Low-Temperature Sintering of (Ba0.6Sr0.4)TiO3

An addition of just 0.4 wt% Li₂O to (Ba_0.6Sr_0.4)TiO₃ powder was able to reduce the sintering temperature to ≤900°C and produce ceramics with a relative density of 97%. Small amounts of two secondary phases were formed during this process: Li₂TiO₃ and Ba₂TiO₄. The addition of Li₂O depresses the ferroelectric character of the (Ba_0.6Sr_0.4)TiO₃ and, as a result, reduces the permittivity, improves the temperature coefficient of permittivity, and reduces the dielectric losses. The tunability shows no significant variation with Li₂O concentration and remains between 16.5% and 13.5%. A low-temperature sintering mechanism was proposed. The mechanism involves the intermediate formation of BaCO₃, its melting and the incorporation of Li⁺ into the BST. The sintering mechanism can be characterized as reactive liquid-phase sintering.     

Crystallographic Facetting in Sintered Barium Titanate

A commercial TiO₂-excess BaTiO₃ powder has been sintered and its microstructure analyzed for crystallographic facetting via both scanning and transmission electron microscopy (SEM and TEM). Facetted grain surfaces are developed initially from {111} at a low temperature of 1215°C, which are then altered to {111} and {100} at 1290°C in the presence of a grain-boundary liquid phase. The grain shape is also modified correspondingly from platelike to polygonal. Facetting of the intragranularly located residual pores in BaTiO₃ along the {141} planes further develops on the (quasi-)equilibrium shape after annealing at 1400°C for 100 h from the initially well-characterized {111}, {110}, and {100} in as-sintered samples sintered at the same temperature for 10 h. The Wulff plots derived from the residual pores in as-sintered and annealed samples are constructed for the 〈011〉 zone. Microstructural analysis also suggests that the shape of grains and intragranular residual pores is modified progressively upon annealing. The initial solid–vapor surface energy has become less anisotropic crystallographically. Abnormal grain growth in relation to the surface energy anisotropy is discussed.     

Faceting of High-Angle Grain Boundaries in Titanium-Excess BaTiO3

The grain boundaries in BaTiO₃ with excess Ti of 0.5, 0.3, and 0.1 at.% sintered at 1300° or 1250°C have been examined by scanning electron microscopy (SEM), electron backscattered diffraction pattern (EBSP), and transmission electron microscopy (TEM). In the 0.1% Ti-excess specimen, large grains growing abnormally form high-angle grain boundaries when they impinge on each other as verified by EBSP. A large fraction of these grain boundaries are faceted with hill-and-valley shapes. In the 0.5% Ti-excess specimen, large grains growing abnormally are elongated in the directions of their {111} double twins. These grains often form flat grain boundaries parallel to their {111} planes with the fine matrix grains, and the grain-boundary segments between the large impinging grains with high misorientation angles are often also parallel to the {111} planes of one of the grains. These grain boundaries are expected to be singular. Most of the grain boundaries between the randomly oriented fine-matrix grains in the 0.3 at.% Ti-excess specimen are also faceted with hill-and-valley shapes at finer scales when observed under TEM. The facet planes are parallel to {111}, {011}, and {012} planes of one of the grain pairs and are also expected to be singular. These high-angle grain boundaries lying on low index planes of one of the grain pairs are similar to those observed in other oxides and metals.     

Effect of Rigid Inclusions on the Densification and Constitutive Parameters of Liquid-Phase-Sintered YBa2Cu3O6+x Powder Compacts

The presence of rigid inclusions in a powder compact leads to a reduction in the densification rate of the compact and may also lead to processing defects. In this paper, the densification rate and the constitutive parameters of both homogeneous YBa₂Cu₃O_{6+ x} and composite powder compacts (YBa₂Cu₃O_{6+ x} powder with 10 vol% dense inclusions of YBa₂Cu₃O_{6+ x} ) are reported. A small amount of liquid phase, which formed during sintering, was present in the samples. However, even with the presence of a liquid phase, the addition of inclusions still reduces the densification rate of the composite and increases its viscosity. The results have been compared with a published analysis of the problem using measured values of the constitutive parameters. Both the viscosity and viscous Poisson's ratio of the porous body have been measured.     

Continuous flash sintering

We develop an algorithm that relates the incubation time for flash initiation to the workpiece velocity as it is pulled through stationary electrodes in a continuous flash sintering experiment. Experiments with a whiteware green body that is sintered in this way are compared with the model. A processing map when the workpiece is drawn at a constant velocity is developed. The parameter space for the map is given by the speed and the current flowing through the workpiece. It distinguishes between the regimes for uniform and inhomogeneous sintering. All experiments were carried out at a furnace temperature of 900°C. The study shows the viability of continuous flash sintering of ceramics at speeds of up to 3 mm s^?1 with electrodes that form a line contact with the workpiece. Remarkably, higher velocities and higher currents yield better sintering.     

Tetragonal Nanocrystalline Barium Titanate Powder: Preparation, Characterization, and Dielectric Properties

Nanocrystalline tetragonal-BaTiO₃ powder was prepared using a hydrothermal method, under moderate conditions, and with a high precursor concentration. Characterization via X-ray diffractometry and differential scanning calorimetry confirmed that the average particle size and tetragonal content of the prepared powder were 70 nm and 80%, respectively. The sintered sample made from the prepared powder had a room-temperature dielectric constant of 6900, which was high for BaTiO₃.     

Sol–Gel Synthesis and Characterization of Ag and Au Nanoparticles in SiO2, TiO2, and ZrO2 Thin Films

Silver and gold nanoparticles were synthesized by the sol–gel process in SiO₂, TiO₂, and ZrO₂ thin films. A versatile method, based on the use of coordination chemistry, is presented for stabilizing Ag⁺ and Au³⁺ ions in sol–gel systems. Various ligands of the metal ions were tested, and for each system it was possible to find a suitable ligand capable of stabilizing the metal ions and preventing gold precipitation onto the film surface. Thin films were prepared by spin-coating onto glass or fused silica substrates and then heat-treated at various temperatures in air or H₂ atmosphere for nucleating the metal nanoparticles. The Ag particle size was about 10 nm after heating the SiO₂ film at 600°C and the TiO₂ and ZrO₂ films at 500°C. After heat treatment at 500°C, the Au particle size was 13 and 17 nm in the TiO₂ and ZrO₂ films, respectively. The films were characterized by UV–vis optical absorption spectroscopy and X-ray diffraction, for studying the nucleation and the growth of the metal nanoparticles. The results are discussed with regard to the embedding matrix, the temperature, and the atmosphere of the heat treatment, and it is concluded that crystallization of TiO₂ and ZrO₂ films may hinder the growth of Ag and Au particles.     

Suppressed grain growth in highly porous barium titanate foams by two‐step sintering

Porous barium titanate has gained significant attention in recent years for their potential use in applications such as scaffolds for bone tissue engineering, stress sensors, gas sensors, and many others. However, there is very little control over the grain size of the material during the sintering processes specially to achieve little or no growth of the starting powders. Here, using the two‐step sintering method barium titanate foams were shown to be synthesized with controlled grain size of the struts without significant differences in the pore structure of the materials. In order to evaluate the applicability of two‐step sintering for a variety of processing methods, highly porous (>80% porosity) foams synthesized through the direct polyurethane foaming method were used to create conditions furthest from bulk where two‐step sintering has shown success. Two‐step sintering parameters were identified and the processing conditions were confirmed to not alter the mechanical properties of the samples due to expected residual stresses or thermal shock resulting from the rapid heating and cooling rates employed.     

A New Glycothermal Process for Barium Titanate Nanoparticle Synthesis

Barium titanate (BaTiO₃) nanoparticles were synthesized at the low temperature of 80°C through a glycothermal reaction using Ba(OH)₂·8H₂O and amorphous titanium hydrous gel as precursors and a solution of 1,4-butanediol and water as solvent. This processing method provides a simple low-temperature route for producing BaTiO₃ nanoparticles, which could also be extended to other systems. It is demonstrated that the size of BaTiO₃ particles can be controlled by reaction conditions, such as reaction temperature and various volume ratios of 1,4-butanediol/water.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

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.     

Effect of Tween-80 on the Control of Particle Size and Shrinkage Properties of Nanoscale α-Alumina Synthesized by Sol–Gel Processing

The concept of tailored interfaces has been applied to the synthesis of nanoscale α-Al₂O₃. Tween-80 (poly-oxyethylene(20) sorbitan monooleate, T-80) was used as a surface modifier in the sol–gel process for this purpose. High-resolution transmission electron microscopy study of the powder obtained with T-80 confirmed the particle size of α-Al₂O₃ (∼55 nm) and morphology (spherical). The exothermic peak temperature in the differential thermal analysis was shifted to a lower temperature (∼917°C) when the powder was derived from a T-80 modifier content of 10 wt%. X-ray diffraction showed that the α-Al₂O₃ phase was the major phase that existed in modifier-derived powder that was sintered at 1000°C. The experiments, based on linear shrinkage, indicated that the powder with T-80 (10 wt%) could be densified at a low temperature.     

Mullite–β-Spodumene Composites from Aluminosilicates

Sintering studies were conducted using kaolin, metakaolin, zeolite 4A, and various synthetic mixtures of Al₂O₃ and SiO₂ in the presence of Li₂CO₃ and LiCl as fluxing agents. Various compositions of the above were prepared, and conventional sintering studies were conducted at temperatures of 900°–1450°C with soaking periods of 1–3 h. Kaolin, metakaolin, and amorphized kaolin in the presence of Li₂CO₃ showed nucleation centers of β-spodumene as pink specks, whereas synthetic mixtures of Al₂O₃ and SiO₂ failed to behave in the same manner. To determine whether the pink specks formed were color centers or F centers, the samples were subjected to UV, IR, and X-ray irradiation; however, the samples showed no tenebrescence properties. External addition of iron as an impurity in a nonlayered system also resulted in pink speck formation. This observation indicated that impurities present in the natural kaolin were the cause of this phenomenon. Moreover, the LiCl-based samples did not result in pink specks, even though the kaolinitic samples contained iron as an impurity. Therefore, although β-spodumene was formed in aluminosilicates in the presence of Li₂CO₃ and LiCl, the pink variety of β-spodumene (kunzite) formation occurred only in the presence of lithium-rich aluminosilicates and in the presence of iron as an impurity. The phase identification and microstructure were explained based on XRD, DTA, and SEM studies.     

High-Strength Porous Alumina Ceramics by the Pulse Electric Current Sintering Technique

High-strength porous alumina has been fabricated with a microstructure control using the pulse electric current sintering (PECS) technique. During sintering the discharge, which is assumed to take place in the voids between the particles, is thought to promote the bridging of particles by neck growth in the initial stages of sintering, leaving high porosity. The effect of dopants (MgO, 200 ppm; TiO₂, 1000 ppm) and of secondary inclusions (3 vol% 3Y-TZP) on the constrained densification and the improvement in the mechanical behavior of porous alumina ceramics has been reported. The porosity of the fabricated porous alumina was controllable between 30% and 50% depending on the sintering temperature. The flexural strength of alumina having 30% and 42% porosity showed impressive values of 250 and 177 MPa, respectively. The dominance of the preferential neck growth of grains over densification significantly improved the mechanical properties of porous alumina, besides leaving high porosity.     

Effect of Silicon Substitution on the Sintering and Microstructure of Hydroxyapatite

The substitution of between 0 and 1.6 wt% silicon (Si-HA) in hydroxyapatite (HA) inhibited densification at low temperatures (1000°–1150°C), with these effects being more significant as the level of silicon substitution was increased. For higher sintering temperatures (1200°–1300°C), the sintered densities of HA and Si-HA compositions were comparable. Examination of the ceramic microstructures by scanning electron microscopy (SEM) showed that silicon substitution also inhibited grain growth at higher sintering temperatures (1200°–1300°C). The negative effect of silicon substitution on the sintering of HA at low temperatures (1000°–1150°C) was reflected in the hardness values of the ceramics. However, for higher sintering temperatures, e.g., 1300°C, where sintered densities were comparable, the hardness values of Si-HA compositions were equal to or greater than that of HA, reflecting the smaller grain sizes observed for the former.     

Migration of Intergranular Liquid Films and Formation of Core-Shell Grains in Sintered TiC–Ni Bonded to WC–Ni

When TiC–20 wt% Ni powder mixtures are sintered at 1400°C, relatively large TiC grains possibly containing some Ni form with near-equilibrium shapes. When these specimens are heat-treated again at 1400°C in contact with sintered WC–20 wt% Ni pieces, the liquid films between the TiC grains in the contact region migrate against their increasing curvatures, forming (Ti,W)C solid solution behind them. These migrating liquid films reverse their directions on further heat-treatment. As in other alloys, this liquid film migration must be driven by the coherency strain energy produced by W diffusion at the surface of the dissolving TiC grains. Shells of (Ti,W)C solid solution also form around the cores of TiC grains near the contact region, and this process is probably driven by both coherency strain energy and free energy of mixing. At some contact regions, (Ti,W)C precipitates nucleate and grow, probably driven mainly by the free energy of mixing. In powder mixtures, the formation of core-shell grains is expected to be driven by the coherency strain energy, the free energy of mixing, and the capillary effect.     

Sintering of (Cu0.25Ni0.25Zn0.50)Fe2O4 Ferrite

A study has been conducted on the sintering of a ceramic ferrite having the composition (Cu_0.25Ni_0.25Zn_0.50)Fe₂O₄. The study analyzes the evolution of ferrite relative to density and microstructure with peak sintering temperature and dwell time at peak temperature. The densification and grain-growth rates are correlated with average grain size, relative density, and temperature. Corresponding rate-controlling diffusion mechanisms are proposed.     

Original Monte Carlo Methodology Devoted to the Study of Sintering Processes

A Monte Carlo methodology different from others based on the Potts model has been developed to solve capillary-driven mass transport involved in the sintering process. The addition of a cohesive energy term to the energetic model enables quantification of the stress gradients within grains, as well as the induced mass fluxes. The study of two-particle sintering involving volume diffusion has been chosen as a first example. The morphological evolution of the two-particle system to a single particle is followed. Real-time-dependent neck growth and shrinkage rates are defined. The rheological behavior of the particles induced by the Monte Carlo procedure is discussed.