Microwave and conventional sintering of rapidly solidified Al2O3-ZrO2 powders

The Al₂O₃-ZrO₂ eutectic composition was rapidly solidified, forming amorphous and crystalline structures. The as-quenched material was crushed and pressed into pellets which were sintered conventionally or with microwaves. Conventional and microwave sintering at temperatures up to 1600 °C resulted in a microstructure where 100–200 nm ZrO₂ grains were present intergranularly in the -Al₂O₃ grains. Larger ZrO₂ grains (1 m) were found intergranularly. The as-quenched lamellar structure spheroidized during sintering at high temperatures. Boron contamination of the powders resulted in more homogeneous and dense as-fired samples but promoted the ZrO₂ tetragonal-to-monoclinic transformation, which was attributed to increased grain boundary diffusivity. Conventional sintering at low temperatures resulted in the formation of rods of an Al₂O₃-rich phase which grew from a low-melting B₂O₃-rich liquid.     

Ceramic eutectics in the systems ZrO2-Ln2O3 (Ln=Lanthanide): unidirectional solidification,microstructural and crystallographic characterization

Unidirectionally solidified refractory eutectics (melting point between 2100 and 2300° C) in the systems ZrO₂-Ln₂O₃ (Ln=Nd, Sm, Dy) were prepared by skull-melting. Depending on the growth conditions, different eutectic microstructures were obtained and studied. In particular, well-aligned lamellar eutectics with a great regularity (interlamellar spacing about 10 m) were observed with sufficiently slow solidification rates (e.g. 0.4 cm h^–1). Preferred crystallographic directions for the eutectic growth and epitaxial relationships between phases were determined by X-ray diffraction. Microhardness measurements showed significant reinforcement for eutectics with regard to the pure lanthanide oxide hardness.     

Low temperature phase equilibria and ordering in the ZrO2-rich region of the system ZrO2-CaO

From co-precipitated powder samples, the solid state reactions occurring between room temperature and 1500° C in the ZrO₂-CaO system have been studied. At low temperatures, compositions containing < 25 mol% CaO show a complex picture of phase transformation and ordering in the system. From the obtained results the following singular reactions have been established. (i) Tetragonal zirconia solid solution decomposes eutectoidally at 7 mol% CaO and 1048 ± 4° C into monoclinic zirconia solid solution and calcium zirconate (CZ). (ii) Cubic zirconia solid solution undergoes a eutectoidal decomposition at 17.5 mol% Cao and 1080 ±20° C into tetragonal solid solution + calcium zirconate. (iii) The monoclinic ordered phase, CaZr₄O₉ (₁), ), undergoes an order-disorder transformation into cubic zirconia solid solution at 1232 ± 5° C. (iv) Cubic zirconia solid solution undergoes a eutectoidal decomposition into two ordered phases, ₁ + ₂ at 21 mol% CaO and 1200 ± 10°C. (v) Hexagonal ordered phase Ca₆Zr₁₉O₄₄ (₂) decomposes peritectoidally into cubic zirconia solid solution + calcium zirconate at 1360 ± 10° C. The two ordered phases ₁ and ₂ seem to be unstable below 1100° C. By using DTA, X-ray diffraction and SEM techniques, the extent of the tetragonal and cubic zirconia solid solution fields have been established. From the above experimental results a new tentative phase diagram is given for the ZrO₂-rich region of the system, ZrO₂-CaO.     

Sintering of pseudo-boehmite and γ-Al2O3

Sintering of pseudo-boehmite, acicular-Al₂O₃ produced by dehydration of pseudo-boehmite, and-Al₂O₃ ex alum was investigated. The sintering process was studied by X-ray diffraction, transmission electron microscopy with selected area electron diffraction and BET surface area measurements. The solid state reaction to-Al₂O₃ causes a steep drop of the surface area to less than 10 m²g^–1. The acicular pseudo-boehmite and-Al₂O₃ supports exhibit an intermediate state where the acicular particles assume a rod-like shape and the surface area falls from about 300 to 100 m²g^–1. It was established that reaction to -Al₂O₃ and, hence, sintering proceeds via a nucleation and growth mechanism. The rate-limiting step is nucleation of -Al₂O₃. Consequently, the contacts between the elementary alumina particles dominate the sinter process. The contact between the acicular elementary particles of pseudoboehmite and-Al₂O₃ studied leads to the reaction to -Al₂O₃ to be almost complete after keeping samples for 145 h at 1050 °C. Decomposition of alum produces very small particles showing negligible mutual contacts. Consequently an elevated thermal stability is exhibited. Treatment of the alumina ex alum with water and drying results in a xerogel in which contact between elementary particles is much more intimate. Accordingly, treatment at 1050 °C causes a sharp drop in surface area.     

Preparation of composite Al2O3-TiO2 particles from organometallic precursors and transformations during heating

Equimolar Al₂O₃-TiO₂ composite powders were prepared via controlled hydrolysis of organometallic precursors, sometimes in the presence of submicrometre commercial-Al₂O₃ or anatase-TiO₂ particles. Variations in the chemical procedures were used aimed at different submicrostructures within the resulting powders. Heating such powders in air shows that structural behaviour is influenced by the micromorphology of the composite particle. Transformation temperatures of the titania phases seem to depend upon some size parameter which would represent their morphology within the powders. Studies performed on a series of non-equimolar Al₂O₃-TiO₂ composite powders showed that the temperature of -Al₂O₃ formation may be decreased by 210° C possibly due to a seeding effect of rutile. Pseudobrookite Al₂TiO₅ was never detected at 1300° C in air.     

Effect of pH on 980 °C spinel phase-mullite formation of Al2O3-SiO2 gels

Different reaction paths of mullite formation via sol-gel processing techniques are reviewed. These variations are due to differences in hydrolysis/gelation behaviours of the silica and alumina components used. Variations of pH during processing without altering other variables follow three different routes of mullite formation. In the highly acidic region(pH 1), the gel does not exhibit a 980 °C exotherm but forms -Al₂O₃. Mullite forms at high temperature by diminution of -Al₂O₃ and -cristobalite, respectively. In the pH range of 3–4.5, gels exhibit a 980 °C exotherm and develop only mullite. In the highly alkaline region (pH 14), the gel produces a Si-Al spinel phase at the 980 °C exotherm and mullite formation at the 1330 °C exotherm takes place from the intermediate Si-Al spinel phase.     

The effect of an added seed on the phase transformation and the powder properties in the fabrication of Al2O3 powder by the sol-gel process

-Al₂O₃ powder was produced by the sol-gel process. The prepared sol-gels were seeded with 1.5 wt% powder (0.12m). The phase transformation of Boehmite into -Al₂O₃ and also the particle size distribution of the transformed -Al₂O₃ were strongly influenced by seeding and the heating rate during calcination. -Al₂O₃ seed particles have been shown to act as a nuclei for the transition of - to -Al₂O₃ and also to increase the driving force of the phase transformation, which consequently lowers the transformation temperature by about 200 °C. The particles derived from the seeded sol-gels retarded the formation of vermicular microstructures and were finer than those in the unseeded case. The seeding and the control of the heating rate during calcination could inhibit the grain growth due to transformation into -Al₂O₃. Fine particles which are homogeneous and have a high sinterability at lower temperatures could be obtained.     

On the formation of thermally sprayed alumina coatings

A model for the fomation of thermally sprayed alumina coatings is proposed. The spreading and crystallization of liquid droplets on impact with the substrate are analysed and the thermal history of individual particles related to the kinetics of nucleation of -Al₂O₃ to other forms. The results suggest that under the usual spraying conditions undercooling of the liquid droplets is such that -Al₂O₃ nucleates in preference to -Al₂O₃ and the cooling rate after solidification is sufficiently rapid to prevent transformation to -Al₂O₃ or -Al₂O₃. Transformation of initially formed -Al₂O₃ to -Al₂O₃ appears to be possible only if the lamellae formed on impact are thicker than about 10 m if the substrate is heated to about 1000° C, or if the thickness is greater than about 20 m on an unheated substrate. The -Al₂O₃ generally observed in thermally sprayed coatings is the result of crystallization from pre-existing nuclei arising from incomplete melting of the feed material.     

Microstructure and Mechanical Properties of ZrO2(2Y)-Toughened Al2O3 Ceramics Fabricated by Spark Plasma Sintering

Spark plasma sintering (SPS) has been performed for 5 min at 1500°C and 30 MPa using submicrometer-sized Al₂O₃/ZrO₂(2Y) composite powders in the Al₂O₃-rich region. Dense ZrO₂-toughened Al₂O₃ (ZTA) ceramics show excellent mechanical strength; the strength of 1620 MPa is achieved in the ZTA with 50 mol% ZrO₂. The grain size of Al₂O₃ in ZTA decreases from 1.5 to 0.6 m with increased ZrO₂ content. Almost all the ZrO₂ grains (0.3 m) are located in the boundaries of the Al₂O₃ grains. Mechanical properties are discussed, with an emphasis on the relation between t-/m-ZrO₂ ratios and microstructures of ZTA.     

Stability of Si3N4-Al2O3-ZrO2 composites in oxygen environments

Oxidation of dense Si₃N₄-Al₂O₃-ZrO₂ and Si₃N₄-Al₂O₃ compacts, at 873–1773 K and 98 KPa air atmosphere, results in two different parabolic oxidation regimes. Oxygen diffusion is likely to be the governing step at low temperature (T<1623 K (H= 100kJ mol^–1)), whereas at T> 1623 K (H = 800kJ mol^–1) metal cation diffusion through the grain boundary phase appears limiting. The excellent stability in oxygen environments of the Si₃N₄-Al₂O₃-ZrO₂ composites compared to other ZrO₂-Si₃N₄ materials derives from (i) absence of easy-to-oxidize Zr-O-N phases; (ii) reduced amount of grain boundary phase, and possibly (iii) decreased solubilization rate of the nitride phases in the high viscous oxide film.     

Surface nucleation and cellular growth kinetics of cordierite glass ceramics containing 3 mol % Y2O3-ZrO2

Cordierite-based glass ceramics of the 2MgO2Al₂O₃5SiO₂ composition with t-ZrO₂ (3 mol% Y₂O₃-ZrO₂) and P₂O₅ addition, was heat-treated isothermally and isochronically for crystallization studies. Major crystalline phases incurred by the heat treatment were t-ZrO₂ and -cordierite. Surface nucleation predominated when edge and corner nucleation in these samples were suppressed regardless of their radii of curvature. Crystallization began with the formation of -quartz S.S. and its transformation to -cordierite was followed by prolonged heating. Cellular growth of -cordierite on the surface of the quenched glass plates, gave a linear kinetics. The activation energy for cellular growth was 410 kJ mol^–1.     

Polymorphism of the Ag8S4O4 and Ag6S3O4 compounds

Experimental results of the reaction occurring between aqueous solutions of AgNO₃ and Na₂S₂O₃ were presented in this work. It has been demonstrated that these reagents form two phases to which the summary formulas: -Ag₈S₄O₄ and -Ag₆S₃O₄ were ascribed. The -Ag₈S₄O₄ phase crystallizes in a tetragonal system and has the following parameters of the unit cell: a = b = 0.72052 nm, c = 0.51140 nm, V = 0.26550 nm³, Z = 1, d_x = 6.60 g/cm³. At 223°C -Ag₈S₄O₄ undergoes an irreversible, endothermic polymorphic transition. The heat of this transition amounts 8.03 × 10^–3 J/mol. A high-temperature polymorphic form -Ag₈S₄O₄ melts at 400°C. The -Ag₆S₃O₄ phase crystallizes in a monoclinic system and has the following parameters of the unit cell:a = 2.09616 nm, b = 0.53118 nm, c = 1.49885 nm, = 102.78°, V = 1.62753 nm³, Z = 8, d_x = 6.59 g/cm³. -Ag₆S₃O₄ also undergoes an irreversible, endothermic polymorphic transition at 221°C. The heat of this transition amounts 7.65 × 10^–3 J/mol. A high-temperature form, -Ag₆S₃O₄, melts at 390°C.     

The ZrO2-rich region of the ZrO2-MgO system

The solubility limits of MgO in tetragonal zirconia were studied by combining the differential thermal analysis data and X-ray disappearing phase method. From these experiments a eutectoid reaction, tetragonal ZrO₂ solid solution monoclinic ZrO₂ solid solution + MgO, at 1120±10 °C and 1.6±0.2 mol% MgO was established. The solubility of MgO in tetragonal ZrO₂ diminished as the temperature increased, and at 1700 °C the solubility was less than 0.5 mol% MgO. The extent of the cubic zirconia solid solution single field was determined by using precise lattice parameter measurements and SEM observations. In this way an invariant eutectoid point, cubic ZrO₂ solid solution tetragonal ZrO₂ solid solution + MgO, was located at 1420±10 °C and 14.8±0.5 mol% MgO.     

The effects of external stress on the cubic-tetragonal transformation in rapidly quenched ZrO2-Y2O3

The effects of the external stress on the displacive cubic (c) to tetragonal (t) transformation, taking place during rapid quenching of ZrO₂-Y₂O₃ alloys by a hammer-anvil unit, were examined through the statistical analysis of the crystallography of the product phases. The initially formed c-phase had no strong texture with respect to the stress direction. However, specific t variants among crystallographically equivalent ones were formed preferentially. From these observations, it is concluded that the applied stress plays an important role on the deformation to change the lattice during the c t transformation.     

Densification of zirconia-containing sialon composites by Sm2O3

Sm₂O₃ was used as an additive for ZrO₂/O-sialon composites and showed remarkably good densification behaviour on sintering. Sm₂O₃ appeared to behave as a densification rather than a stabilization additive and the low eutectic temperature in this system facilitated densification before zircon dissociation. An important advantage is that the final sintering temperature is then determined by the minimum temperature at which full conversion from -Si₃N₄ to O-sialon can be achieved. At this temperature (1500–1550 °C), grain growth of zirconia is minimal, and this allows control of small grain size for the zirconia particles.     

The modulated structure formed by isothermal ageing in ZrO2-5.2 mol % Y2O3 alloy

The modulated structure produced by isothermal ageing of ZrO₂-5.2 mol % Y₂O₃ alloy was examined mainly by electron microscopy. It was found that the modulated structure was formed at ageing temperatures between 1400 and 1600° C, but not at 1700° C. The structure is developed by spinodal decomposition, which produces compositional fluctuation in the elastically soft 111 direction in cubic zirconia. The hardness increase caused by the development of modulated structure during ageing is larger than the hardening by precipitation of tetragonal phase in the cubic matrix.Graduate Student, Tohoku Univerisy, Sendai, Japan.     

Low-temperature synthesis,pyrolysis and crystallization of tantalum oxide gels

Tantalum oxide gels in the form of transparent monoliths and powders have been prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC₂H₅)₅C₂H₅OHH₂OHCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide water HCl ratio, the time of gel formation increased with the alcohol to alkoxide molar ratio. Thermal evolution of the physical and structural changes in the gel has been monitored by differential thermal analysis, thermogravimetric analysis, X-ray diffraction, and infrared spectroscopy. On heating to 400 °C, the amorphous gel crystallized into the low-temperature orthorhombic phase -Ta₂O₅, which transformed into the high-temperature tetragonal phase -Ta₂O₅ when further heated to 1450 °C. The volume fraction of the crystalline phase increased with the firing temperature. The -Ta₂O₅ converted back into the low-temperature phase, -Ta₂O₅, on slow cooling through the transformation temperature of 1360 °C, indicating a slow but reversible transformation.     

Diffusional cubic-to-tetragonal phase transformation and microstructural evolution in ZrO2-Y2O3 ceramics

The diffusional cubic-to-tetragonal (c-t) phase transformation and microstructural evolution were studied on ZrO₂-Y₂O₃ ceramics with 4 to 6 mol% Y₂O₃ annealed in the two phase (c + t) region for longer periods of time. It was shown that in early stages of annealing a tweed structure of t-ZrO₂ was developed. With increasing annealing time this tweed structure becomes coarser and changes into internally twinned colony structure. The colonies can grow to large sizes but their twin-spacing remains almost constant. The effect of increasing annealing temperature was shown to be more obvious than prolonging annealing time in the transition from tweed to colony structure. The mechanism of the diffusional c-t transformation was discussed.     

The effect of a Cr2O3-addition on the phase transformation and catalytic properties of γ-Al2O3 in treatment of lean-burn exhausts

The solid-state thermal behaviour of -Al₂O₃ doped with 10 mol% Cr (oxide) was studied with respect to phase-transition behaviour and the co-ordination of the dopant Cr cations. A series of transformations: -Al₂O₃ -Al₂O₃ -Al₂O₃ -Al₂O₃ was observed for Cr₂O₃-doped alumina samples between 500 °C and 1100 °C. Rapid grain growth occurred at temperatures close to 1100 °C. The electron spin resonance (ESR) spectra for the sample heat-treated at 500 °C corresponded to the resonance of -Cr³⁺ in an amorphous Cr oxide impregnated onto the - and -alumina support. The change of ESR spectrum indicated the existence of Cr³⁺, suggesting the formation of a solid solution with the same structures as -Al₂O₃ and/or -Al₂O₃ at 800–1000 °C. The evaluation of catalytic activities for model exhaust was performed under lean-burn (an excess of oxygen) condition of air/fuel ratio A/F = 18 and space velocity SV = 100 000 h^–1 . The modified Al₂O₃ catalyst heat-treated at 1000 °C in air showed removal conversion of 100% for hydrocarbon (C₃H₆), 92% for CO and 5% for NO at 550 °C. Present results suggest that Cr-modification to Al₂O₃ leads to catalytic improvement with good thermal durability.     

Infrared transmission of sintered 3 mol% Y2O3-ZrO2 gel

Translucent ZrO₂ film was successfully prepared by gelling hydrothermally produced nano-ZrO₂ powders. The film (300 m thick) was found to transmit light to 6.5 m (40% transmission) when sintered at 1200 °C, but transmission was totally lost after sintering at 1300 °C for 1 h. Residual organic material such as urea, which was used for preparing the powder, dominated the transmission of the film in the region between 1.3 and 4.5 m when sintered below 1000 °C. When sintered above 1000 °C, the microstructure controlled the transmission. Both organic residuals and the microstructure of the zirconia were found to determine the transmission in 4.5–6.5 m region.