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.     

Influence of Bi2O3/TiO2, Sb2O3 and Cr2O3 doping on low-voltage varistor ceramics

The influence of the amount of Bi₂O₃ and TiO₂ additions at a TiO₂/Bi₂O₃ ratio of 1, as well as Sb₂O₃ and/or Cr₂O₃ doping, on the microstructural development and electrical properties of varistor ceramics in the ZnO–Bi₂O₃–TiO₂–Co₃O₄–Mn₂O₃ system was investigated. In samples with a low level of Bi₂O₃ and TiO₂ (0·3 mol%) and therefore small amount of liquid phase, exaggerated growth of the ZnO grains results in high microstructural inhomogeneity. Co-doping with Sb₂O₃ significantly changes the phase composition of TiO₂ doped low-voltage varistor ceramics. The Bi₃Zn₂Sb₃O₁₁ type pyrochlore phase forms at the expense of the γ-Bi₂O₃ and Bi₄Ti₃O₁₂ phases and decreases the amount of liquid phase in the early stages of sintering. Already small amounts of Sb₂O₃ and/or Cr₂O₃ added to a TiO₂ doped low-voltage varistor ceramics limit ZnO grain growth and increase the threshold voltage V_T of the samples.     

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.     

Effects of Sb and Nb dopants on electrical and microstructural properties of low-voltage varistor ceramics based on SnO2

It is shown that an addition of Sb₂O₅ or Nb₂O₅ (0.05–0.15?mol%) to the system SnO₂–CoO–Cr₂O₃–Bi₂O₃ leads to the enhancement of grain growth. This effect is associated with the presence of the liquid Bi-phase in ceramics during sintering. The obtained ceramics possess non-linear current-voltage characteristics and can be used for preparing low voltage varistors. The non-linearity coefficient α reaches 22 and the characteristic electric field 692?V/cm for Nb-doped materials and 11 and 421?V/cm respectively for Sb-doped ceramics materials. The results of dc and ac electrical measurements, as well as scanning electron microscopy are presented and discussed in terms of the known barrier model for varistors.     

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.     

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, electrical properties, and aging behavior of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-Er2O3 varistor ceramics

The microstructure, electrical properties, and aging behavior of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-Er₂O₃ varistor ceramics were investigated for different contents of Er₂O₃. The microstructure consisted of ZnO grain and an intergranular layer (Pr, Y, and Er-rich phases) as a secondary phase. The increase of Er₂O₃ content decreased the average grain size and increased the sintered density. As the Er₂O₃ content increased, the breakdown field increased from 4206 V/cm to 5857 V/cm and the nonlinear coefficient increased from 32.6 to 48.6. The varistor ceramics added with 1.0 mol% Er₂O₃ exhibited excellent stability by exhibiting −0.2% in the variation rate of the breakdown field and −2.7% in the variation rate of the nonlinear coefficient for aging stress of 0.95 E_1 mA/150 °C/24 h.     

Plasma dynamic synthesis of composite ZnO-Bi2O3 material with a core-shell structure for varistor ceramics

Zinc oxide has been studied for many years and found many applications in different areas, including the power engineering, where the ZnO-based ceramics could be used as a varistor. However, there is a necessity to add different oxides to ZnO to make a uniform ceramics structure with well enough nonlinear characteristics. In this regard, the uniform distribution of additives in the structure of a composite based on ZnO becomes an urgent task to prepare the high-quality ceramics. This work shows the possibility to obtain the composite powdered material with the uniformly distributed Bi₂O₃ addition in the ZnO crystallites by a plasma dynamic method. The features of this method and flowing reactions allow forming the ZnO-Bi₂O₃ particles with the core-shell structure. The spark plasma sintering of the ZnO-Bi₂O₃ composite material with such particles structure provides the production of varistor ceramics characterized by a fine-grained ZnO structure (average grain size is about 1?µm) with uniformly filled intergranular spaces by Bi₂O₃. The comparison of voltage-current characteristics with the ceramics made of ball-milled commercial powders showed the prospects of using as-prepared ZnO-Bi₂O₃ composite with core-shell structure.     

Texture development and dielectric relaxor behavior of 0.80Na0.5Bi0.5TiO3–0.20K0.5Bi0.5TiO3 ceramics templated by plate-like NaNbO3 particles

Plate-like NaNbO₃ particles were used as templates to fabricate grain-oriented 0.96(0.8Na_0.5Bi_0.5TiO₃–0.2 K_0.5Bi_0.5TiO₃)–0.04NaNbO₃ (NKBT) ceramics. The effects of the sintering temperature and the soaking time on the grain orientation and the microstructure of the textured NKBT ceramics were investigated, and the dielectric relaxor behavior is discussed. The results show that textured ceramics were successfully obtained with orientation factor more than 0.8. The textured ceramics have a microstructure with strip-like grains aligning in the direction parallel to the casting plane. The degree of grain orientation increases initially, then decreases with increasing sintering temperature, and increases continuously with increasing soaking time. The textured NKBT ceramics shows obvious dielectric relaxor characteristics which can be well explained by microdomain–macrodomain transition theory with calculating criterion K. The results show that formation of texture is beneficial to microdomain–macrodomain transition, which lead to weaken relaxor behavior and raise the dielectric constant at T_tr.     

Thermoelectric properties of Bi2O3-added WO3 ceramics

Tungsten trioxide (WO₃) ceramics were prepared by firing Bi₂O₃-added WO₃ compacts with atomic ratios of Bi/W?=?0.00, 0.01, 0.03, or 0.05, in which Bi₂O₃ was mixed as a sintering agent. Dense ceramics consisting of remarkably grown WO₃ grains were obtained for Bi-containing samples with Bi/W?=?0.01, 0.03, and 0.05. The grain growth was enhanced by the liquid phase of Bi₂W₂O₉ formed among the WO₃ grains while firing. The XRD patterns did not show evidence for Bi inclusion into the WO₃ lattice, but the SEM-EDX showed an intensive distribution of Bi into the grain boundaries. Electrical conductivity σ and Seebeck coefficient S were measured in a temperature range of 373–1073?K. The temperature dependences indicated that the Bi₂O₃-added WO₃ ceramics were n-type semiconductors. It was considered that the electron carriers were generated from oxygen vacancies included into the WO₃ grains. The thermoelectric power factors S²σ for the ceramics ranged from 1.5?×?10^?7 W?m^?1 K^?2 to 2.8?×?10^?5 W?m^?1 K^?2, and the highest value occurred at 970?K for the ceramic with Bi/W?=?0.01.     

Grain Growth Control in Sb2O3-Doped Zinc Oxide

Microstructure development in Sb₂O₃-doped ZnO was studied to evaluate the influence of inversion boundaries (IBs) on ZnO grain growth. In general, the addition of Sb₂O₃ is believed to inhibit the ZnO grain growth via the formation of spinels and IBs, but we have shown that even the conditions of exaggerated grain growth can be created in this system. We designed an experiment for diffusional doping of ZnO under slightly increased partial pressure of Sb₂O₃. In the high-concentration regime we observed no spinels, and yet the ZnO grains were small and inhibited in growth, while in the low-concentration regime we found huge grains, several times larger than normal ZnO grains, showing an obvious exaggerated growth. By controlling the number of nuclei with IBs we can design coarse-grained microstructures even with Sb₂O₃ doping, which has far-reaching implications in the production of low-voltage varistor devices.     

Unique interface-driven crystallization mechanism and element-resolved structure imaging of ZnO-Ge2Sb2Te5 nanocomposites

Amorphous Ge₂Sb₂Te₅ thin films doped with ZnO were prepared and their crystallization behaviors were investigated. Our results showed that thermal annealing of amorphous ZnO-Ge₂Sb₂Te₅ nanocomposites produced face centered-cubic Ge₂Sb₂Te₅-nanocrystals embedded between interfaces. An increase in crystallization temperature and electrical resistance ratio were attributed to the increase of specific interfacial energies and inhomogeneous strain at the oxide/Ge₂Sb₂Te₅ interfaces. The formation of the interfaces not only accelerated crystallization, but also limited the grain growth due to the one-dimensional growth mode. We proposed a crystallization model to elucidate the derived kinetic mechanism of the nanocrystal growth in the Ge₂Sb₂Te₅ matrix. These experimental observations suggest that ZnO-Ge₂Sb₂Te₅ nanocomposites are a good candidate for the applications in phase change memory.     

Effect of TiO2 on phase evolution and microstructure of MgAl2O4 spinel in different atmospheres

The effect of TiO₂ on the formation and microstructure of magnesium aluminate spinel (MgAl₂O₄) at 1600 °C in air and reducing conditions were investigated. Under reducing conditions, stoichiometric MgAl₂O₄ spinel shifted toward alumina-rich types owing to volatilization of MgO, resulting in an increase in the porosity of fired samples. Addition of graphite to mixtures of MgO and Al₂O₃ intensified the reducing conditions and accelerated the formation of non-stoichiometric MgAl₂O₄. For TiO₂-containing samples on addition of MgAl₂O₄, magnesium aluminum titanium oxide (Mg_xAl_2(1−x)Ti_(1+x)O₅, x = 0.2 or 0.3) was detected as a minor phase. Under reducing conditions, XRD peak shifts were smaller for TiO₂-containing samples than for samples without TiO₂ owing to the formation of a solid solution of TiO₂ in MgAl₂O₄ and establishment of alumina-rich spinel, which have opposite effects on increasing the lattice parameter. In bauxite-containing samples, MgAl₂O₄ spinel, corundum, magnesium orthotitanate spinel (Mg₂TiO₄) and amorphous phases were identified. Mg₂TiO₄ spinel formed a complete solid solution with MgAl₂O₄ spinel but Mg₂TiO₄ remained as a distinct phase owing to the heterogeneous microstructure of bauxite-containing samples. Also dense microstructure established in air fired TiO₂ containing samples. The results are discussed with emphasis on the application and design of alumina-magnesia-carbon refractory materials, which are used in the steel industry.     

Effect of TiO2 addition on grain shape and grain coarsening behavior in 95Na1/2Bi1/2TiO3-5BaTiO3

Grain coarsening behavior in the 95Na_1/2Bi_1/2TiO₃-5BaTiO₃ system has been studied as a function of the addition of TiO₂. As the amount of added TiO₂ was increased, the grain shape changed to a more faceted cube, indicating an increase in the step free energy of the facets, and hence a rise in the critical driving force for appreciable growth of grains. Grain coarsening behavior also changed from pseudo-normal to abnormal with an increasing TiO₂ concentration and thus increased faceting. The pseudo-normal behavior observed in the system without TiO₂ addition also changed to quite abnormal behavior during extended sintering. These observations support our theoretical prediction based on the coupling effects between the maximum driving force for growth and the critical driving force for appreciable growth.     

Intermediate phases formation during the synthesis of Bi4Ti3O12 by solid state reaction

In this work, the formation of Bi₄Ti₃O₁₂ by solid state reaction from Bi₂O₃ and TiO₂ starting powders has been studied. The Bi₄Ti₃O₁₂ formation occurs through an intermediate Bi₁₂TiO₂₀ sillenite phase formed at temperatures sligthly over 300 °C. This sillenite phase is stable up to ∼750 °C, but in the presence of TiO₂ reacts to form Bi₄Ti₃O₁₂ at temperatures >500 °C. Raman spectroscopy has been used to evidence the amorphization of TiO₂, demonstrating that the Bi₄Ti₃O₁₂ formation occurs through the reaction of sillenite Bi₁₂TiO₂₀ and TiO₂.     

Effects of MgO and Fe2O3 additives on the microstructure and fracture properties of aluminium titanate flexible ceramics

Aluminium titanate (Al₂TiO₅, AT) flexible ceramics were prepared from Al₂O₃–TiO₂ powder system with MgO and Fe₂O₃ as additives through solid-state method. The effects of addition level of MgO and Fe₂O₃ on phase compositions, sintering behavior, microstructure and fracture properties of AT flexible ceramics were systematically investigated. The experimental results show that the introduction of additives can promote the formation of AT and improve the densification by forming solid solution. The addition of MgO could effectively refine AT grains since the formed MgAl₂O₄ spinel grains could pin at the AT grain boundary and inhibit the growth of AT grains. Conversely, the addition of Fe₂O₃ could promote the AT grain growth. And the simultaneous addition of MgO and Fe₂O₃ is beneficial to develop elongated rod-like AT grains. With that, the improved fracture properties can be obtained. Due to pining effect of spinel and better densification, the flexural strength of modified AT flexible ceramics is about 34 times higher than that of virgin. In addition, thanks to the microcracked structure and high grain aspect ratio, events of crack deflection, crack branching, grains pull-out and grains bridging are more likely to occur, leading to an increase in the flexibility by about 133%.     

Spinelisation and properties of Al2O3–MgAl2O4–C refractory: Effect of MgO and Al2O3 reactants

The effect of particle size of MgO and Al₂O₃ on the spinel formation associated with permanent linear change on reheating (PLCR) and microstructure of Al₂O₃–MgAl₂O₄–C refractory is investigated as a function of heating cycle at 1600 °C with 2 h holding at each cycle. It was found that rate of spinel formation and associated volume expansion is very much dependent on the reactivity and particle size of the reactant. When the reactants are very fine and reactive there is considerable amount of spinel formation, whereas coarser reactants with lower reactivity show negligible formation of spinel phase and associated expansion. Magnesia and alumina with moderate reactivity develops optimum PLCR of the refractory. It continuously increases with the number of heating cycles. The SEM photomicrographs show that in Al₂O₃–MgAl₂O₄–C refractory the spinel phase is formed in between the calcined bauxite grain and the EDX analysis indicates that the spinel phase formed is stoichiometric in nature.     

Grain growth kinetics in microwave sintered graphene platelets reinforced ZrO2/Al2O3 composites

The grain growth kinetics and mechanical properties of graphene platelets(GPLs) reinforced ZrO₂/Al₂O₃(ZTA) composites prepared by microwave sintering were investigated. The calculated grain growth kinetics exponent n indicated that the GPLs could accelerate the process of the Al₂O₃ columnar crystal growth. And the grain growth activation energy of the Al₂O₃ columnar crystal indicated that the grain growth activation energy of the GPLs doped ZTA composites is much higher than those of pure Al₂O₃ and ZTA in microwave sintering. The optimal mechanical properties were achieved with 0.4?vol% GPLs, whose relative density, Vickers hardness and fracture toughness were 98.76%, 18.10?GPa and 8.86?MPa?m^1/2, respectively. The toughening mechanisms were crack deflection, bridging, branching and pull-out of GPLs. The results suggested that GPLs-doped are good for the Al₂O₃ columnar crystal growth in the ZTA ceramic and have a potentially improvement for the fracture toughness of the ceramics.     

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.