Low-temperature reaction-sintering of mullite ceramics with an Y2O3 addition

Mullite ceramics were fabricated at relatively low temperatures from powder mixtures of -Al₂O₃ and quartz, with an Y₂O₃ addition. The mullitization process was analyzed by X-ray diffraction. The densification behavior was investigated as a function of the Y₂O₃ content, sintering temperature and holding time as well as mullite seeds. It has been shown that mullitization occurs via a nucleation and growth mechanism within an yttrious aluminosilicate glass, but lattice and grain-boundary diffusion becomes important during the densification process. Moreover, the incorporation of mullite seeds was observed to enhance both mullitization and densification. At 1400°C for 5 h or 1450°C for 2 h, 15 mol% Y₂O₃-doped and 5 mol% mullite-seeded specimens can be sintered to almost full density.     

Yb2O3 and Y2O3 co-doped zirconia ceramics

A suspension stabilizer-coating technique was employed to prepare x mol% Yb₂O₃ (x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y₂O₃ co-doped ZrO₂ powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb₂O₃ and Y₂O₃ co-doped zirconia ceramics. Fully dense ZrO₂ ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb₂O₃ content and the sintering parameters. Polycrystalline tetragonal ZrO₂ (TZP) and fully stabilised cubic ZrO₂ (FSZ) were achieved in the 1.0 mol% Y₂O₃ stabilised ceramic, co-doped with 1.0 mol% Yb₂O₃ and 4.0 mol% Yb₂O₃, respectively. The amount of stabilizer needed to form cubic ZrO₂ phase in the Yb₂O₃ and Y₂O₃ co-doped ZrO₂ ceramics was lower than that of single phase Y₂O₃-doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m^1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb₂O₃ and 1.0 mol% Y₂O₃ ceramic at 1450 °C for 1 h.     

Preparation, sintering, microstructure, and thermal stability of Y2O3- and CeO2-doped tetragonal zirconia ceramics

Yttria- and ceria-doped tetragonal zirconia polycrystals ((Y, Ce)-TZP) with compositions 2·5 mol% YO_1·5-4 mol% CeO₂---ZrO₂, 4 mol% YO_1·5-4 mol% CeO₂---ZrO₂, and 2·5 mol% YO_1·5-5·5 mol% CeO₂---ZrO₂ were prepared from zirconia sols obtained hy hydrolysis of ZrOCl₂ solution, and their sintering, microstructure and thermal stability were studied. Sintered bodies with 99% TD were obtained by firing at 1400°C for 2 h in air. The grain size of (Y, Ce)-TZP increased with decreasing Y₂O₃ content in Y₂O₃---CeO₂---ZrO₂. (Y, Ce)-TZP was resistant to tetragonal-to-monoclinic (t → m) phase transformation during low temperature ageing as compared with 3Y-TZP.     

Microstructures and mechanical properties of 8Y-FSZ ceramics with BaTiO3 additive

The microstructure and mechanical properties of 8 mol% Y₂O₃ fully stabilized zirconia (8Y-FSZ) with BaTiO₃ additive were investigated. The introduction of BaTiO₃ additive would significantly increase the density and the grain size of 8Y-FSZ ceramics. XRD, Raman spectroscopy, and dielectric measurement were performed. A rhombohedral Ba(Ti_1−xZr_x)O₃ ferroelectric phase resulted in the composite with 5 mol% additive, while for those with higher additive content, the secondary phase changes to cubic Ba(Ti_1−xZr_x)O₃. The fracture toughness of the xBaTiO₃/(1−x)8Y-FSZ composites reached a maximum and then decreased with increasing the amount of additive. The highest value reached 6.1 MPa m^1/2 for 0.05BaTiO₃/0.95(8Y-FSZ) sintered at 1475 °C for 3 h, where the piezoelectric/ferroelectric secondary phase toughening played an important role. Moreover, the fracture toughness of the composites increased firstly and then decreased with increasing sintering temperature.     

Thermal evolution and crystallisation of polydimethylsiloxane–zirconia nanocomposites prepared by the sol–gel method

Polydimethylsiloxane–zirconia nanocomposites have been prepared by hydrolysis of diethoxydimethylsilane and zirconium n-propoxide in different molar ratios. Transparent, homogeneous and non-porous xerogels have been obtained up to 70 mol% ZrO₂ content. The starting xerogels have been pyrolyzed under argon atmosphere up to 1400°C and the structural evolution of samples treated at different temperatures has been followed by X-ray diffraction, transmission electron microscopy, infrared and ²⁹Si solid state nuclear magnetic resonance spectroscopies, thermal analyses and N₂ sorption measurements. The polymer-to-ceramic conversion leads to the structural rearrangement of the siloxane component with the production at 600°C of high surface area materials with pore sizes below 3 nm. Samples are amorphous up to 800°C. At 1000°C, the structural evolution of the silicon moiety produces an amorphous oxycarbide phase whereas the primary crystallisation of tetragonal zirconia takes place, with crystallinity and crystallite sizes depending on the ZrO₂ content. At 1400°C, the silicon oxycarbide phase generates a mixture of amorphous silica and crystalline silicon carbide polymorphs. In this matrix, tetragonal and monoclinic ZrO₂ phases are present with ZrO₂ average crystallite dimensions never exceeding 20 nm, for ZrO₂ content ≤50 mol%. The tetragonal/monoclinic ratio as well as the crystallite sizes appear strictly related to the chemical composition. ©     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia powder from sucrose derived organic precursors

An organic precursor synthesis of 8 mol% yttria stabilized zirconia (YSZ) powder from Zr–Y composite nitrate solution and sucrose has been studied. Oxidation of sucrose in Zr–Y composite nitrate solution containing excess nitric acid in situ generates hydroxy carboxylic acids that forms a white sol which showed peaks at 1640 cm⁻¹ and 1363 cm⁻¹ in IR spectrum corresponding to hydroxy carboxylic acid complexes of Zr and Y. Precursor mass obtained by drying the sol on calcinations at 600 °C produced loosely agglomerated particles of cubic YSZ. Deagglomerated YSZ contain submicron particles with D₅₀ value of 0.5 μm and the particles are aggregates of nanocrystallites of nearly 10 nm size. Compacts prepared by pressing the YSZ powder sintered to 96.7% TD at 1450 °C. The sintered YSZ ceramic showed an average grain size of 2.2 μm.     

Fabrication of electrolyte materials for solid oxide fuel cells by tape-casting

In this research, solid oxide fuel cell electrolytes were fabricated by aqueous tape-casting technique. The basic compositions for SOFC electrolyte systems were focused on yttria-stabilized zirconia (YSZ) system. The powders used in this study were from different sources. ZrO₂-based system doped with 3, 8, and 10 mol% of Y₂O₃, and 8YSZ electrolyte tape illustrated the desirable properties. The grain size of the sintered electrolyte tapes was in the range of 0.5–1 μm with 98–99% of theoretical density. Phase and crystal structure showed the pure cubic fluorite structure for 8–10 mol% YSZ and tetragonal phase for 3 mol% doped. The electrolyte tapes sintered at 1450 °C for 4 h had the highest ionic conductivity of 30.11 × 10⁻³ S/cm which was measured at 600 °C. The flexural strengths were in the range of 100–180 MPa for 8–10 mol% YSZ, and 400–680 MPa for 3 mol% YSZ.     

Formation of Y3Al5O12–Al2O3 eutectic microstructure with off-eutectic composition

Homogeneous-eutectic microstructure of Y₃Al₅O₁₂–Al₂O₃ system without coarse primary crystals was formed at an off-eutectic composition. This method utilizes a low migration rate in an amorphous phase. A mixture of Y₂O₃ and Al₂O₃ having the off-eutectic composition was melted and quenched rapidly to form an amorphous phase. A heat-treatment of the amorphous phase at 1000 °C and 1300 °C for 30 min formed Y₃Al₅O₁₂ and Al₂O₃ phases. SEM observation of this material, which was formed from the amorphous phase at 1300 °C for 30 min, showed homogeneous eutectic-like microstructure. The formation of the primary crystals (coarse Al₂O₃), which are always observed in the off-eutectic compositions by ordinary method, was completely suppressed.     

Hot isostatic pressing of SiC/Si3N4 composite with rare earth oxide additions

SiC/Si₃N₄ composites with rare earth oxide additions have been prepared by glass encapsulated hot isostatic pressing at 1850 °C and 200 MPa pressure. Mechanical properties and microstructures of the sintered samples have been studied. It is shown that different molar ratios of La₂O₃ to Y₂O₃ and the total amount of La₂O₃ and Y₂O₃ additions can affect the mechanical properties significantly. With 3 wt% La₂O₃ + Y₂O₃ additions, lower La₂O₃/Y₂O₃ molar ratio exhibits higher bending strength and median fracture toughness, but relatively lower Vickers hardness. For addition of 6 wt% La₂O₃ + Y₂O₃, the higher bending strength, Vickers hardness and fracture toughness correspond to a certain La₂O₃/Y₂O₃ molar ratio of 1.5, 1.0 and 0.5, respectively. SEM observation shows that the SiC matrix composite with fine grain size and homogeneous microstructure can be obtained.     

Electrical properties of (Bi2O3)0.75(RE2O3)0.25 ceramics (RE=Dy, Y, Ho, Er and Yb)

Five kinds of rare earth stabilized bismuth oxide ceramics, (Bi₂O₃)_0.75(RE₂O₃)_0.25 (RE=Dy, Y, Ho, Er and Yb), were synthesized by sintering a mixture of Bi₂O₃ and RE₂O₃ at 900–1100 °C and their electrical properties were investigated. The bulk density and the lattice constant linearly increased with an increase in the atomic weight of RE and the ionic radius of RE³⁺, respectively. The electrical conductivity at 300 °C slightly increased with the increasing ionic radius of RE³⁺, while at 500 and 700 °C, it was constant regardless of the ionic radius of RE³⁺. The migration activation energy and the association activation energy showed a maximum value and a minimum value at RE=Er, respectively.     

Reforming of methane with carbon dioxide to synthesis gas over supported Rh catalysts

Reforming of methane with carbon dioxide to synthesis gas (CO/H₂) has been investigated over rhodium supported on SiO₂, TiO₂, γ-Al₂O₃, MgO, CeO₂, and YSZ (ZrO₂ (8 mol% Y₂O₃)) catalysts in the temperature range of 650–750°C at 1 bar total pressure. A strong carrier effect on the initial specific activity, deactivation rate, and carbon accumulation was found to exist. A strong dependence of the specific activity of the methane reforming reaction on rhodium particle size was observed over certain catalysts. Tracing experiments (using ¹³CH₄) coupled with temperature-programmed oxidation (TPO) revealed that the carbon species accumulated on the surface of the Rh/Al₂O₃ catalyst during reforming reaction at 750°C are primarily derived from the CO₂ molecular route. The amount of carbon present on the working catalyst surface which is derived from the CH₄ molecular route is found to be very small.     

Densification and properties of zirconia prepared by three different sintering techniques

Densification of nanocrystalline yttria stabilized zirconia (YSZ) powder with 8 mol% Y₂O₃, prepared by a glycine/nitrate smoldering combustion method, was investigated by spark plasma sintering, hot pressing and conventional sintering. The spark plasma sintering technique was shown to be superior to the other methods giving dense materials (≥96%) with uniform morphology at lower temperatures and shorter sintering time. The grain size of the materials was 0.21, 0.37 and 12 μm after spark plasma sintering, hot pressing and conventional sintering, respectively. Total electrical conductivity of the materials showed no clear correlation with the grain size, but the activation energy for spark plasma sintered materials was slightly higher than for materials prepared by the two other densification methods. The hardness, measured by the Vickers indentation method, was found to be independent on grain size while fracture toughness, derived by the indentation method, was slightly decreasing with increasing grain size.     

Effect of γ-alumina crystallinity on the state of rhodium during high-temperature treatments in oxygen and hydrogen

Rhodium catalysts, supported on six γ-Al₂O₃ supports with different crystallinities, were exposed to sequential treatments in hydrogen at 500°C, in oxygen at 760°C, in hydrogen at 500°C and at 760°C, respectively. Samples were characterized by X-ray diffraction and hydrogen chemisorption at various stages in the sequential treatment. Based on the characterization results, it is concluded that the formation of crystalline Rh₂O₃ is a function of γ-Al₂O₃ crystallinity; formation of crystalline Rh₂O₃ increased with increasing crystallinity of γ-Al₂O₃ during treatment in oxygen at 760°C. The crystalline Rh₂O₃ formed during treatment in oxygen at 760°C was reduced to Rh metal by hydrogen at 500°C, but most of the Rh did not adsorb hydrogen at room temperature. Subsequent treatment in hydrogen at 760°C increased the hydrogen adsorption capacity by as much as a factor of three. X-ray line broadening measurements showed that oxygen treatment of reduced Rh/γ-Al₂O₃ at 760°C followed by hydrogen reduction at 500°C resulted in significant increases in Rh crystal size; further treatment in hydrogen at 760°C resulted in additional sintering of Rh.     

Effect of La on the thermal stability of Pd/γ-Al2O3 catalytic membranes

Lanthanum-doped Pd/γ-Al₂O₃ and Pd/γ-Al₂O₃ membranes were prepared by sol-gel methods. The thermal stability of the unsupported Pd/γ-Al₂O₃ and La/Pd/γ-Al₂O₃ membranes was investigated with BET (including average pore size, pore volume and BET surface area), XRD, and DTA techniques. The average pore size of the Pd/γ-Al₂O₃ membranes increased sharply after sintering at temperatures higher than 1000°C. Addition of 3 mol% lanthanum can raise the temperature of the γ-Al₂O₃ to-Al₂O₃ phase transformation significantly. This improves the thermal stability of the Pd/γ-Al₂O₃ catalytic membranes.     

The effect of thermal cycling on oxide scale structure and morphology on a hot-pressed silicon nitride

Dense Si₃N₄ hot-pressed with the aid of 9 wt% Y₂O₃ was oxidised in ‘dry’ synthetic air at both 1000 and 1200°C for up to 500 h under thermal cycling conditions. The experiments revealed that thermal cycling has little effect on oxidation kinetics although the morphology of surface oxidation products is affected by the cycling frequency. Cracks formed in the oxide layers on cooling healed immediately on re-exposure to high temperature, and there was no apparent change in the oxidation rate controlling mechanism over the time period investigated. The exposure of the material at 1000°C did not result in catastrophic oxidation as observed for some other Y₂O₃-doped hot-pressed Si₃N₄ compositions. Additionally, it was observed that crystallisation of the oxide layer with time (assisted in part by the outward diffusion of intergranular phase cations from the bulk ceramic to the surface scale) leads to non-parabolic kinetics owing to reduced rates of diffusion through crystalline phases in the surface scale. ©     

Processing and mechanical properties of ZrO2–TiB2 composites

In this paper, a strategy is described to develop high toughness yttria-stabilised tetragonal zirconia polycrystalline (Y-TZP) composites reinforced with hard TiB₂ particles. The experimental results revealed that fully dense Y-TZP composites with 30 vol.% TiB₂ can be obtained with a moderate hardness of 13 GPa, a high strength up to 1280 MPa and an excellent indentation toughness up to 10 MPa m^1/2 by hot pressing in vacuum at 1450 °C. The toughness of the composites can be tailored between 4 and 10 MPa m^1/2 by varying the yttria stabiliser content of the ZrO₂ matrix between 3 and 2 mol%. An optimum composite toughness was achieved for a ZrO₂ matrix with an overall yttria content of 2.5 mol%, obtained by mixing pure monoclinic and 3 mol% Y₂O₃ co-precipitated ZrO₂ starting powders. An important observation is that the thermal residual tensile stress in the ZrO₂ matrix due to the TiB₂ addition, needs to be taken into account when optimising the transformability of the ZrO₂ matrix in order to develop high toughness Y-TZP composites.     

Synthesis, sintering and characterization of PNZST ceramics from high-energy ball milling process

Pb_0.99Nb_0.02[(Zr_0.60Sn_0.40)_0.94Ti_0.06]_0.98O₃ powders were synthesized from oxide mixtures of Pb₃O₄, Nb₂O_5, ZrO₂, SnO_2, and TiO₂ using a Fritsch P4™ vario-planetary ball milling system. The perovskite structure of PNZST powder can be obtained well after 14 h milling and crystallite size of the powders greatly reduced to 20–30 nm. The resultant powders have better sinterability characteristics to obtain dense ceramic bodies at low temperature. The dielectric constant of samples shows a maximum at 1150 °C and the PE_MC to PE_SC transformation temperature shifts to higher temperature with an increase in grain size. The field-induced strain reaches maximum longitudinal strain of 0.32% and the P–E hysteresis loop shows much higher squareness at 1150 and 1200 °C. The measured dielectric and antiferroelectric properties of the PNZST ceramics were found to be comparable to those from other processing techniques.     

Microstructure and properties of various fluorine-containing SiAlON ceramics synthesized by HIPing

An attempt was made to prepare various F-doped β-, O-, X-, and -SiAlONs from a mixture of Si₃N₄, SiO₂, Al₂O₃, AlN, or Y₂O₃ using AlF₃ or topaz as the fluorine source by HIPing at 1500–1800°C and 150 MPa. The phases were identified and the z, x, and m/n values determined for β-, O-, and -SiAlONs by X-ray diffraction. When AlF₃ was used, a single phase ceramic (O-SiAlON) was produced from a mixture of -Si₃N₄ and SiO₂ at 1500°C, with a mixture of O- and β-SiAlONs formed at 1700°C. A mixture of -Si₃N₄, AlN, and Y₂O₃ with AlF₃ produced β-/Y--SiAlON ceramics at 1730°C. The use of topaz produced the β-SiAlON ceramic with a trace of mullite from a mixture of -Si₃N₄ and AlN at 1770°C and mixed phase β-/O-SiAlON ceramics from -Si₃N₄ and SiO₂ at 1700°C. Single phase X-SiAlON could not be obtained under the present conditions. The microstructures of the single phase O- and β-SiAlON ceramics and the β-/Y--SiAlON mixture showed the growth of O- and β-SiAlON and Y--SiAlON crystals with hexagonal and/or long rod-like or platy shapes in a matrix of F-containing glassy phase. The compositions of the SiAlON crystals and the glass phase were semi-quantitatively determined by EDX; the total glass phase was estimated by a quantitative Rietveld XRD powder method. The F-doped β-SiAlON ceramics showed better corrosion resistance towards NaCl vapor and lower Vickers hardnesses.     

Selection of Materials for Use at Temperatures above 1500°C in Oxidizing Atmospheres

The purpose of this work was to select materials for applications in oxidizing atmospheres at temperatures of a minimum of 1500°C. Several requirements had to be fulfilled, e.g. long-term oxidation resistance, low vapour pressure, high creep resistance and low gas permeability. Another important point was to avoid reactions and sintering in material combinations with silica forming materials. The investigation was based on a detailed literature screening, followed by compatibility tests at 1600°C in air with potential materials (Al₂O₃, ZrO₂, CeO₂, La₂O₃, Y₂O₃, HfO₂, MgO·Al₂O₃) and Mosi₂ as an example of a silica-forming material. The result of these experiments was, that only Y₂O₃ and HfO₂ did not show severe reactions in contact with MoSi₂. Since most of the materials available did not fulfill all the requirements, some new materials were investigated: CIPed MoSi₂ with different additives (SiC, ZrB₂) and recrystallized SiC (RSiC) with a polymer (polysiloxane) derived MoSi₂-filled coating. The oxidation behaviour of these materials was evaluated by continuous thermogravimetric measurements at 1500°C over a period of 100 h in air and by detailed postexperimental investigations.     

Ceria-doped zirconia-graphite as possible refractory for tundish nozzles in steelmaking

In zirconia-graphite refractories, calcia-stabilized zirconia is sensitive to silica coming from oxidized additives (Si, SiC). Accordingly, ceria is considered here as an alternative cheap stabilizer.

Ceria-doped zirconia has been prepared and the monoclinic/tetragonal distribution has been analysed. At 1500°C in oxygen, the solution of ceria in zirconia is sluggish; to obtain a pure tetragonal phase, a 16 mol% ceria concentration (equal to the solubility limit) is necessary. Such samples are stable below 1050°C, in spite of previous claims to the contrary.

At 1300°C, silica does not destabilize these samples, even in reducing conditions. However, at low oxygen pressure, the pyrochlore Ce₂Zr₂O₇ is formed, and the remaining zirconia transforms into the monoclinic modification. Nevertheless, below 1175°C, a metastable, purely tetragonal modification is obtained, because the activation energy needed for the formation of Ce₂Zr₂O₇ is too high.

In any case, the reduction does not destroy the polycrystalline texture. This fact, combined with the resistance to silica, favours the use of these materials in steelmaking.