Sintering of surfactant modified ZnO–Bi2O3 based varistor nanopowders

Surfactant modified nano-origin ZnO–Bi₂O₃ varistor powder was prepared in presence of cetyltrimethyl ammonium bromide (CTAB) surfactant through an aqueous reflux reaction at 100 °C. The compacted varistor discs made from the nano-origin powders were subjected to step-sintering, microwave sintering and solid-state sintering. The influences of CTAB in different sintering methods were analyzed from the densification characteristics, evolution of sintered microstructures and associated varistor properties (I–V). The conventional solid-state sintering produced 96% theoretical sintered dense samples at 1100 °C. The step and microwave sintered samples showed 93% and 99% sintered densities, respectively, with controlled microstructures having grain sizes in the range of 2–6 μm at the given conditions. The CTAB advantages were clearly seen in grain structuring and grain boundary properties, in addition to the enhanced densification and homogenous microstructures for obtaining high breakdown voltage and non-linearity coefficient.     

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.     

Effect of dual liquid phase sintering aids on the densification and microstructure of low temperature sintered alumina ceramics

Alumina ceramics was prepared by pressureless sintering technology in which a CuO–TiO₂–Bi₂O₃ mixture (0–4.0 wt% Bi₂O₃ and 4.0 wt% CuO and TiO₂) was added as dual liquid phase sintering aids. The phase compositions, microstructural feature, and sintering behaviour of the alumina ceramics were analyzed. The results showed that adding 2.5 wt% Bi₂O₃ to alumina ceramics can increase the contribution rate of initial stage of sintering to the sintering process. The relative density of the sample reached 97.63% after sintering at 1200 °C for 90 min. Measurements from differential scanning calorimetry, with the addition of CuO–TiO₂–Bi₂O_3, demonstrated the formation of two liquid phase points, 827.4 and 936.8 °C. Notably, the solid solution temperature of TiO₂ and Al₂O₃ ceramics diminished thanks to the dual liquid phase sintering aids, and at the same time the activation energy required also dropped from 368.96 to 137.31 kJ/mol. Research indicates that the combined action of dual liquid phase sintering and solid-state reaction sintering has promoted the densification of alumina ceramics during the sintering process while at the same time inhibiting the growth of abnormal grains so that a homogeneous microstructure can be formed.     

Low-temperature sintering and microwave dielectric properties of 3Z2B glass–Al2O3 composites

A potential low temperature co-fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and Al₂O₃ filler was investigated with regard to phase development and microwave dielectric properties as functions of the glass content and sintering temperature. The densification mechanism for 3Z2B–Al₂O₃ composites was reported. The linear shrinkage of 3Z2B glass–Al₂O₃ composites exhibited a typical one-stage densification behavior. XRD patterns showed that a new crystalline phase, ZnAl₂O₄ spinel, formed during densification, indicating that certain chemical reaction took place between the 3Z2B glass matrix and the alumina filler. Meanwhile, several zinc borate phases, including 4ZnO·3B₂O₃, crystallized from the glass matrix. Both of the reaction product phase and crystallization phases played an important role in improving the microwave dielectric properties of composites. The optimal composition sintered at 850–950 °C showed excellent microwave dielectric properties: ?_r = ∼5.0, Q·f₀ = ∼8000 GHz, and τ_f = ∼−32 ppm/°C at ∼7.0 GHz.     

Densification behaviors of Al2O3 ceramics during flash sintering

The densification behaviors of MgO-doped-Al₂O₃ ceramics in the flashing stage and the steady stage were investigated using the classic kinetic model. The results show that the most densification of MgO-doped Al₂O₃ was completed during the flashing stage. The densification mechanism transferred from particle rearrangement resulted from Columbic force among particles under the effect of electrical field in the flashing stage to the lattice diffusion in the steady stage. Therefore, the densification rate in the steady stage dramatically decreased. Additionally, the estimated densification activation energy in the steady stage of flash sintering is 396 kJ/mol, much lower than the activation densification of lattice diffusion measured from conventional sintering, likely due to the effect of electric field/current-induced point defects on the diffusion.     

Exploring the potential of the mechanical/thermal properties and co-shielding ability of Bi2O3-doped aluminum borate ceramics against neutron/gamma radiation

The efficient optimisation of radiation shielding materials (RSMs), which protect people from potential radiant threats, is highly desirable; however, it remains challenging. This study addresses the low-cost fabrication of the ceramic-based RSMs, aluminium borate-based ceramics using Bi₂O₃ as a novel simultaneous shielding agent and sintering promoter. The phase compositions, microstructures, sintering kinetics, and performances of the as-prepared Bi₂O₃ doped aluminium borate ceramics (BDABCs) are systematically researched. Finally, co-shielding tests for neutron and gamma radiation are performed. The results demonstrate that Bi₂O₃ can positively influence the sintering densification process of BDABCs via the evident reduction in the sintering activation energy. The migration of the Bi₂O₃–B₂O₃ liquid phase affects the pore structure, crystal morphology, and thermal conductivity of the samples. The obtained BDABCs exhibited highly reliable mechanical properties with a maximum elastic modulus and modulus of rupture of 124.3 GPa and 54.9 MPa, respectively; controllable thermal conductivity from 1.32 to 6.16 W m^?1 K^?1; and 12 wt% Bi₂O₃-doped sample (1400 °C × 3 h, 1.5 cm) shows the best radiation shielding performance, including 58.6% neutron and 26.6% γ rays. The obtained results manifest the enormous potential of BDABCs as structural materials and functional RSMs.     

Thermodynamics and kinetics of sintering of Y2O3

Surface energy (γ_S) and grain boundary energy (γ_GB) of yttrium oxide (Y₂O₃) were determined by analyzing the heat of sintering (ΔH_sintering) using differential scanning calorimetry (DSC). The data allowed quantification of sintering driving forces, which when combined with a thorough kinetic analysis of the process, provide better understanding of Y₂O₃ densification as well as insights into effective strategies to improve its sinterability. The quantitative thermodynamic study revealed moderate thermodynamic driving force for densification in Y₂O₃ (as compared to other oxides) represented by a dihedral angle of 152.7° calculated from its surface and grain boundary energies. The activation energy was determined as 307 ± 61 kJ/mol, consistent with activation energies previously reported for processes relevant to sintering of Y₂O_3, such as Y³⁺ diffusion and grain boundary mobility. Finally, we propose that a refined deconvolution study on the DSC curve for Y₂O₃ sintering, combined with the associated material's microstructure evolution, may help identify shifts in sintering mechanisms, and therefore, specific activation energies at increasing temperatures.     

Densification of fine-grained alumina ceramics doped by magnesia,yttria and zirconia evaluated by two different sintering models

The influence of various dopants (500 ppm MgO and Y₂O_3; 250 ppm ZrO₂) on sintering of fine-grained alumina ceramics was evaluated by high-temperature dilatometry. The apparent activation energy of sintering was estimated with the help of Master Sintering Curve and a model proposed by Wang and Raj. The densification kinetics was controlled by at least two mechanisms operating at low (higher activation energy) and high (lower activation energy) densities. Good agreement between the activation energies calculated with both models was observed for low as well as for high densities. The lowest value of activation energy exhibited undoped alumina; the addition of MgO resulted in slight increase of the activation energy. Y₂O₃ and ZrO₂ significantly inhibited the densification, which was reflected in the higher sintering activation energies. The low activation energies in the final sintering step indicates the importance of proper choice of sintering temperature, namely in the two-step sintering process.     

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.     

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.     

Rapid microwave sintering of zinc oxide-based varistor ceramics

Samples of ZnO + Bi₂O₃ + Sb₂O₃ varistor ceramics were microwave sintered using gyrotron systems operating at a frequency of 24 GHz. The microwave power was automatically regulated to implement heating at a constant heating rate of 10–130 °C/min up to a temperature of 1100–1300 °C with no isothermal hold. The final sintered density of the samples was 95–96 % of the theoretical value. Manifestations of the thermal instability associated with the liquid phase formation were observed at a temperature of about 600 °C. The estimated volumetrically absorbed power density at the onset of instability was ≥20 W/cm³, and the temperature difference measured between the center and periphery of the samples reached 200 °C. Correlation has been revealed between the thermal instability occurrence and the shift of densification curves towards lower temperatures. A mechanism underlying enhanced densification in electromagnetic field-assisted sintering processes is suggested.     

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.     

Microwave versus conventional sintering: Estimate of the apparent activation energy for densification of α-alumina and zinc oxide

A comparative study between the conventional and 2.45 GHz microwave multimode sintering behavior of insulator (α-Al₂O₃) and semi-conductive ceramic (ZnO) was systematically investigated. The apparent activation energy of nonisothermal sintering was determined by way of the Arrhenius plot of densification data at constant heating rates (CHR) and the concepts of Master Sintering Curves (MSCs), respectively. During microwave densification process, the apparent activation energy was about 90 kJ/mol less than the value for conventional sintering of Al₂O₃ applying these two estimation methods. However, an opposite result was obtained in the case of ZnO, although its densification process had been also accelerated by microwave as well as Al₂O₃. The significant differences in activation energy give a good proof of the difference in diffusion mechanism induced by the electromagnetic field underlying microwave sintering.     

Constrained Sintering of a Low‐Fire,Polycrystalline Bi2(Zn1/3Nb2/3)2O7 Dielectric

The densification behavior of a low‐fire, polycrystalline Bi₂(Zn_1/3Nb_2/3)₂O₇ (BZN) dielectric under constrained sintering at 800°C–900°C is investigated. Although the constrained densification is retarded in relative to free sintering, a high sintered density of >95% is obtained at 900°C. No significant anisotropy with similar grain sizes is developed under free and constrained sintering. The densification behavior and stress development during constrained sintering of BZN is thus analyzed by using the well‐known isotropic constitutive laws.     

Thick film ZnO based varistors prepared by screen printing

Thick film varistors based on the system ZnO–Bi₂O₃–Sb₂O₃ have been prepared by screen printing technology on dense alumina substrates. Different processing strategies have been designed in order to control the excessive volatilization of Bi₂O₃ in varistor films during the sintering, due to the high area–volume ratio, and as a means to improving their electrical response. Starting powders were selected and pre-treated in different ways to obtain different phases and control the Bi-rich liquid phase formation. Significant differences have been observed in the electrical properties which are related to the selection of the starting powders.     

Effect of Bi2O3 content on sintering and crystallization behavior of low-temperature firing Bi2O3–B2O3–SiO2 glasses

The sintering behavior of a Pb-free Bi₂O₃–B₂O₃–SiO₂ glass system was examined as a function of Bi₂O₃ content. The glass transition temperature and the crystallization temperature of the glasses decreased with different decreasing gradients as the Bi₂O₃ content increased. The change in temperature affected the sintering behaviors of the glasses. In the case of the 40 mol% Bi₂O₃ addition, large pore accompanied over-firing phenomenon was observed when the sample was sintered over the optimum sintering temperature. However, over-firing was not observed in the sample with 45 mol% of Bi₂O₃ because of the crystallized phases during sintering. When the Bi₂O₃ content was 50–55 mol%, the crystallization temperature became lower than the glass transition temperature, which resulted in the crystallization of glass and it hindered densification.     

Phase formation during liquid phase sintering of ZnO ceramics

ZnO doped with Bi₂O₃ and Sb₂O₃ (ZBS), is the basic system for ceramic varistors. Phase formation during sintering of ZBS was measured in situ, using 1 mm thick samples and synchrotron X-rays. Sintering shrinkage was measured in different atmospheres by an optical method. Thermodynamic calculations were performed to explain phase formation, composition, stability of additive oxides and influence of the oxygen fugacity on sintering. Sb₂O₄, pyrochlore, trirutile and spinel were formed at temperatures of 500–800 °C. The oxidation of antimony was controlled by the oxygen partial pressure and affected both, phase formation and sintering kinetics, in the ZBS system.     

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.     

Effects of alumina on the crystallization behavior, densification and dielectric properties of BaO–ZnO–SrO–CaO–Nd2O3–TiO2–B2O3–SiO2 glass–ceramics

The alumina addition effects on the crystallization, sintering behaviors and dielectric properties of BaO–ZnO–SrO–CaO–Nd₂O₃–TiO₂–B₂O₃–SiO₂ (Ba–Zn–Sr–Ca–Nd–Ti–B–Si) glass powder were investigated using the differential thermal analyzer (DTA), thermo-mechanical analyzer (TMA), X-ray diffractometer (XRD). The results showed that the addition of alumina powder into Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass changed the crystallization sequence from Nd₂Ti₄O₁₁–Nd_0.66TiO₃ to Nd₂Ti₃O_8.7–Nd₂Ti₂O₇–Nd₂Ti₄O₁₁and increased the densification activation energy due to the dissolution of Al³⁺ ions into the glass structure. Fully densified 30 vol.% alumina-added Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass can be obtained via glass viscous flow before the second and third crystalline phases, Nd₂Ti₂O₇ and Nd₂Ti₄O₁₁crystallization. The 30 vol.% alumina-added Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass–ceramics sintered at 900 °C exhibited a high dielectric constant of 17 and a quality factor of about 820, which provided a promising candidate for LTCC applications.     

One-pot synthesis of antimony oxide and bismuth oxide nanocomposites for the selective electrochemical determination of the anticancer drug methotrexate in biomedical samples

Methotrexate (MTRX) is an anticancer drug that is also used for several chronic illnesses; however, a high dosage of MTRX can cause adverse effects, so it is necessary to monitor the MTRX level in blood and urine samples. This work reports the electrochemical determination of MTRX based on Sb₂O₃ and Bi₂O₃ composite material (Sb₂O₃@Bi₂O₃)modified electrodes. The one-pot sonohydrolysis synthesis method is employed for the preparation of the Sb₂O₃@Bi₂O₃ composite, which reveals high crystallinity with mixed phases of monoclinic Bi₂O₃ and cubic Sb₂O₃. Furthermore, the phases are identified by XRD, Raman spectroscopy, XPS, and HRTEM analysis. This composite reveals nanoneedle and nanocube morphologies. The Sb₂O₃@Bi₂O₃modified GCE shows excellent electrochemical activity for the detection of the anticancer drug methotrexate (MTRX). The activity is compared with the individual Sb₂O₃ and Bi₂O₃ compounds. Sb₂O₃@Bi₂O₃/GCE shows good electroanalytical characteristics in chronoamperometric analysis. Sb₂O₃@Bi₂O₃/GCE exhibits a linear range of approximately 0.01 μM to 174.6 μM, a sensitivity of 1.46 μA cm^-2μM^-1, and an LOD of 2.9 nM. Moreover, Sb₂O₃@Bi₂O₃/GCE delivered high selectivity among highly interfering compounds in blood and urine samples.