Ultra-Fine Ba2Ti9O20 Powders Synthesized by Inverse Microemulsion Processing and their Microwave Dielectric Properties

A double–inverse microemulsion (IME) process is used for synthesizing nano-sized Ba₂Ti₉O₂₀ powders. The crystallization of powders thus obtained and the microwave dielectric properties of the sintered materials were examined. The IME-derived powders are of nano-size (∼21.5 nm) and possess high activity. The BaTi₅O₁₁, intermediate phase resulted when the IME-derived powders were calcined at 800°C (4 h) in air. However, high-density Ba₂Ti₉O₂₀ materials with a pure triclinic phase (Hollandite like) can still be obtained by sintering such a BaTi₅O₁₁ dominated powders at 1250°C/4 h. The phase transformation kinetics for the IME-derived powders were markedly enhanced when air was replaced by O₂ during the calcinations and sintering processes. Both the calcination and densification temperatures were reduced by around 50°C compared with the process undertaken in air. The microwave dielectric properties of sintered materials increase with the density of the samples, resulting in a large dielectric constant ( K ≅39) and high-quality factor ( Q × f ≅28 000 GHz) for samples possessing a density higher than 95% theoretical density, regardless of the sintering atmosphere. Overfiring dissociates Ba₂Ti₉O₂₀ materials and results in a poor-quality factor.     

Effect of Glass Additions on BaO–TiO2–WO3 Microwave Ceramics

The effect of glass addition on the properties of BaO–TiO₂-WO₃ microwave dielectric material N-35, which has Q = 5900 and K = 35 at 7.2 GHz for samples sintered at 1360°C, was investigated. Several glasses including B₂O₃, SiO₂, 5ZnO–2B₂O₃, and nine other commercial glasses were selected for this study. Among these glasses, one with a 5 wt% addition of B₂O₃ to N-35, when sintered at 1200°C, had the best dielectric properties: Q = 8300 and K = 34 at 8.5 GHz. Both Q and K increased with firing temperature as well as with density. The Q of N-35, when sintered with a ZnO–B₂O₃ glass system, showed a sudden drop in the sintering temperature to about 1000°C. The results of XRD, thermal analysis, and scanning electron microscopy indicated that the chemical reaction between the dielectric ceramics and glass had a greater effect on Q than on the density. The effects of the glass content and the mixing process on the densification and microwave dielectric properties are also presented. Ball milling improved the densification and dielectric properties of the N-35 sintered with ZnO–B₂O₃.     

Sintering of Partially Stabilized Zirconia by Microwave Heating Using ZnO–MnO2–Al2O3 Plates in a Domestic Microwave Oven

Partially stabilized zirconia (PSZ) powders were fully densified by microwave heating using a domestic microwave oven. Pressed powder compacts of PSZ were sandwiched between two ZnO–MnO₂–Al₂O₃ ceramic plates and put into the microwave oven. In the first step, PSZ green pellets were heated by self-heating of ZnO–MnO₂–Al₂O₃ ceramics (1000°C). In the second step, the heated PSZ pellets absorbed microwave energy and self-heated up to a higher temperature (1250°C), leading to densification. The density of PSZ obtained by heating in the microwave oven for 16 min was 5.7 g/cm³, which was approximately equal to the density of bodies sintered at 1300°C for 4 h or 1400°C for 16 min by the conventional method. The average grain size of the sample obtained by this method was larger than the average grain size of samples sintered by the conventional method with a similar heating process.     

Densification Behavior in Microwave-Sintered Silicon Nitride at 28 GHz

Si₃N₄ powders were sintered using a 28 GHz gyrotron source, with Y₂O₃, Al₂O₃, and MgO as sintering aids, in an attempt to investigate the effect of microwave radiation on densification behavior. The microwave-sintered samples were compared with identical samples produced by conventional pressureless sintering. The effect of sintering on the microstructural development and grain growth of the samples was assessed using scanning electron microscopy. Phase transformation behavior was assessed using X-ray diffractometry. In the microwave-sintered samples, densification and α→β transformation occurred at temperatures ∼200°C lower than those of the conventionally sintered samples. More importantly, at comparable stages of densification, the microstructures of the microwave-sintered and conventionally sintered samples were significantly different, with the microwave-sintered samples showing the development of elongated β grains at a much earlier stage of the α→β transformation. It was concluded that the effect of microwave radiation on sintering was not simply a decrease in sintering temperatures, but in possibly a different sintering mechanism, clearly related to localized heating within the grain-boundary phase.     

Pressureless Densification of Zirconium Diboride with Boron Carbide Additions

Zirconium diboride (ZrB₂) was densified (>98% relative density) at temperatures as low as 1850°C by pressureless sintering. Sintering was activated by removing oxide impurities (B₂O₃ and ZrO₂) from particle surfaces. Boron oxide had a high vapor pressure and was removed during heating under a mild vacuum (∼150 mTorr). Zirconia was more persistent and had to be removed by chemical reaction. Both WC and B₄C were evaluated as additives to facilitate the removal of ZrO₂. Reactions were proposed based on thermodynamic analysis and then confirmed by X-ray diffraction analysis of reacted powder mixtures. After the preliminary powder studies, densification was studied using either as-received ZrB₂ (surface area ∼1 m²/g) or attrition-milled ZrB₂ (surface area ∼7.5 m²/g) with WC and/or B₄C as a sintering aid. ZrB₂ containing only WC could be sintered to ∼95% relative density in 4 h at 2050°C under vacuum. In contrast, the addition of B₄C allowed for sintering to >98% relative density in 1 h at 1850°C under vacuum.     

Pressureless Sintering of Zirconium Diboride: Particle Size and Additive Effects

Zirconium diboride (ZrB₂) was densified by pressureless sintering using <4-wt% boron carbide and/or carbon as sintering aids. As-received ZrB₂ with an average particle size of ∼2 μm could be sintered to ∼100% density at 1900°C using a combination of boron carbide and carbon to react with and remove the surface oxide impurities. Even though particle size reduction increased the oxygen content of the powders from ∼0.9 wt% for the as-received powder to ∼2.0 wt%, the reduction in particle size enhanced the sinterability of the powder. Attrition-milled ZrB₂ with an average particle size of <0.5 μm was sintered to nearly full density at 1850°C using either boron carbide or a combination of boride carbide and carbon. Regardless of the starting particle size, densification of ZrB₂ was not possible without the removal of oxygen-based impurities on the particle surfaces by a chemical reaction.     

Fabrication and Characterization of Anode-Supported Tubular Solid-Oxide Fuel Cells by Slip Casting and Dip Coating Techniques

High-performance anode-supported tubular solid-oxide fuel cells (SOFCs) have been successfully developed and fabricated using slip casting, dip coating, and impregnation techniques. The effect of a dispersant and solid loading on the viscosity of the NiO/Y₂O₃–ZrO₂ (NiO/YSZ) slurry is investigated in detail. The viscosity of the slurry was found to be minimum when the dispersant content was 0.6 wt% of NiO/YSZ. The effect of sintering temperature on the shrinkage and porosity of the anode tubes, densification of the electrolyte, and performance of the cell at different solid loadings is also investigated. A Ni/YSZ anode-supported tubular cell fabricated from the NiO/YSZ slurry with 65 wt% solid loading and sintered at 1380°C produced a peak power output of ∼491 and ∼376 mW/cm² at 800°C in wet H₂ and CH₄, respectively. With the impregnation of Ce_0.8Gd_0.2O₂ (GDC) nanoparticles, the peak power density increased to ∼1104 and ∼770 mW/cm² at 800°C in wet H₂ and CH₄, respectively. GDC impregnation considerably enhances the electrochemical performance of the cell and significantly reduces the ohmic and polarization resistances of thin solid electrolyte cells.     

Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

Pressureless Sintering of SiC-Whisker-Reinforced Al2O3 Composites: II, Effects of Sintering Additives and Green Body Infiltration

Pressureless sintering of SiC-whisker-reinforced Al₂O₃ composites was investigated. In Part II of the study, the effects of Y₂O₃/MgO sintering additives and green body infiltration on densification behavior and microstructure development are reported. Both sintering additives and green body infiltration resulted in enhanced densification. However, the infiltration approach was more effective for samples with high SiC whisker concentrations. Samples with 27 vol% whiskers could be pressureless sintered to ∼93% relative density and ∼3% open porosity. Fracture toughness values and microstructural features (e.g., grain size) for the infiltrated samples remained approximately the same as observed in the uninfiltrated samples.     

Preparation of High-Silica Glasses from Colloidal Gels: II, Sintering

The sintering of dried colloidal SiO₂ gels, whose preparation and properties are reported in Part I, is described. The effects of various sintering parameters were studied and the conditions for achievement of the best optical quality include the use of: a pretreatment of the SiO₂ at ∼925°C, moderate heating rate (∼400°C/h), He+CI₂ atmosphere, 1500° to 1600°C sintering temperature, and 1 to 4 h sintering time. Dynamic sintering kinetic studies (heating rate=400°C/h) show that this SiO₂ sinters to nearly theoretical density by about 1380°C. However, optical transparency is achieved by removal of minor residual porosity at above 1500°C. Isothermal sintering data fit to a model assuming interconnecting cylinders of SiO₂ predict the proper activation energy for the viscosity if initial stages of sintering are considered. Residual porosity in sintered glasses is related to large interstices in the unsintered gel.     

Finite Size Effect on the Sinterability and Dielectric Properties of ZnNb2O6–ZBS Glass Composites

ZnNb₂O₆ (ZN) is a columbite-structured niobate compound showing excellent dielectric properties and comparatively low sintering temperatures (∼1200°C). Hence it is a good candidate for possible low-temperature cofired ceramics (LTCC) applications. In the present investigation, ZnNb₂O₆ was synthesized in the form of micrometer-sized powder using a conventional solid-state ceramic synthesis route as well as in the form of nanosized powder by a polymer complex method. The finite size effect of ZN particles on sinterability and microwave dielectric properties of sintered pellets was evaluated. The phase formation was confirmed from the X-ray diffraction (XRD) analysis. The particle size distribution of the nanoparticles was found to be of the order of 18–20 nm by using high-resolution transmission electron microscopy analysis and 30 nm by analyzing the XRD patterns using Debye Scherrer's formula, after correcting for the instrument broadening effects. A ZN–60ZnO–30B₂O₃–10SiO₂ (ZBS) composite was made by adding predetermined amounts of glasses. The microstructures of the sintered pellets of ZN and ZN–ZBS composites were examined using scanning electron microscopy and analyzed using image analysis. The nano-ZN–ZBS composites were sintered to 93% of the reported density at 925°C/2 h, with microwave dielectric properties of ɛ_r=22.5, Q × f ∼12 800 GHz, and τ_f=−69.6 ppm/°C, emerging as a potential material for possible LTCC applications.     

Pressureless Sintering of High-Density ZrB2–SiC Ceramic Composites

Ultra-high-temperature ceramic composites of ZrB₂ 20 wt%SiC were pressureless sintered under an argon atmosphere. The starting ZrB₂ powder was synthesized via the sol–gel method with a small crystallite size and a large specific surface area. Dry-pressed compacts using 4 wt% Mo as a sintering aid can be pressureless sintered to ∼97.7% theoretical density at 2250°C for 2 h. Vickers hardness and fracture toughness of the sintered ceramic composites were 14.82±0.25 GPa and 5.39±0.13 MPa·m^1/2, respectively. In addition to the good sinterability of the ZrB₂ powders, X-ray diffraction and scanning electron microscopy results showed that Mo formed a solid solution with ZrB₂, which was believed to be beneficial for the densification process.     

Effect of Li2CO3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Mg2V2O7 Ceramics

Li₂CO₃ was added to Mg₂V₂O₇ ceramics in order to reduce the sintering temperature to below 900°C. At temperatures below 900°C, a liquid phase was formed during sintering, which assisted the densification of the specimens. The addition of Li₂CO₃ changed the crystal structure of Mg₂V₂O₇ ceramics from triclinic to monoclinic. The 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic was well sintered at 800°C with a high density and good microwave dielectric properties of ɛ _r=8.2, Q × f =70 621 GHz, and τ_f=−35.2 ppm/°C. Silver did not react with the 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic at 800°C. Therefore, this ceramic is a good candidate material in low-temperature co-fired ceramic multilayer devices.     

Pressureless Sintering of SiC-Whisker-Reinforced Al2O3 Composites: I, Effect of Matrix Powder Surface Area

Pressureless sintering of SiC-whisker-reinforced Al₂O₃ composites was investigated. In Part I of the study, the effect of the matrix (Al₂O₃) powder surface area on densification behavior and microstructure development is reported. Compacts prepared with higher surface area Al₂O₃ powder showed enhanced densification at lower whisker concentrations (5 and 15 vol%). Samples with 15 vol% whiskers could be pressureless sintered to ∼97% relative density with zero open porosity and ∼1.6-μm matrix average grain intercept size.     

Mg–Cu–Zn Ferrites for Multilayer Inductors

Mg–Cu–Zn ferrites can be sintered at T ≤950°C to sufficient density and display adequate permeability profiles for application in multilayer ferrite inductors. The permeability and Curie temperature have to be optimized by proper selection of composition. Ferrites with <50 mol% Fe₂O₃ reveal enhanced densification behavior. Submicrometer powders prepared by fine milling show good sintering activity and density after firing at 900°C. Nano-size ferrite powders prepared by coprecipitation or flame synthesis lead to high density; maximum shrinkage already occurs at T <800°C. The use of Bi₂O₃ as a sintering additive further improves the densification, but also affects the microstructure and, hence, the permeability. A maximum permeability of μ_i=450–500 is obtained.     

Some Roles of MgO and TiO2 in Densification of a Sinterable Alumina

Sinterability of undoped, MgO-doped, and TiO₂-doped Al₂O₃ has been examined by applying reported sintering equations. The order of sinterability was MgO-doped ∼ undoped≪ TiO₂-doped Al₂O₃ in the initial and intermediate stages of sintering, but a relative sintered density at 1600°C for 1 h occurred in the order undoped < TiO₂-doped < MgO-doped AI₂O₃. The dispersion of thermal grooving angles increased in the order MgO-doped < undoped < TiO₂-doped Al₂O₃, The change of sinterability by the dopants is explained in terms of mobility of mass transfer estimated from a densification rate in the initial- and intermediate-stage sintering and of dispersed driving forces of densification and grain growth qualitatively evaluated from the width of the dispersion of thermal grooving angles.     

Microstructure and Bending Strength of 3Y-TZP/12Ce-TZP Ceramics Fabricated by Liquid-Phase Sintering at Low Temperature

With the addition of 1 wt% of MgO–Al₂O₃–SiO₂ glass as a sintering aid, 3Y-TZP/12Ce-TZP ceramics (composed from a mixture of 3Y-TZP and 12Ce-TZP powder) have been fabricated via liquid-phase sintering at 1250°–1400°C. In the sintered bodies, the grain growth of Y-TZP is almost unaffected, whereas that of Ce-TZP is inhibited. MgO·Al₂O₃ spinel and an amorphous phase that contains Al₂O₃ and SiO₂ (from the sintering aid) fully fill the grain junctions. The bending strength of 3Y-TZP/12Ce-TZP, when sintered at 1250°–1300°C, is ∼800–900 MPa, which is greater than that of 3Y-TZP ceramics without Ce-TZP particles. Ce-TZP grains and MgO·Al₂O₃ spinel in 3Y-TZP/12Ce-TZP ceramics may impede crack growth, and the bending strength is enhanced.     

Pressureless Sintering of Boron Carbide

B₄C powder compacts were sintered using a graphite dilatometer in flowing He under constant heating rates. Densification started at 1800°C. The rate of densification increased rapidly in the range 1870°–2010°C, which was attributed to direct B₄C–B₄C contact between particles permitted via volatilization of B₂O₃ particle coatings. Limited particle coarsening, attributed to the presence or evolution of the oxide coatings, occurred in the range 1870°–1950°C. In the temperature range 2010°–2140°C, densification continued at a slower rate while particles simultaneously coarsened by evaporation–condensation of B₄C. Above 2140°C, rapid densification ensued, which was interpreted to be the result of the formation of a eutectic grain boundary liquid, or activated sintering facilitated by nonstoichiometric volatilization of B₄C, leaving carbon behind. Rapid heating through temperature ranges in which coarsening occurred fostered increased densities. Carbon doping (3 wt%) in the form of phenolic resin resulted in more dense sintered compacts. Carbon reacted with B₂O₃ to form B₄C and CO gas, thereby extracting the B₂O₃ coatings, permitting sintering to start at ∼1350°C.     

Spark Plasma Sintering of Bismuth Titanate Ceramics

Spark plasma sintering (SPS) was used to fabricate bismuth titanate (Bi₄Ti₃O₁₂) ceramics. The densification, microstructure development and dielectric properties were investigated. It was found that the densification process was greatly enhanced during SPS. The sintering temperature was 200°C lower and the microstructure was much finer than that of the pressureless sintered ceramics, and dense compacts with a high density of over 99% were obtained at a wide temperature range of 800°–1100°C. Dielectric property measurement indicated that the volatilization of Bi³⁺ was greatly restrained during SPS, resulting in an unprecedented low dielectric loss for pure Bi₄Ti₃O₁₂ ceramics.     

Preparation of Dense Lead Magnesium Niobate–Lead Titanate (Pb(Mg1/3Nb2/3)O3–PbTiO3) Ceramics by Spark Plasma Sintering

The effect of spark plasma sintering (SPS) on the densification behavior of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ ceramics has been investigated. Specimens with a density of >99% of the theoretical density (TD) were obtained using SPS treatment at 900°C. Through normal sintering at 1200°C, however, the density of the specimen was only ∼92% of TD.