Electric-Field Effects on Sintering and Reaction to Form Aluminum Titanate from Binary Alumina–Titania Sol–Gel Powders

The field-activated sintering technique (FAST) was applied to simultaneously sinter and react sol–gel amorphous powders to form Al₂TiO₅. Densities close to theoretical and conversion to Al₂TiO₅ (to 92.5%) have been achieved using FAST at 1050°–1200°C for 10 min. Conventional sintering of the same powders at 1300°C for 2 h resulted in 88.9% Al₂TiO₅ and ∼75% of theoretical density. The enhanced sintering and compound formation using FAST have been explained by the synergistic effects of precursor reactivity, nanosized powders, and electric-field effects.     

Enhanced Properties of Tin(IV) Oxide Based Materials by Field-Activated Sintering

The densification of SnO₂ (0.9 mol)–Sb₂O₃ (0.1 mol) solid solution without any additives was studied by conventional and field-activated sintering technique (FAST). FAST sintering achieved a relative density value of 92.4% at 1163 K for 10 min versus 61.3% in conventional sintering at 1273 K for 3 h. An abnormal reduction of the IR transmittance and a semiconductor defect structure with only one donor level in the SnO₂ energy gap were noticed in the FAST-sintered as compared with the conventionally sintered Sn_0.82Sb_0.18O₂ solid solution. A high charge carrier concentration (i.e., electronic conduction) was shown in the FAST-sintered sample by conductivity measurements and the negative values of the Seebeck coefficient.     

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.     

Positive Temperature Coefficient of Resistivity Effect in Highly Donor–Doped Barium Titanate

BaTiO₃ ceramics doped with different La concentrations (0–12 mol%) were prepared by sintering under the reducing conditions of a nitrogen atmosphere containing 1% hydrogen. The critical donor concentration that causes blocking of the exaggerated grain growth was observed to be ∼10 mol% La. The samples, which were semiconducting after sintering under reducing conditions, were subsequently reoxidized by annealing in air to induce the positive temperature coefficient of resistivity (PTCR) effect. After reoxidation at 1150°C a noticeable PTCR effect was observed in the samples doped with La concentrations as high as 2.5 mol%. The room-temperature resistivity after reoxidation was found to increase with increasing donor concentration due to an increase in the thickness of the insulating layers at the grain boundaries. TEM analysis showed that reoxidation of the samples caused precipitation of the Ti-rich compound Ba₆Ti₁₇O₄₀ inside the doped BaTiO₃-matrix grains.     

Low-Temperature Pressureless Sintering of Sr- and Mg-Doped Lanthanum Gallate Ceramics by Sintering Atmosphere Control

The present investigation reports a new processing technique that can reduce the sintering temperature of Sr- and Mg-doped lanthanum gallate (LSGM), a good candidate material for the electrolyte of the solid oxide fuel cell (SOFC). When LSGM was sintered at 1623 K for 5 h in N₂ or O₂, the samples were densified over 98% relative density. In contrast, only 93% relative density was achieved after sintering in air, the conventional sintering atmosphere. As a result of better densification in N₂ or O₂, the electrical conductivity of the N₂-sintered and air-annealed or the O₂-sintered sample was higher than that of the air-sintered sample by 30%. This result shows the beneficial effect of N₂ or O₂ sintering of LSGM and provides a high possibility of a low-temperature preparation of an LSGM-based SOFC.     

Dielectric Properties of Microstructure-Controlled Ba2Ti9O20 Resonators

Thermal schedules for sintering ZrO₂- and SnO₂-doped Ba₂Ti₉O₂₀ resonators to minimum porosity were developed using a shrinkage-rate-controlled dilatometer. Efficient sintering schedules were formulated that circumvented pore formation via grain-boundary/triple-point liquid-phase volatilization. A densification rate (0.5%/min) for the early stages of sintering, which minimized intragranular porosity, was chosen. For the later stages of sintering, a densification rate (0.01%/min) that minimized specimen slumping via the liquid phase permitted sintering to high density. These schedules were successfully upscaled to heat treatment in a conventional furnace. The dielectric constants, quality factors, and selected temperature coefficients of 0.82- and 1.64-mol%-SnO₂-, and 1.64-mol%-ZrO₂-doped monophase Ba₂Ti₉O₂₀ were reported.     

Effect of Europium Concentration on Densification of Transparent Eu:Y2O3 Scintillator Ceramics Using Hot Pressing

Europium (Eu) was found to act as a solid-state sintering aid in Y₂O₃ optical ceramics by controlling ionic diffusivity, which in turn leads to enhanced optical transparency. Transparent ceramic samples of Eu-doped Y₂O₃, with no additional additives, were sintered by uniaxial vacuum hot pressing under 40 MPa and maximum temperature of 1580°C. Optical attenuation was found to decrease with increasing Eu concentrations between 0 and 5 at% for ceramics processed under the same sintering conditions. In order to study the effect of Eu concentration on ceramic densification, the strain rate and grain size during sintering at constant temperature and varied pressure were measured. A diffusional flow densification model was used to derive instantaneous effective diffusion constants for the densification process. Diffusion constants were found to increase with increasing Eu concentration according to a log–linear relationship. Eu²⁺ was detected in samples after hot pressing through fluorescence spectroscopy, and the extrinsic defect chemistry was found to be dominated by the reduced Eu in solid solution with Y₂O₃. A sintering model with diffusion rate limited by yttrium interstitial transport and controlled by the incorporation of Eu²⁺ onto the cation sublattice was found to be in good agreement with experimental diffusivity data.     

Fabrication and Microstructure Characterization of Ti3SiC2 Synthesized from Ti/Si/2TiC Powders Using the Pulse Discharge Sintering (PDS) Technique

Ti/Si/2TiC powders were prepared using a mixture method (M) and a mechanical alloying (MA) method to fabricate Ti₃SiC₂ at 1200°–1400°C using a pulse discharge sintering (PDS) technique. The results showed that the Ti₃SiC₂ samples with <5 wt% TiC could be rapidly synthesized from the M powders; however, the TiC content was always >18 wt% in the MA samples. Further sintering of the M powder showed that the purity of Ti₃SiC₂ could be improved to >97 wt% at 1250°–1300°C, which is ∼200°–300°C lower than that of sintered Ti/Si/C and Ti/SiC/C powders using the hot isostatic pressing (HIPing) technique. The microstructure of Ti₃SiC₂ also could be controlled using three types of powders, i.e., fine, coarse, or duplex-grained, within the sintering temperature range. In comparison with Ti/Si/C and Ti/SiC/C mixture powders, it has been suggested that high-purity Ti₃SiC₂ could be rapidly synthesized by sintering the Ti/Si/TiC powder mixture at relatively lower temperature using the PDS technique.     

Investigation of High-Alumina Spinel: Effect of LiF and CaCO3 Addition

This work examines the effects of LiF or LiF/CaCO₃ additives on the phases, microstructure, sintering temperature, and activation energy of MgO-Al₂O₃ spinel formation. According to these results, the spinel formation temperature decreases and the spinel phase content increases by incorporating sintering additives. Such an effect is due to the formation of liquid phases at sintering temperatures. The Al composition in spinel is substantially higher in samples containing LiF or LiF/CaCO₃ than in samples without sintering additives. Results obtained from the Arrhenius equation and Jander's model indicate that the activation energy for forming spinel decreases by incorporating LiF or LiF/CaCO₃.     

Effect of Fe and Cr Addition on the Sintering Behavior of ZrB2 Produced by Self-Propagating High-Temperature Synthesis

An investigation of the sintering behavior of ZrB₂ powder with Fe and Cr (0 to 20 wt%) addition was conducted. It was observed that Fe addition helps to enhance the density of ZrB₂ only up to 10 wt%. Further addition of Fe degrades the sintering by segregation of Fe-rich phases. Formation of a eutectic phase containing a Fe:Zr ratio of 92.57:7.43 was also found in Fe-added samples. The addition of Cr to a ZrB₂ matrix was found to result in swelling of the samples, leading to several cracks.     

Microstructural Evolution of Crystalline-Oriented (K0.5Na0.5)NbO3 Piezoelectric Ceramics with a Sintering Aid of CuO

The microstructural development of crystalline-oriented (K_0.5Na_0.5)NbO₃ (KNN)-based piezoelectric ceramics during sintering was investigated. The addition of CuO as a sintering aid was found to be effective for fabricating highly oriented and dense KNN ceramics. KNN specimens containing 0.5–1.0 mol% CuO sintered at 1100°C for 1 h were found to have relative densities and pseudo-cubic {100} orientation degrees of 95% or higher. In the early stages of sintering, KNN is formed in the reaction between complementary reactants NaNbO₃ and KNbO₃, after which oriented grain growth proceeds at a relative density of more than 90%. In addition, the results of transmission electron microscopy observation showed that textured KNN ceramics have a unique pectinate-like domain structure with domain walls consisting of {101} planes.     

Constrained Densification of Alumina/Zirconia Hybrid Laminates, I: Experimental Observations of Processing Defects

Various forms of damage were observed in pressure-less-sintered Al₂O₃/ZrO₂symmetric laminates and asymmetric laminates (bilayers) fabricated by tape casting and lamination. These defects included channel cracks in the ZrO₂ layers, Al₂O₃ edge-effect cracks parallel to the layers, delamination in the Al₂O₃layers, and debonding between the Al₂O₃and ZrO₂layers. Based on detailed microscopic observations, the defects were attributed to sintering rate and thermal expansion mismatch between the layers. Cracks or cracklike defects were formed in the early stages of densification, and these cracks either opened during sintering or acted as preexisting flaws for thermal expansion mismatch cracks. Consequently, the extent of cracking could be reduced or even eliminated by decreasing mismatch stresses during the sintering and cooling stages. This can be accomplished by reducing the heating and/or cooling rates or by adding Al₂O₃in the ZrO₂layers. The sintering mismatch stresses were estimated from the degree of curling in asymmetric laminates and from layer viscosities that were obtained by cyclic loading dilatometry. The measured curvature was an indication of the mismatch in sintering strain between Al₂O₃and ZrO₂and were consistent with the dilatometric data that were obtained for the component layers.     

Journal Effect of a Liquid Phase on the Sintering of Heterogeneous YBa2Cu3O6+x Compacts

Dense, polycrystalline YBa₂Cu₃O_6+x inclusions were incorporated into YBa₂Cu₃O_6+x: powder in order to investigate the effect of nondensifying inclusions on the sintering behavior of the matrix. The presence of these inclusions caused a significant reduction in the densification rate of the matrix, as well as some microstructural damage. However, when approximately 2.5 vol% of a liquid phase was present during sintering, there was some retardation of densification in the early stages, but this disappeared with time. Also, the final sintered microstructures were damage-free and essentially identical to those of samples containing no inclusions. Possible roles for the liquid phase in correcting this microstructural damage are briefly discussed.     

Influence of SiO2 Addition on the Dielectric Properties and Microstructure of (Ba0.96Ca0.04)(Ti0.85Zr0.15)O3 Ceramics

In this study, the effect of SiO₂ doping on the sintering behavior, microstructure, and dielectric properties of BaTiO₃-based ceramics was investigated. Silica was added to (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ (BCTZ) powder prepared using the solid-state method. SiO₂-doped BCTZ ceramics with a high density and a uniform grain size were obtained and sintered at 1220°C in a reducing atmosphere. A second phase (BaTiSiO₅) existed in samples when SiO₂ was added in excess of 1%. The amount of the second phases was observed to increase as the number of SiO₂ additives increased. It was found that BCTZ ceramics sintered with SiO₂ are helpful in reducing the sintering temperature for a typical thick film and MLCC applications. However, there were disadvantageous effects on the dielectric properties with mere addition of SiO₂ addition (3% and 5%) due to higher formation of BaTiSiO₅. Doping with a small amount of silica can improve the sintering and dielectric properties of BCTZ ceramics. In addition, to understand the effect of the BaTiSiO₅ phase on the dielectric properties of BCTZ ceramics, the BaTiSiO₅ composition was synthesized from individual BaCO₃, TiO₂, and SiO₂ powders using conventional solid-state methods. X-ray diffraction results show the presence of mainly the crystalline phase, BaTiSiO₅, in the sintered ceramics.     

Microstructures and Piezoelectric Properties in the Li2O-Excess 0.95(Na0.5K0.5)NbO3–0.05LiTaO3 Ceramics

As a candidate for lead-free piezoelectric materials, Li₂O-excess 0.95(Na_0.5K_0.5)NbO₃–0.05LiTaO₃ (NKN–5LT) ceramics were developed by a conventional sintering process. The sintering temperature was lowered by adding Li₂O as a sintering aid. Abnormal grain growth in NKN–5LT ceramics was observed with varying Li₂O content. This grain-growth behavior was explained in terms of interface reaction-controlled nucleation and growth. In the 1 mol% Li₂O excess NKN–5LT samples sintered at 1000°C for 4 h in air, the electromechanical coupling factor and the piezoelectric constant of NKN–5LT ceramics were found to reach the highest values of 0.37 and 250 pC/N, respectively.     

Dielectric Properties of Lead-Magnesium Niobate Ceramics

Dielectric properties are reported for lead magnesium niobate (PbMg_1/3Nb_2/3/O₃) ceramics which were prepared as single phase (i.e., without pyrochlore) with an improved technique. Dielectric constants of 18000 for pure PMN and 31000 for PMN with 10% PbTiO₃ were achieved; these values are 50% larger than those reported in the literature. The dielectric constant of PMN ceramics was found to increase with both sintering temperature and excess MgO, and subsequent analysis of the microstructures confirmed that this was due to an increase in grain size. This grain-size dependence is explained as a consequence of low-permittivity grain boundaries.     

Microstructural Evolution during Pressureless Sintering of Lead Lanthanum Zirconate Titanate Ceramics with Excess Lead(II) Oxide

The early stages of sintering of lead lanthanum zirconate titanate (PLZT) 9/65/35 ^† ceramics prepared with 10 wt% excess PbO were monitored by quenching uniaxially pressed pellets after a variety of heat treatments. TEM revealed a PbO-rich amorphous film covering the particle surfaces and interparticle porosity in pellets quenched after 5 min at 1125° to 1180°C. This amorphous phase is indicative of the presence of a high-temperature liquid phase with composition approximately Pb_0.87Zr_0.15Ti_0.04O_1.19. The liquid composition moves toward the PbO-TiO₂ eutectic as sintering progresses. After 10 to 30 min at 1180°C, the liquid composition was approximately Pb_0.9Zr_0.04Yi_0.06O_l.1 and crystallized on quenching. High densities of dislocations with = 1/2〈110〉 and low-angle boundaries were observed in samples quenched from 1180°C after 10 to 30 min. Mechanisms for the formation of these dislocations are suggested.     

Sintering of Lead Titanate Using a Spark-Plasma-Sintering Technique

Lead titanate (PbTiO₃) is difficult to sinter without additives, even when a spark-plasma-sintering technique is applied. The high tetragonality, c / a , of PbTiO₃ causes destructive strain after sintering. We found that a sintered body of PbTiO₃ could be obtained, when the PbO/TiO₂ value was <0.9. However, decreasing the ratio did not increase the bulk density; rather, it caused a decrease in the grain size. The mechanical strain that resulted from the phase change from cubic, at the sintering temperature, to tetragonal, at room temperature after the sintering, was released by the decrease in the grain size.     

Fabrication of High-Curie-Point Barium-Lead Titanate PTCR Ceramics

High-Curie-point semiconducting barium-lead titanate positive temperature coefficient of resistivity (PTCR) ceramics of composition Ba_0.897Pb_0.1La_0.003TiO₃ and Ba_0.5Pb_0.5La_0.003TiO₃ were prepared. The starting powders were synthesized by reacting commercial BaTiO₃, PbO, and TiO₂. To avoid the nonstoichiometry due to the volatilization of Pb during the sintering process, a lead atmosphere sintering approach with PbTiO₃ as packing powder was used. The samples being fabricated by this method show a PTCR effect of 3 to 4.5 orders of magnitude above the Curie point. The curie points were about 180°C for Ba_0.897Pb_0.1La_0.003TiO₃ and about 360°C for Ba_0.497Pb_0.5La_0.003TiO₃.     

Liquid-Phase-Assisted Sintering of Calcium-Doped Lanthanum Chromites

Investigations have been made on the low-temperature sinterability of calcium-doped lanthanum chromites which are to be used as interconnectors in solid oxide fuel cells (SOFCs). Nominally chromium deficient lanthanum calcium chromites (La_0.7Ca_0.3Cr₁-_yO₃, y = 0.02) were found to be sinterable to 94% theoretical density at 1573 K in air, whereas no densification was observed for samples with y = 0. The two-step shrinkage process suggests a liquid phase sintering mechanism with calcium oxychromates playing an important role as the liquid phase. After sintering at 1573 K, calcium-rich substances remained at grain boundaries.