Hot-Pressed (Pb,La)(Zr,Ti)O3 Ferroelectric Ceramics for Electrooptic Applications

Transparent ferroelectric ceramic materials suitable for a variety of electrooptic applications were found in the quaternary (Pb,La)(Zr,Ti)O₃ system. These PLZT materials are prepared from mixed oxides and hot-pressed typically at 1100°C for 16 h at 2000 psi. Modifying the lead zirconate-titanate system with lanthana linearly reduces the Curie point with increasing lanthana. Transmission measurements in the visible and infrared show that these materials exhibit a nearly constant response from the absorption edge of 0.37 μ to ∼6 μm. The highest transmission values, essentially 100% (neglecting reflection losses of ∼18%) for thin polished plates, were noted for compositions containing 8 at.% La or more. Specific compositions within the system display electrooptic memory or conventional linear or quadratic electrooptic effects; on the basis of the magnitude of the electrooptic effects, they compare quite favorably with single crystals.     

In Situ Processing of Silicon Carbide Layer Structures

A novel route to low-cost processing of silicon carbide (SiC) layer structures is desribed. The processing involves pressureless liquid-phase cosintering of compacted power layers of SiC, containing alumina (Al₂O₃) and yttria (Y₂O₃ sintering additives to yield and yttrium aluminum garnet (YAG) second phase. By adjusting the β:α SiC phase ratios in the individual starting powders, alternate layers with distinctively different microstructures are produced: (i) "homogeneous" microstructures, with fine equiaxed SiC grains, designed for high strength; and (ii) "heterogeneous: microstructures with coarse and elongate SiC grains, designed for high toughness. By virtue of the common SiC and YAG phases, the interlayer interfaces are chemically compatible and strongly bonded. Exploratory Hertzian indetation tests across a bilayer interface confirm the capacity of the tough heterogeneous layer to inhibit potentially dangerous cracks propagating through the homogeneous layer. The potential for application of this novel processing approach to other layer architectures and other ceramic systems is considered.     

Spherical Yttrium Aluminum Garnet Embedded in a Glass Matrix

Containerless processing was used to investigate the glass-forming behavior of Al₂O₃–Y₂O₃ glass. The amorphous bulk samples were obtained at compositions with 25–37.5 mol% yttria when the melt was cooled at a cooling rate of ∼250 K/s. Although small spherical particles (∼10 μm) with the same composition of the matrix were detected in the amorphous samples with 32.5–37.5 mol% yttria, the microfocus X-ray diffraction result indicated that the small spherical particles were crystalline Y₃Al₅O₁₂ garnet (YAG), rather than being amorphous. This observation suggested that small YAG particles could not grow larger after their nucleation, because of the high viscosity at high undercooling and the high cooling rate, which would graze the nose of the continuous cooling temperature diagram of YAG.     

Resistance of Alumina-Spodumene Ceramics to Thermal Shock

A processing strategy is presented for obtaining alumina-spodumene ceramics with controlled microstructures from a new, low-cost alumina powder and spodumene (Li₂OAl₂O₃·4SiO₂) mineral, both being produced in Western Australia. The addition of 15 wt%β-spodumene to alumina is used to produce ceramics with (i) high thermal expansion mismatch and (ii) a glassy phase to aid in liquid-phase sintering. Specifically, the effects of spodumene addition and grain size on tolerance to thermal shock are addressed. The thermal shock resistance of the alumina-spodumene ceramics is evaluated by water quenching and subsequent three-point bend testing of strength diminution. Comparisons are made with results from parallel experiments conducted using a pure monolithic alumina ceramic. The reference alumina shows the expected substantial strength losses when thermally quenched from ∼200°C above room temperature. By contrast, the alumina-spodumene ceramics, while displaying reduced strength relative to the reference aluminas, exhibit minimal strength degradation under severe thermal shock conditions.     

Processing of Cellular Glasses Using Glass Microspheres

A new processing route for the manufacture of cellular glasses has been developed. The strategy adopted for making the cellular glasses entails the following steps: (i) fabricating a formed body by combining glass powder and glass microspheres, and (ii) sintering the formed body. By controlling the sintering temperature and the microsphere content, it was possible to adjust the porosity so that it ranged from ∼42% to ∼62%. The compressive strengths of the cellular glasses with ∼42% and ∼60% porosities were ∼150 and ∼60 MPa, respectively. The superior compressive strengths were attributed to the homogeneous distribution of small (≤35 μm), spherical cells with dense struts in the cellular glasses.     

Wet Erosive Wear of Alumina Densified with Magnesium Silicate Additions

A study was made of the wet erosive wear of polycrystalline alumina of mean grain size >1 μm, containing up to 10 wt% of magnesium silicate sintering aid. For pure polycrystalline alumina, the dominant wear mechanism was grain-boundary microfracture, leading to partial or complete grain removal. In the case of the liquid-phase-sintered materials, wear rates could be as low as 25% of those of pure alumina of the same mean grain size, and the main material removal mechanism was transgranular fracture combined with tribochemical wear. The use of Cr³⁺ photoluminescence line broadening showed much higher levels of local stress in the magnesium silicate-sintered materials (∼450 MPa) than in the pure-alumina materials (∼200 MPa). Grain-boundary compressive hoop stresses, caused by the thermal expansion mismatch between a continuous magnesium silicate film and the alumina grains, provided an explanation for the improved wear resistance of the alumina sintered with magnesium silicate.     

Fabrication of Transparent Tellurite Glasses Containing Potassium Niobate Crystals by an Incorporation Method

To fabricate transparent oxide glasses containing ferroelectric KNbO₃ crystals, a new method in which KNbO₃ particles are directly incorporated into TeO₂─K₂O─Nb₂O₅ glasses has been developed. Transparent TeO₂-based glasses containing KNbO₃ crystals with a diameter of ∼ 10 μm have been first successfully fabricated by adjusting temperature and time for incorporation. A small difference in the refractive indexes, n , between TeO₂-based matrix glasses ( n = 2.0) and incorporated KNbO₃ crystals ( n = 2.21) is a significant reason for the transparency. This new method is applicable for the fabrication of new transparent glasses containing other functional materials with high refractive indexes.     

Microstructural Development and Creep Deformation in an Alumina–5% Yttrium Aluminum Garnet Composite

An alumina–5 vol% yttrium aluminum garnet (YAG) composite was obtained through in situ reaction of alumina and yttria during sintering. Analysis of creep experiments together with microstructural data indicated that both pure alumina and alumina–5 vol% YAG composite deform by a Coble grain boundary diffusion creep process. Comparison with other data suggests that at temperatures greater than ∼1650 K, an isolated or interconnected fine-grained YAG phase does not significantly affect creep in alumina. However, an isolated YAG phase retards both static and dynamic grain growth in the composite.     

Graded Casting of Materials with Continuous Gradients

A process is introduced for producing continuously graded materials by slip casting with a continuous flow of slip of changing composition. The approach has been tested using alumina and zirconia slips to produce alumina/zirconia composites with a graded composition. Observation of the microstructure has shown that the phases are relatively well dispersed. Compositional analysis revealed a relatively smooth transition in composition through the thickness of sintered bodies. Results have also indicated that for flow rates up to ∼ 60 cm/min, the highest linear flow rate tested, the casting rate of alumina slips containing 38.6 vol% solids was not affected.     

Effects of Yttrium on the Sintering and Microstructure of Alumina–Silicon Carbide "Nanocomposites"

Alumina and alumina-based "nanocomposites" with 2 and 5 vol% silicon carbide and varying amounts of yttria (0–1.5 wt%) have been prepared by pressureless sintering in the temperature range 1450°–1650°C. The effects of composition and sintering temperature on density and microstructure are reported. Yttria inhibited sintering in alumina, but enhanced the sinterability of the nanocomposites. It also induced abnormal grain growth in both alumina and nanocomposites, but strongly bimodal grain size distributions could be prevented by careful choice of the composition and the sintering temperature. Fully dense (>99%), fine-grained alumina–5 vol% SiC–1.5 wt% yttria nanocomposites were produced from uniaxially pressed powders with a yttria content of 1.5 wt% and a sintering temperature of 1600°C. Reasons for this behavior are discussed, and it is suggested that the enhancement of sintering in the alumina–SiC materials is because of the reaction of silica on the surface of the silicon carbide particles with alumina, yttria, and possibly magnesia, modifying the grain boundary composition, resulting in enhanced grain boundary diffusion. scanning transmission electron microscopy/energy-dispersive X-ray data show that such co-segregation does occur in the yttria-containing nanocomposites.     

Relative Acidities of Glasses Containing Al2O3 and TiO2 as Determined by the Oxygen Electrode

The oxygen electrode has been utilized to determine the relative acidities of sodium and potassium silicate glasses containing alumina and titania in the temperature range 300° to 500° C. The acidity of a potassium or sodium silicate glass is increased by substituting alumina or titania for the soda or potassia. The first additions of alumina tend to increase the acidity of both glasses by forming A1O₄ tetrahedra which utilize a portion of the nonbridging oxygen ions to fulfill the coordination requirements. The results indicate further that the Ti⁴⁺ ion is in both fourfold and sixfold coordination in the sodium and potassium glasses. Titania increases the acidity when it is in sixfold coordination but tends to decrease it when in fourfold coordination. Both titania and alumina increase the acidity of the potassium glasses more than that of the sodium glasses. This is interpreted on the basis that the oxygen network of the potassium glass, being initially the looser, is tightened more than that of the sodium glass. However, the polymerization of the A1O₄ tetrahedra at the higher alumina concentrations causes a loosening of the oxygen network. Previous assumptions that the oxygen electrode reaction is independent of the metal used for the electrodes have been verified by reproducing the data using platinum foil as the electrode material in place of silver foil.     

Mechanical Characterization of Sol–Gel-Derived Silicon Oxycarbide Glasses

Silicon oxycarbide glasses have been fabricated, in the shape of thin rods suitable for flexural test experiments, by pyrolysis in an inert atmosphere at 1000° and 1200°C of solgel precursors containing Si–CH₃ and Si–H bonds. The amount of carbon in the silicon oxycarbide network has been controlled by varying the carbon load in the precursor gel. Density and surface area analysis revealed that all of the samples pyrolyzed at 1200°C were well-densified silicon oxycarbide glasses whereas for the glasses treated at 1000°C, compositions with low carbon loads showed the presence of a residual fine porous phase. The elastic modulus ( E ), flexural strength (MOR), and Vickers hardness ( H_v ) increase markedly with the amount of carbon in the oxycarbide glasses reaching the maximum values ( E ∼ 115 GPa, MOR ∼ 550 MPa, and H_v ∼ 9 GPa) for samples with the highest carbon content. The experimental elastic modulus values of the silicon oxycarbide glasses compare well with the theoretical estimations obtained using the Voigt and Reuss models assuming the disordered network formed by the corresponding thermodynamic compositions.     

Toughening Behavior in Sic-Whisker-Reinforced Alumina

The development of hot-pressed Sic-whisker-reinforced alumina has resulted in composites with fracture toughness values ∼;8.7 MPa·m¹¹² at 20 vol% SiC. Whisker orientation during processing leads to anisotropy in both fracture toughness and fracture strength. Fracture strengths are also limited by the ability to disperse the Sic whiskers; however, use of both fine alumina powders and ultrasonic dispersion techniques yields strengths ∼;800 MPa.     

Oxyfluoronitride Glasses with High Elastic Modulus and Low Glass Transition Temperatures

The preparation and properties of novel calcium aluminosilicate glasses containing both nitrogen and fluorine are reported. Nitrogen increases Young's modulus and microhardness of oxide glasses by ∼25%. However, one of the major disadvantages of the use of oxynitride glasses for high-stiffness applications is the fact that nitrogen also increases glass viscosity. Melting temperatures of the order of ∼1700°C are required to achieve sufficiently low viscosities for glass forming and drawing processes. Fluorine substitution for oxygen in Ca–Si–Al–O–N glasses yields significant decreases in glass transition temperature and glass melting temperature as well as increasing nitrogen solubility to levels much higher than that previously reported for glasses made by melting CaO, SiO₂, Si₃N₄, and Al₂O₃ powder mixtures. The important effect that N results in increased elastic modulus is not diminished by the addition of fluorine. Thus, it is possible to produce novel oxyfluoronitride glasses with a high elastic modulus but melting and working can be carried out at more conventional glass processing temperatures.     

Low-Temperature Sintering of Alumina with Liquid-Forming Additives

Simultaneous application of colloidal processing and liquid-forming additives to alumina resulted in a sintered density of >99% in 1 h at a temperature as low as 1070°C for a commercial high-purity alumina powder at a total dopant level of 2 mol%. The additives were 0.9% CuO + 0.9% TiO₂+ 0.1% B₂O₃+ 0.1% MgO. At higher temperatures or after prolonged sintering, the doped alumina ceramic developed a duplex microstructure containing large elongated grains and exhibited a relatively high fracture toughness of ∼ 3.8 MPa · m^1/2 as compared to a value of ∼ 2.6 MPa · m^1/2 for the undoped alumina.     

Chemical and microstructural characterisation of HfO2-Y2O3 ceramics with high amount of Y2O3 (33, 40 and 50 mol. %) manufactured using spark plasma sintering

Hafnia based ceramics are potential promising candidates to be used as thermal barrier coatings (TBC) for applications in the field of propulsion. In this study, Spark Plasma Sintering (SPS) of fully stabilised hafnia with yttrium oxide (yttria) was investigated to provide a better understanding of the effect of manufacturing parameters, on the crystallography, chemistry and microstructure of the material. Several hafnia powders, containing different amounts of yttria (33 mol. %, 40 mol. % or 50 mol. %), were sintered by SPS at different temperature levels ranging from 1600 °C to 1850 °C. On these materials, X-ray diffraction patterns associated with scanning electron micrographs have highlighted the influence of both the sintering temperature and the amount of yttria on the final composition, the lattice parameter and the microstructure of hafnia-based materials. In the end, it is established that, for all quantities of yttrium employed, the main phase is Y₂Hf₂O₇ with very high densification levels.     

Hydrogen production for fuel cell by oxidative reforming of diesel surrogate: Influence of ceria and/or lanthana over the activity of Pt/Al2O3 catalysts

A series of Pt catalysts supported on Al₂O₃ (Pt/A), Al₂O₃-CeO₂ (Pt/A-C), Al₂O₃-La₂O₃ (Pt/A-L) and Al₂O₃-La₂O₃-CeO₂ (Pt/A-L-C) have been prepared and tested in the oxidative reforming of diesel surrogate with the aim of studying the influence of ceria and lanthana additives over the activity and stability toward hydrogen production for fuel cell application. Several characterization techniques, such as adsorption-desorption of N₂, X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed reduction, H₂ chemisorption, and thermogravimetric analysis, have been used to define textural, structural, and surface properties of catalysts and to establish relationships with their behaviour in reaction. This physicochemical characterization has shown that lanthana inhibits the formation of α phase in alumina support and decreases ceria dispersion. Activity results show a better performance of ceria-loaded catalysts, being the Pt/A-C sample the system that offers higher H₂ yields after 8 h of reaction. The greater H₂ production for ceria-loaded catalysts, particularly in the case of the system Pt/A-C, is attributed to the Pt-Ce interaction that may change the electronic properties and/or the dispersion of active metal phase. Also, the Ce^III form of Ce^IV/Ce^III redox pair enhances the adsorption of oxygen and water molecules, thus increasing the catalytic activity and also decreasing coke deposition over surface active Pt phases. Stability tests showed that catalysts in which Pt crystallites are deposited on the alumina substrate covered by a lanthana monolayer, give rise to an increase in stability toward H₂ production.     

Melt Processing and Properties of Barium-Sialon Glasses

Bulk oxynitride glasses in the system Ba-Sialon were prepared by cooling homogenized melts from ∼1740°C at ∼50°C/min. The microchemistry, microstructure, and properties of these materials were studied by DTA, dilatometry, electron microscopy, and energy dispersive X-ray analysis. Up to ∼ 7 at.% nitrogen was retained in the glasses by the conventional glass-processing techniques used. Microscopically homogeneous glasses were obtained despite macroscopic segregation of millimeter-sized metallic spheres consisting of Si and Fe. Incorporation of nitrogen in the glass network led to decreasing thermal expansion coefficients, higher glass-transition temperatures, and greater values of indentation hardness with increasing nitrogen content.     

Preparation and Properties of Silver Borate Glasses

Silver borate Basses containing 0 to 30 mol% Ag₂O were formed. Properties measured include density, thermal expansion coefficient, glass transformation and dilatometric softening temperatures, transformation-range viscosity, dc electrical conductivity, and helium permeability and diffusivity. Optical spectroscopy revealed that the color of these glasses results from absorption bands at ∼407, ∼310, and ∼250 nm. Each band increased in intensity as the silver oxide content of the glass was increased. The properties of these glasses were consistent with the structural model currently used to describe the structure of alkali borate glasses. No evidence for the existence of phase separation was found for the conditions of the present study.     

Glass Properties in the Yttria-Alumina-Silica System

The glass formation region in the yttria-alumina-silica system was investigated. Properties of glasses containing 25 to 55 wt% yttria were measured and the effect of the composition was determined. The density, refractive index, thermal-expansion coefficient, and microhardness increased with increasing yttria content. The dissolution rate in IN HCl increased with increasing yttria content and temperature. These glasses were also found to have high electrical resistivity.