

Influence of Nd2O3 Doping on the Reaction Process and Sintering Behavior of BaCeO3 Ceramics

The influence of Nd₂O₃ doping on the reaction process and sintering behavior of BaCeO₃ is investigated. Formation of BaCeO₃ is initiated at 800°C and completed at 1000°C. When Nd₂O₃ is added to the starting materials, the formation of BaCe_1–xNd_xO_3–δ is delayed and the temperature for complete reaction is increased to 1100°C. Only a BaCe_1-xNd_xO_3–δ solid solution with an orthorhombic crystal structure is present in the specimens for x ≤ 0.1. A secondary phase rich in Ce and Nd is formed within grains and at grain boundaries, when the Nd₂O₃ content is greater than the solubility limit (x ≥ 0.2). Pure BaCeO₃ is difficult to sinter, even at 1500°C, and only a porous microstructure could be obtained. However, doping BaCeO₃ with Nd₂O₃ markedly enhances its sinterability. The enhancement of the sinterability of Nd₂O₃-doped specimens at x ≤ 0.1 is attributed to the increase in the concentration of oxygen ion vacancies, which increases the diffusion rate. At x ≥ 0.2, the grain size is abnormally coarsened, which is caused by the formation of a liquid phase. While this liquid phase accelerates sintering, its beneficial effect on densification is counteracted by the segregation of the secondary grain-boundary phase which inhibits sintering.