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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Effect of Particle Sizes of Starting Materials on Microstructure Development in Textured Bi0.5(Na0.5K0.5)0.5TiO3

Microstructure development in Bi_0.5(Na_0.5K_0.5)_0.5TiO₃ prepared by a reactive-templated grain growth process was dependent on the sizes of platelike Bi₄Ti₃O₁₂ (BiT) and equiaxed TiO₂ particles used as starting materials. Calcined compacts were composed of large, platelike template grains and small, equiaxed matrix grains, the sizes of which were determined by those of the BiT and TiO₂ particles, respectively. Texture was developed by the growth of template grains at the expense of matrix grains during sintering, and a new mechanism of grain growth was proposed on the basis of microstructure observation. The grain growth rate was determined by the template and matrix grain sizes, and a dense ceramic with extensive texture was obtained using small BiT and TiO₂ particles.     

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.     

Microwave Dielectric Properties and Chemical Resistance of Low-Temperature-Sintered CaZrB2O6 Ceramics

Dolomite-type borate ceramics consisting of CaZrB₂O₆ were synthesized via a conventional solid-state reaction route; low-temperature sintering was explored using Bi₂O₃–CuO additives of 1–7 wt% for low-temperature co-fired ceramics applications. For several sintering temperatures, the microwave dielectric properties and chemical resistance of the ceramics were investigated. The CaZrB₂O₆ ceramics with 3 wt% Bi₂O₃–CuO addition could be sintered below 925°C, and the microwave dielectric properties of the low-temperature samples were ɛ_r=10.55, Q × f =87,350 GHz, and τ_f=+2 ppm/°C. The chemical resistance test result showed that both CaZrB₂O₆- and Bi₂O₃–CuO-added CaZrB₂O₆ ceramics were durable in basic solution but were degraded in acid solution.     

Effect of La Doping on the Phase Conversion, Microstructure Change, and Electrical Properties of Bi2Fe4O9 Ceramics

Undoped and La-doped Bi₂Fe₄O₉ ceramics were synthesized using a soft chemical method. It is observed that in calcining La-doped Bi₂Fe₄O₉, Bi(La)FeO₃ phase rather than Bi_{2− x} La _x Fe₄O₉ gradually increases with increasing La doping content. The phase conversion from mullite-type structure of Bi₂Fe₄O₉ to rhombohedrally distorted perovskite one of Bi(La)FeO₃ with increasing La doping content indicates that La doping can stabilize the structure of BiFeO₃. This is further evidenced that Bi₂Fe₄O₉ can be directly converted to Bi(La)FeO₃ by heating the mixtures of nominal composition of Bi₂Fe₄O₉/ x La₂O₃. Furthermore, the microstructure changes and the room temperature hysteresis loops and leakage current for Bi_{2− x} La _x Fe₄O₉ with x =0 and 0.02 were characterized.     

Effects of La2O3/ZnO Additives on Microstructure And Microwave Dielectric Properties of Zr0.8Sn0.2TiO4 Ceramics

Dielectric ceramics of Zr_0.8Sn_0.2TiO₄ containing La₂O₃ and ZnO as sintering aids were prepared and investigated for microstructure and microwave dielectric properties. Low-level doping with La₂O₃ and ZnO (up to 0.30 wt%) is good for densification and dielectric properties. These additives do not affect the dielectric constant and the temperature coefficient. Dielectric losses increase significantly at additive levels higher than 0.15 wt%. The combined additives La₂O₃ and ZnO act as grain growth enhancers. With 0.15 wt% additives, a ceramic having a dielectric constant, a quality factor, and a temperature coefficient of frequency at 4.2 GHz of 37.6, 12 800, and –2.9 ppm/°C, respectively, was obtained. The quality factor was considerably improved by prolonged sintering.     

Effects of Excess Bi2O3 on the Ferroelectric Behavior of Nd-Doped Bi4Ti3O12 Thin Films

Effects of excess Bi₂O₃ content on formation of (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) films deposited by RF sputtering were investigated. The microstructures and electrical properties of BNT thin films are strongly dependent on the excess Bi₂O₃ content and post-sputtering annealing temperature, as examined by XRD, SEM, and P – E hysteresis loops. A small amount of excess bismuth improves the crystallinity and therefore polarization of BNT films, while too much excess bismuth leads to a reduction in polarization and an increase in coercive field. P – E loops of well-established squareness were observed for the BNT films derived from a moderate amount of Bi₂O₃ excess (5 mol%), where a remanent polarization 2P _r of 25.2 μC/cm² and 2E _c of 161.5 kV/cm were shown. A similar change in dielectric constant with increasing excess Bi₂O₃ content was also observed, with the highest dielectric constant of 304.1 being measured for the BNT film derived from 5 mol% excess Bi₂O₃.     

Phase Relations in the System Bi2O3-WO3

Phase relations in the system Bi₂O₃-WO₃ were studied from 500° to 1100°C. Four intermediate phases, 7Bi₂O₃· WO₃, 7Bi₂O₃· 2WO₃, Bi₂O₃· WO₃, and Bi₂O₃· 2WO₃, were found. The 7B₂O · WO₃ phase is tetragonal with a ₀= 5.52 Å and c ₀= 17.39 Å and transforms to the fcc structure at 784°C; 7Bi₂O₃· 2WO₃ has the fcc structure and forms an extensive range of solid solutions in the system. Both Bi₂O₃· WO₃ and Bi₂O₃· 2WO₃ are orthorhombic with (in Å) a ₀= 5.45, b ₀=5.46, c ₀= 16.42 and a ₀= 5.42, b ₀= 5.41, c ₀= 23.7, respectively. Two eutectic points and one peritectic exist in the system at, respectively, 905°± 3°C and 64 mol% WO₃, 907°± 3°C and 70 mol% WO₃, and 965°± 5°C and 10 mol% WO₃.     

Subsolidus Phase Equilibria in the System Bi2O3-TiO2-Nb2O5

The subsolidus phase equilibria in the system Bi₂O₃-TiO₂-Nb₂O₅ at 1100°C were determined by solid-state reaction techniques and X-ray powder diffraction methods. The system was found to contain 4 ternary compounds, i.e. Bi₃TiNbO₉, Bi₇Ti₄NbO₂₁, a cubic pyrochlore solid solution having a compositional range of 3Bi₂O₃· x TiO₂ (7– x )Nb₂O₅ where x ranges from 2.3 to 6.75, and an unidentified phase, 4Bi₂O₃·11TiO₂·5Nb₂O₅.     

Dielectric Properties of the Fluorite-like Bi2O3–Nb2O5 Solid Solution and the Tetragonal Bi3NbO7

Our analysis of the microwave dielectric properties of the δ-Bi₂O₃–Nb₂O₅ solid solution (δ-BN_ss) showed a continuous increase in permittivity and dielectric losses with an increasing concentration of Nb₂O₅. The only discontinuity was found for the temperature coefficient of resonant frequency, which is negative throughout the entire homogeneity range but reaches a minimum value for the sample with 20 mol% Nb₂O₅. At the same composition there is a discontinuity in the grain size of the δ-BN_ss ceramics. For the sample containing 25 mol% Nb₂O₅ two structural modifications were observed. A single-phase tetragonal Bi₃NbO₇, in the literature referred to as a Type-III phase, is formed in a very narrow temperature range from 850° to 880°C. A synthesis performed below or above this temperature range resulted in the formation of the end member of the δ-BN_ss homogeneity range. Compared with the δ-BN_ss the Bi₃NbO₇ ceramics exhibit lower microwave dielectric losses, an increased conductivity, and a positive temperature coefficient of resonant frequency.     

Properties and Structure of Glasses in the System Bi2O3-SiO2-GeO2

In the system Bi₂O₃-SiO₂-GeO₂, good glasses can be formed only from limited compositional regions consisting of 2 narrow strips along the lines x Bi₂O₃-(100-:t) GeO₂ ( x ≤40) and 40Bi₂O₃ y SiO₂ (60- y )GeO₂ (mol%); such glass is dark brown. Compositions from a large region (Bi₂O₃ content <40 mol%) showed immiscibility. In the binary system Bi₂O₃-GeO₂, density and refractive index vary linearly with composition (mol%). Negative deviations of molar volume from ideality suggest that the coordination of a significant number of Ge ions is changing from 4-fold to 6-fold. Thermal expansion and electrical resistivity data are also reported.