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.     

Investigation of grain boundary diffusion and grain growth of lithium zinc ferrites with low activation energy

Activation energy and diffusion kinetics are important factors for grain growth and densification. Here, Bi₂O₃ was introduced into Li_0.43Zn_0.27Ti_0.13Fe_2.17O₄ ferrite ceramics via a presintered process to lower the reaction activation energy and to achieve low temperature sintering. Interestingly, Bi³⁺ ions entered the lattice and substituted for Fe³⁺ in the B‐site (i.e., a pure LiZn spinel ferrite). Also, SEM image results show that Bi₂O₃‐substituted LiZn ferrite ceramics have low critical temperature for grain growth (920°C), which is very advantageous for LTCC technology. This indicates that Bi₂O₃ is an excellent dopant for ceramics. Furthermore, to promote normal grain growth of the ceramics at low temperatures, different volumes of V₂O₅ additive were added at the final sintering stage. Results indicate that an optimal volume of V₂O₅ additive promotes grain growth (with no abnormal grains) and enhances magnetic performances of the ceramics at low sintering temperature. Finally, adding the optimal volume of V₂O₅ additive resulted in a homogeneous and compact LiZnTiBi ferrite ceramic with larger grains (average size of ~8 μm), high 4πM_s (~4100 gauss), and low ΔH (~190 Oe) obtained (at 900°C). Moreover, the doping method reported in this study also provides a reference for other low temperature sintered ceramics.     

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.     

Influence of WO3‐Doping on the Microstructure and Electrical Properties of ZnO–Bi2O3 Varistor Ceramics Sintered at 950°C

The phase evolution, microstructure, and electrical properties of WO₃‐doped ZnO–Bi₂O₃‐based varistors were investigated for different amounts x (0 ≤ x ≤ 1.60 mol%) of the dopant. When x was less than 0.40, the dissolved W⁶⁺ in the β‐Bi₂O₃ acted as a donor in the grain boundaries and reduced the electrical properties of the ZnO varistors. However, when x was 0.40 mol%, which meant an amount of WO₃ equal to that of Bi₂O₃, the electrical properties dramatically increased, which means the W⁶⁺ donor effect is removed at the grain boundaries because a new Bi₂WO₆ phase was formed in the grain‐boundary regions. The Bi₂WO₆ phase has high oxygen conductivity at high temperatures; it transfers more oxygen to the grain boundaries in order to further enhance the electrical properties. For x values higher than 0.40 (i.e., an addition of WO₃ that is greater than the content of Bi₂O₃), the electrical properties were steadily reduced in comparison to the composition with x = 0.40. This could be explained by the reduced amount of Co, Mn, and Al at the grain boundaries and in the ZnO grains as a result of their incorporation into the ZnWO₄ phase. The electrical properties of the ZnO grains and the grain boundaries were in agreement with the results of the impedance spectroscopy analysis.     

Field cycling-induced evolution of functional properties in bismuth samarium ferrite ceramics

The field-controlled phase transition is a promising concept for the design of novel multiferroic materials. Rare-earth samarium-modified bismuth ferrite (Bi_1−xSm_xFeO₃) possesses a morphotropic phase boundary (MPB) that has similar free energies between the polar and nonpolar phases, making it an exceptional candidate. In this study, we investigated the electric field cycling-dependent behavior of ferroelectricity in Bi_1−xSm_xFeO₃ ceramics near MPB. During electric field cycling, a significantly enhanced remanent polarization was observed. Cycled Bi_0.86Sm_0.14FeO₃ and Bi_0.84Sm_0.16FeO₃ exhibited enhanced ferroelectric (remanent polarization >30 μC/cm²) and magnetic (remanent magnetization >0.20 emu/g) properties at room temperature. Through a systematic study of dynamic hysteresis measurements and a structural analysis, these results were attributed to a field cycling-induced nonpolar-to-polar phase transition. In situ high temperature measurements showed a previously unreported sharp anomaly of the piezoelectric coefficient (d₃₃) near the magnetic transition point (T_N). These results indicated a strong magnetoelectric coupling in rare earth-modified bismuth ferrite materials, suggesting the possibility of magnetically modulated piezoelectricity.     

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.     

Microstructural and electromagnetic study of low temperature fired nano crystalline MgCuZn ferrite with Bi2O3 addition

The present study investigates electromagnetic properties, as well as microstructural and thermal stability, of low temperature fired MgCuZn ferrite with the addition of various amounts of Bi₂O₃. To achieve better performance at low sintering temperature, ceramic specimens were fabricated using nano-sized precursor powders through the nitrate-citrate auto-combustion method. X-ray diffraction study shows the formation of single phase spinel structure without any impurity phases. Compared with the additive-free sample, the addition of Bi₂O₃ increases the density of all specimens. Scanning electron microscopy micrographs of samples indicate that Bi₂O₃ content significantly affects densification through grain growth promotion. Excessive amounts of Bi₂O₃, however, lead to abnormal grain growth. Moreover, the sample with 0.25 wt% Bi₂O₃ shows the highest density and grain shape uniformity as well as the lowest porosity. Dynamic magnetic properties were studied in a frequency range of 1–90 MHz, using an impedance analyzer. Results reveal that the sample with a low amount of additive (0.25 wt%) has the highest saturation magnetization, initial permeability (at 1 MHz), and quality factor, whereas it's Curie temperature slightly decreases. With the further increase of Bi₂O₃ content, however, the initial permeability and saturation magnetization of samples deteriorate gradually.     

Bi2O3 Addition Effects on the Sintering Mechanism,Magnetic Properties,and DC Superposition Behavior of NiCuZn Ferrites

The Bi₂O₃ addition effects on the densification mechanism, magnetic properties, and DC superposition behavior of NiCuZn ferrites are investigated in this study. Bi₂O₃ addition can effectively promote NiCuZn ferrite densification. The densification controlling mechanism is dominated by the liquid formation resulting from the Bi₂O₃ and Bi₂CuO₄ eutectic reaction as Bi₂O₃ addition is increased above 2wt%. A suitable compromise between the initial permeability and DC‐bias superposition characteristic can be obtained by adding a proper amount of Bi₂O₃ to adjust the nonmagnetic copper and bismuth‐rich precipitate thickness at the grain boundaries.     

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.     

The effect of SiO2 on electrical properties of low‐temperature‐sintered ZnO–Bi2O3–TiO2–Co2O3–MnO2‐based ceramics

ZnO–Bi₂O₃–TiO₂–Co₂O₃–MnO₂‐based (ZBTCM) varistors were fabricated via the conventional solid‐state method, and the effect of SiO₂ content on the phase transformation, microstructure, and electrical properties of the ZBTCM had been investigated. Results showed that this varistor can be sintered at a low temperature of 880°C with a high sintering density above 0.95 of the ZnO theoretical density. In these components, SiO₂ acts as a controller in ZnO grain growth, decreasing the grain size of ZnO from 3.67 to 1.92 μm, which in turn results in an increase in breakdown voltage E_1mA from 358.11 to 1080 V/mm. On the other hand, SiO₂ has a significant influence on the defect structure and component distribution at grain‐boundary regions. When SiO₂ content increases from 0 to 4 wt%, the value of the interface state density (N_s) increases sharply. At the same time, the electrical properties are improved gradually, and reach an optimized value with the nonlinear coefficient (α) up to 54.18, the barrier height (?_b) up to 2.90 eV, and the leakage current (I_L) down to 0.193 μA/cm².     

Nanocrystalline/Nanosized Ni1−γFe2+γO4 Ferrite Obtained by Contamination with Fe During Milling of NiO–Fe2O3 Mixture. Structural and Magnetic Characterization

The nanocrystalline nickel ferrite (NiFe₂O₄) was synthesized by reactive milling starting from equimolar mixture of oxides. The iron contamination during milling leads to a solid state reaction between Fe and NiFe₂O₄ spinel. This reaction starts for a milling time longer than 30 h. A mixed nickel–iron ferrite (Ni_1?γFe_2+γO₄) and elemental Ni are obtained. The evolution of the nickel–iron mixed ferrite during milling and its properties were investigated using X‐ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), Laser Particles Size Analyzer and magnetic measurements. Annealing treatment (350°C/4 h in vacuum) is favorable to the reaction between phases. Replacement of Ni²⁺ cations by iron cations provided by contamination leads to the increase of lattice parameter value of the spinel structure. The magnetization of the nickel–iron mixed ferrite newly formed is larger than the nickel ferrite magnetization (13.6 μ_B/f.u. and 6.22 μ_B/f.u., respectively), due to the magnetic moment of Fe²⁺ cation which is double as compared to the Ni²⁺ cation. Magnetization of the milled samples decreases during milling due to the structural changes induced by milling in the nickel–iron mixed ferrite. The annealing induces a reordering of the cations which leads to a larger magnetization.     

Performance Evaluation of Doped Titanium Oxide for Low‐Voltage Applications

Varistors are the electronic devices which are used in various industries to protect the electrical and electronic systems from sudden surges. In this research, the electrical properties of titanium dioxide (TiO₂) doped with tantalum pentoxide (Ta₂O₅), tungsten trioxide (WO₃), cobalt oxide (Co₃O₄), and bismuth oxide (Bi₂O₃) and fired at different temperatures were investigated for low‐voltage applications. The adequate amount of dopants at suitable sintering temperature had beneficial effect in improving the properties of TiO₂. The relative density was found to be more than 97% of theoretical density when samples sintered between 1300°C and 1400°C for all composition compared to undoped samples. On the other hand, the addition of dopants enhanced hardness and compressive strength of varistor disks. The average grain size was also increased with the dopants system, making it suitable for low‐voltage application. Furthermore, the current–voltage characteristic of the TiO₂ revealed a significantly high value of nonlinearity of 19.6. A high dielectric constant of 10⁴ with minimum dissipation factor of 0.002852 at 1 kHz was also obtained, thereby making it suitable for low‐voltage application.     

Perovskite‐Structured BiFeO3–Bi(Zn1/2Ti1/2)O3–PbTiO3 Solid Solution Piezoelectric Ceramics with Curie Temperature About 700°C

In this article, perovskite‐structured BiFeO₃–Bi(Zn_1/2Ti_1/2)O₃–PbTiO₃ (BF–BZT–PT) ternary solid solutions were prepared with traditional solid‐state reaction method and demonstrated to exhibit a coexistent phase boundary (CPB) with Curie temperature of T_C~700°C in the form of ceramics with microstructure grain size of several micron. It was found that those CPB ceramics fabricated with conventional electroceramic processing are mechanically and electrically robust and can be poled to set a high piezoelectricity for the ceramics prepared with multiple calcinations and sintering temperature around 750°C. A high piezoelectric property of T_C = 560°C, d₃₃ = 30 pC/N, ε₃₃^T/ε₀ = 302, and tanδ = 0.02 was obtained here for the CPB 0.53BF–0.15BZT–0.32PT ceramics with average grain size of about 0.3 μm. Primary experimental investigations found that the enhanced piezoelectric response and reduced ferroelectric Curie temperature are closely associated with the small grain size of microstructure feature, which induces lattice structural changes of increased amount ratio of rhombohedral‐to‐tetragonal phase accompanying with decreased tetragonality in the CPB ceramics. Taking advantage of structural phase boundary feature like the Pb(Zr,Ti)O₃ systems, through adjusting composition and microstructure grain size, the CPB BF–BZT–PT ceramics is a potential candidate to exhibit better piezoelectric properties than the commercial K‐15 Aurivillius‐type bismuth titanate ceramics. Our essay is anticipated to excite new designs of high–temperature, high–performance, perovskite‐structured, ferroelectric piezoceramics and extend their application fields of piezoelectric transducers.     

A novel economical grain boundary engineered ultra-high performance ZnO varistor with lesser dopants

A varistor having ultra-high performance was developed from doped ZnO nanopowders using a novel composition consisting of only three (Bi, Ca and Co oxides) dopants. Improved varistor properties were obtained (breakdown field (E_b) 27.5?±?5?kVcm^?1, coefficient of nonlinearity (α) 72?±?3 and leakage current density (L_c) 1.5?±?0.06?μAcm^?2) which are attributed to the small grain size and grain boundary engineering by phases such as Ca₄Bi₆O₁₃ and Ca_0.89Bi_3.11O_5.56 along with Co⁺² doping in the ZnO lattice. Complex impedance data indicated three relaxations at 25?°C and two relaxations at high temperature (>100?°C). The complex impedance data were fitted into two parallel RC model to extract electrical properties. Two stages of activation energy for DC conductivity were observed in these varistor samples where region I (<150?°C) is found to be due to shallow traps and region II (<225?°C) is due to deep traps. The novel composition is useful for commercial exploitation in wide range of surge protection applications.     

Characteristics of ZnO-based varistor ceramics doped with Al2O3

The influence of Al₂O₃ doping in the range 0.00–0.83 mol% on the microstructure and current–voltage characteristics of ZnO-based varistor ceramics sintered at 1200 °C for 2 h was studied. The threshold voltage V_T (V/mm) increased up to a dopant level of about 0.08 mol% Al₂O₃; the nonlinear coefficient α was significantly increased by additions of up to 0.04 mol% Al₂O₃, although larger additions of Al₂O₃ caused it to decrease; and the leakage current increased sharply with increasing amounts of Al₂O₃. Doping with Al₂O₃ up to about 0.12 mol% Al₂O₃ resulted in a significantly decreased ZnO grain size, which is mainly responsible for the significantly increased threshold voltage, V_T. No ZnAl₂O₄ spinel phase was detected in any of the samples, and EDXS and WDXS analyses showed that most of the added Al₂O₃ distributed between the Zn₇Sb₂O₁₂ spinel phase and the ZnO phase, while only trace amounts were detected in the Bi₂O₃-rich phase. The spinel phase incorporates an appropriate amount of Al₂O₃; however, with an increasing amount of added Al₂O₃, more of it remains outside the spinel phase in the Bi₂O₃-rich liquid, where it can incorporate into the growing ZnO grains at the sintering temperature. The amount of Al in the ZnO grains was determined. A mechanism for the grain growth inhibition resulting from the small amounts of Al₂O₃ in the Bi₂O₃-rich liquid phase is also proposed.     

Microstructures and Microwave Dielectric Properties of Bi2O3‐Deficient Bi12SiO20 Ceramics

The Microstructure and microwave dielectric properties of Bi₂O₃‐deficient Bi₁₂SiO₂₀ ceramics were investigated. A small amount of unreacted Bi₂O₃ phase melted during sintering at 825°C and assisted with densification and grain growth in all samples. The melted Bi₂O₃ reacted with remnant SiO₂ during cooling to form a Bi₄Si₃O₁₂ secondary phase. The nominal composition of Bi_11.8SiO_19.7 ceramics sintered at 825°C for 4 h had a high relative density of 97% of the theoretical density, and good microwave dielectric properties: ε_r = 39, Q × f = 74 000 GHz, and τ_f = ?14.1 ppm/°C. Moreover, this ceramic did not react with Ag at 825°C.     

Microstructure,magnetic, and power loss characteristics of low-sintered NiCuZn ferrites with La2O3-Bi2O3 additives

Low-temperature-sintered Ni_0.5Cu_0.125Zn_0.375Fe_1.98O₄ ferrites co-added with x wt% (x = 0.00-0.25 wt%) La₂O₃ and 0.25 wt% Bi₂O₃ were successfully prepared via conventional solid-phase reaction method. The phase composition, microstructure, magnetic properties, and especially power loss variation of the samples were systematically studied. The results showed that all samples possessed a single spinel phase structure at a sintering temperature of 900°C, exhibiting high degree of densification and uniform grains. The appropriate amount of La₂O₃ additive improved the saturation flux density and permeability of NiCuZn ferrites, simultaneously reducing the coercivity and power loss. The maximum permeability and the lowest power loss were achieved at x = 0.15 wt%. The corresponding sample had the homogeneous microstructure and excellent magnetic properties, being a promising low-temperature co-fired ferrite candidate for magnetic power components.     

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.     

The Cobalt Zinc Spinel Ferrite Nanofiber: Lightweight and Efficient Microwave Absorber

To solve the heavy mass problem of the traditional spinel ferrite using as the microwave absorber, the Co_xZn_(1?x)Fe₂O₄ (x = 0.2, 0.4, 0.6, 0.8) ferrite nanofibres were synthesized by electrospinning method. The phase composition, morphology, and electromagnetic properties were analyzed. The results showed that all the as‐prepared Co_xZn_(1?x)Fe₂O₄ ferrites exhibited the homogeneous nanofibrous shape. The saturation magnetization and coercivity were enhanced by tuning the Co²⁺ content. The electromagnetic loss analysis indicated that the Co_0.6Zn_0.4Fe₂O₄ ferrite nanofiber performed the strongest microwave attenuation ability. The microwave absorbing coating containing 15 wt% of Co_0.6Zn_0.4Fe₂O₄ ferrite nanofiber showed the reflection loss less than ?10 dB in the whole X‐band and 80% of the Ku‐band frequencies. Meanwhile, the surface density was only 2.4 Kg/m².     

Dielectric Properties and Relaxation of Bi2Ti2O7

The dielectric properties of Bi₂Ti₂O₇ were explored as a function of temperature and frequency. A comparison between the dielectric response of the well‐known Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) pyrochlore and the recently available Bi₂Ti₂O₇ sintered ceramic revealed considerable differences, which indicate that chemical disorder, and not atomic displacement on its own, is chiefly responsible for the dielectric relaxation in bismuth pyrochlores. A low‐frequency (<10 kHz) and relatively high‐temperature (~125 K) dielectric relaxation was observed in Bi₂Ti₂O₇. An Arrhenius function was used to model the relaxation behavior and yielded an activation energy of 0.162 eV and an attempt jump frequency of ~1 MHz. This response is consistent with space charge polarization and not the result of dipolar or ionic disorder.