Detection of tetragonal zirconia in alumina–zirconia powders by thermoluminescence

The thermoluminescence (TL) after excitation by UV or X-rays radiation of alumina-zirconia powders is investigated. The composites present five of the characteristic peaks of zirconia at −170, −145, −90, 0 and 95 °C. After a thermal treatment of mixed oxides, a new peak is observed at −35 °C in TL. This peak reveals the presence of stabilized tetragonal zirconia in the material. Moreover by comparing this analysis with those realised by X-ray diffraction (XRD), it can by shown that the TL has one better limit of detection than the XRD.     

Fractal analysis of cracks in alumina–zirconia composites

The crack paths, induced by Vickers indentation in alumina–zirconia composites, were analyzed using fractal geometry. The fractal dimension n_S was calculated for each crack. This parameter refers to a corresponding three-dimensional fracture surface and indicates how its geometry varies by changing the magnification. An interesting correlation between K_IC and n_S was found: it suggests that the samples with high percentages of alumina and also the pure zirconia are characterized by an intergranular fracture mode, while the composites with high zirconia content present a transgranular fracture mode. This result is confirmed by analyzing the energies of fracture calculated using both the classical and fractal approaches. The results obtained in this research not only made it possible to understand the fracture behavior of the analyzed composites, but also confirmed the good potential of fractal analysis to explain complex mechanisms such as those involved in the fracture of brittle materials.     

Mechanochemical synthesis of alumina–zirconia nanocomposite powder

Abstract

The alumina–zirconia nanocomposite powder has been synthesised by mechanical activation of a dry powder mixture of AlCl₃, ZrCl₄ and CaO. Mechanical milling of the above raw materials with the conditions adopted in this study resulted in the formation of a mixture consisting of crystalline CaO and amorphous aluminium and zirconium chlorides phases. There was no sign of chemical reaction occurring during milling stage as evidenced by X-ray diffraction (XRD) studies. Subsequent heat treatment of the milled powder at 350°C resulted in the occurrence of displacement reaction and the formation of ZrO₂ and Al₂O₃ particles within a water soluble CaCl₂ matrix. The effect of higher temperature calcination on the phase development in this powder mixture was followed by XRD analysis. Scanning electron microscopy and differential thermal analysis were also used in the characterisation of the powders. Perhaps the most important observation in this study was the formation of α-Al₂O₃ phase at a very low temperature of 400°C.     

Two-step sintering of fine alumina–zirconia ceramics

This work investigates the feasibility to the fabrication of high density of fine alumina–5 wt.% zirconia ceramics by two-step sintering process. First step is carried out by constant-heating-rate (CHR) sintering in order to obtain an initial high density and a second step is held at a lower temperature by isothermal sintering aiming to increase the density without obvious grain growth. Experiments are conducted to determine the appropriate temperatures for each step. The temperature range between 1400 and 1450 °C is effective for the first step sintering (T₁) due to its highest densification rate. The isothermal sintering is then carried out at 1350–1400 °C (T₂) for various hours in order to avoid the surface diffusion and improve the density at the same time. The content of zirconia provides a pinning effect to the grain growth of alumina. A high ceramic density over 99% with small alumina size controlled in submicron level (0.62–0.88 μm) is achieved.     

Phase composition of alumina–mullite–zirconia refractory materials

Refractories in the Al₂O₃–SiO₂–ZrO₂ system are widely used in many applications, for ceramic rollers in particular, and are characterized by high mechanical strength, excellent thermal shock resistance, resistance to corrosion by alkaline compounds and low creep at high temperature. Their performances greatly depend on the amount and chemical composition of crystalline and glassy phases, which were investigated by quantitative XRPD (RIR–Rietveld) and XRF in order to assess the effect of various Al₂O₃/SiO₂ ratios of starting batches and different alumina particle size distributions. Refractories consist of mullite, corundum, zirconia polymorphs and a vitreous phase in largely variable amounts. The mullite percentage, unit cell parameters and composition vary with sintering temperature, being mostly influenced by the Al₂O₃/SiO₂ ratio of the batch. Its orthorhombic unit cell increased its volume from 1400 to 1500 °C, while its stoichiometry became more aluminous. The corundum stability during firing is strongly affected by the Al₂O₃/SiO₂ ratio, but not by the particle size distribution of alumina raw materials. Zirconia raw materials are involved in the high temperature reactions and about one-third of the available ZrO₂ is dissolved in the glassy phase, ensuring excellent resistance to alkali corrosion, mainly depending on the fraction of coarse alumina. The phase composition of the vitreous phase increased with sintering temperature, being over 20% when the fractions of coarse alumina in the starting batch are between 0.2 and 0.5.     

Effective diffusion constant and adsorption constant of synthesized alumina,zirconia, and alumina–zirconia composite material

In this study, Al₂O₃, ZrO₂, and Al₂O₃–ZrO₂ composite materials were prepared with the sol–gel technique. X-ray diffraction analysis, differential scanning calorimetry–thermogravimetry, scanning electron microscopy–energy-dispersive X-ray spectrometry, nitrogen adsorption isotherm measurements, and helium pycnometry were used to characterize the resultant materials. Effective diffusion coefficients of helium and hydrogen and the adsorption equilibrium constant of hydrogen in the resultant materials were determined using single-pellet moment technique. The effective diffusivities of helium and hydrogen in both ZrO₂ and Al₂O₃–ZrO₂ composite pellets were found to be smaller than the value found for Al₂O_3, due to the lower tortuosity factor values of the Al₂O₃ pellet. It was found that hydrogen was weakly adsorbed on all resultant materials.     

Processing of different alumina–zirconia composites by slip casting

Two Al₂O₃–ZrO₂ mixture preparation routes: classical powder mixing and addition of a Zr (IV) precursor solution to a well dispersed Al₂O₃ suspension, were used to produce alumina (Al₂O₃)–zirconia (ZrO₂) slip cast composites. For the conventional powder mixing route, two commercial 3 mol% yttria-partially stabilized zirconia powders, 0.3 wt% Al₂O₃-doped (Al-doped Y-PSZ) and without Al₂O₃ (Y-PSZ), were employed. The influence of the zirconia content and the solid loading on the rheological properties of concentrated aqueous Al₂O₃–ZrO₂ slips were investigated. The density of green samples was studied and related to the degree of slip dispersion. In addition, the influence of the processing conditions on the density and microstructure development of sintered samples were investigated. By using the Zr (IV) precursor route, nano-sized ZrO₂ (ZN) particles homogeneously distributed on the Al₂O₃ particle surfaces were obtained; however, it let to aggregates of some Al₂O₃ particles with very fine ZrO₂ uniformly distributed. The viscosity and yield stress values of Al₂O₃–ZN suspensions were markedly higher than those of Al₂O₃–Al-doped Y-PSZ and Al₂O₃–Y-PSZ ones, for all the compositions and solid loading studied and resulted in a less dense packing of cast samples. However, for the composite with 10.5 vol% ZN a high sintered density and a smaller ZrO₂ grain size distribution compared with the conventional powder mixing route could be obtained.     

Sintering,microstrusture and hardness of different alumina–zirconia composites

Two commercial 3 mol% yttria-partially stabilized zirconia powders, 0.3 wt% Al₂O₃-doped (Al-doped Y-PSZ) and without Al₂O₃ (Y-PSZ), were used to produce alumina (Al₂O₃)-zirconia (ZrO₂) slip cast composites. The influence of the substitution of Al₂O₃ either by different Al-doped Y-PSZ contents or 50 vol% Y-PSZ on the sintering kinetic at the intermediate stage was investigated. In addition, the microstructure of Al₂O₃ and the different composites at temperatures in the range of 1100–1600 °C was studied and related to the sample hardness. An increase in the sintering rate was observed when Al-doped Y-PSZ increased from 22 to 50 vol% or when 50 vol% Y-PSZ was substituted by 50 vol% Al-doped Y-PSZ. 50 vol% ZrO₂ was the most effective concentration to reduce the rate of Al₂O₃ grain growth in the final sintering stage; the Al₂O₃ grain growth began at lower temperatures and became greater with decreasing the Al-doped Y-PSZ content. On the contrary, the ZrO₂ grain growth slightly increased with increasing the Al-doped Y-PSZ concentration. However, for 50 vol% Al-doped Y-PSZ a smaller ZrO₂ grain size distribution compared with 50 vol% Y-PSZ could be achieved. As the average Al₂O₃ grain size of the sintered samples became greater than about 1 µm a markedly decrease in the hardness was found; this occurred at temperatures higher than 1400 °C and 1500 °C for Al₂O₃ and the composite with 10.5 vol% Al-doped Y-PSZ, respectively.     

Dispersion,rheology and aqueous tape casting of alumina–zirconia composites

Abstract

Alumina and zirconia were dispersed individually in aqueous media using Darvan C as the dispersant and at optimised pH condition. Based on sedimentation, rheology, yield stress, electrodeposition and zeta potential measurements, 2 wt-% of the dispersant and a pH of 10·5 were found to be the optimum condition for the codispersion of alumina and zirconia. Aqueous tape casting slurries with a solid loading of 32 wt-% were prepared under the optimised conditions of dispersion. Alumina–zirconia (50 : 50) composite tapes of 40 μm thickness and 56% green density were obtained.     

In situ growth of carbon nanotubes in alumina–zirconia nanocomposite matrix prepared by solution combustion method

In this work successful synthesis of multiwall carbon nanotube (CNT) using solution combustion and chemical vapor deposition (CVD) methods are reported. Ceramic nanocomposite samples of (Al_2?xFe_xO₃)–(y)ZrO₂ formula with x = 0.017, 0.034 and 0.17 and y = 0.15 were initially prepared. These were then subjected to CVD process during which the in situ reduction of iron oxide to metallic iron (Fe/Fe₃C) phase/s provided the necessary catalyst for the CNT formation. The formation of long flexible filaments with a smooth and regular surface bridging between alumina–zirconia (AZ) grains could be detected. The diameters of the formed filaments were in the range of ～70 to ～320 nm and length of the order of some tens of micrometers. However, transmission electron microscope (TEM) examinations also revealed the existence of small amounts of Bamboo-like carbon along with more or less straight CNTs. This could be related to the lack of strong interactions between the metallic iron phase/s and the nanocomposite support.     

On the determination of the stress-free temperature for alumina–zirconia multilayer structures

Internal residual stresses can enhance the fracture resistance and mechanical reliability of layered ceramics. The magnitude of the stresses depends on the elastic and thermal properties of the layers and the typically assumed reference (stress-free) temperature, below which internal stresses develop. A novel combined experimental and numerical simulation approach has been developed to determine the reference temperature and experimentally proved in alumina–zirconia ceramic laminates. Dilatometric data of monolithic phases are input for the numerical simulation and experimental data on the laminate properties are used for the stress-free temperature determination. In contrast to typical assumptions, reference temperature very near the sintering temperature (i.e. approx. T_ref≈1470 °C) was found, which should be considered for the estimation of internal (residual) stresses in alumina/zirconia-based layered ceramics.     

Elastic properties and damping behavior of alumina–zirconia composites at room temperature

Alumina–zirconia composite ceramics (AZ composites) have been prepared in the whole range of compositions from pure alumina to zirconia (in steps of 10 vol.%) by slip casting, followed by sintering at 1350 °C and microstructural characterization via the Archimedes method (relative densities 0.93–0.99). Young's modulus has been measured at room temperature via the impulse excitation technique (IET) and, after appropriate porosity correction (linear, power-law, exponential), found to be in good agreement with the Hashin–Shtrikman bounds. The damping factor (internal friction), which has been measured for dense AZ composites (also via IET at room temperature), is found to increase with increasing zirconia content. Damping factors measured for porous AZ composites with porosities 25–71%, prepared with corn starch as a pore former, have been found to depend only slightly on porosity, unless the porosities are extremely high (>70%). At these porosities, however, where the Young's moduli approach zero, the damping factors exhibit a steep increase.     

Use of a design-of-experiments approach for preparing ceria–zirconia–alumina samples by sol–gel process

In this work we successfully obtained ceria–zirconia–alumina samples by the sol–gel technique. These materials were prepared under acidic or basic conditions, using either nitric acid or ammonium hydroxide as the catalyst. A design-of-experiments approach was used in order to optimize the specific surface area, pore structure, and thermal stability of the prepared samples. It was observed that the addition of ceria and zirconia did not affect the formation of γ-Al₂O₃. The highest surface areas and smallest pore sizes were observed for specimens obtained under acidic conditions and with low to intermediate concentrations of cerium and water. The increase of the heat treatment temperature from 600 °C to 1000 °C led to both a decrease of the surface area and an increase of the mean pore size. This behavior is due to the coalescence of pores upon calcination. Samples with a high concentration of ceria showed an expressive thermal instability at high temperatures. On the other hand, the addition of zirconia increased the thermal stability of these materials. In general, samples with improved thermal stabilities were obtained under basic conditions.     

Properties of alumina 10 vol% zirconia composites—The role of zirconia starting powders

Zirconia toughened alumina (ZTA) materials are applied for cutting tools, wear parts and in biomedical applications. Due to the constraint of the rigid alumina matrix, ZTA materials with up to 10 vol% zirconia addition (AZ10) do not require addition of stabilizer oxides. AZ10 materials based on submicron sized alumina and four different submicron to nanoscale zirconia powders were manufactured by hot pressing at temperatures between 1475?1600 °C. Results show that the powder choice has a strong influence on mechanical properties, evolution of microstructure and phase composition. Best results with strength up to 850 MPa, fracture toughness values of 8.5 MPa√m and invulnerability to overfiring were obtained with zirconia powders showing the coarsest yet most homogeneous primary particle size and a low degree of agglomeration. Ultrafine but hard agglomerated powders lead to materials with extremely inhomogeneous microstructure and inferior properties.     

Mesoporous ceria–zirconia–alumina nanocomposite-supported copper as a superior catalyst for simultaneous catalytic elimination of NO–CO

A series of transition metal (Mn, Fe, Co, Ni, Cu and Ag) oxides supported on ceria–zirconia–alumina nanocomposite catalysts were prepared through wetness impregnation method. The catalytic performance of these catalysts were evaluated in the catalytic elimination of NO–CO. Activity results revealed supported copper catalyst gave the optimal catalytic activity, which was related to high dispersion of copper species (XRD and Raman), low-temperature reducibility (TPR), and more oxygen vacancies (DRS).     

Tri-reforming of surrogate biogas over Ni/Mg/ceria–zirconia/alumina pellet catalysts

The performance of catalytic tri-reforming under industrially relevant situations (e.g., pellet catalysts, pressurized reactor) was investigated using surrogate biogas as the feedstock. Tri-reforming using Ni/Mg/Ce_0.6Zr_0.4O₂/Al₂O₃ pellet catalysts was studied in a bench scale fixed-bed reactor. The feed molar ratio for CH₄:CO₂:air was fixed as 1.0:0.70:0.95. The effects of temperature (800–860°C), pressure (1–6?bar), and H₂O/CH₄ molar feed ratio (0.23–0.65) were examined. Pressure has substantial impact on the reaction and transport rates and equilibrium conversions, making it a key variable. At 860°C, CO₂ conversion increased from 4 to 61% and H₂/CO molar ratio decreased from 2.0 to 1.1 as the pressure changed from 1 to 6?bar. CO₂ conversion and H₂/CO molar ratio were also influenced by the temperature and H₂O/CH₄ molar ratio. At 3?bar, CO₂ conversion varied between 4 and 43% and the H₂/CO molar ratio varied between 1.2 and 1.9 as the temperature changed from 800 to 860°C. At 3?bar and 860°C, CO₂ conversion decreased from 35 to 8% and H₂/CO molar ratio increased from 1.7 to 2.4 when the H₂O/CH₄ molar ratio was increased from 0.23 to 0.65. This work demonstrates that the tri-reforming technology is feasible for converting biogas under scaled-up conditions in a fixed-bed reactor.     

Phase equilibria in the zirconia–yttria/gadolinia–silica systems

Phase equilibria in ZrO₂-YO_1.5-SiO₂ (ZYS) and ZrO₂-GdO_1.5-SiO₂ (ZGS) were experimentally assessed at 1400?°C and 1600?°C as they can offer insight on reactions between thermal barrier coatings (TBCs) based on ZrO₂-YO_1.5/GdO_1.5 and molten silicate deposits in gas turbine engines. Features shared in both systems include the absence of ternary compounds and no ternary solubility in the binary phases. In ZYS however, a quaternary invariant reaction was observed that eliminates the zircon-disilicate equilibrium at higher temperatures. The results suggest no appreciable difference in the reactions between silica and thermal barrier oxides based on ZrO₂-YO_1.5 or ZrO₂-GdO_1.5, or environmental barrier coatings based on the corresponding Y/Gd silicates. The phase diagrams derived from these experiments are part of a broader effort to develop thermodynamic databases that can help guide the design of next-generation TBCs.     

ZrB2 – SiC ceramics: Residual stresses and mechanical properties

The stress-strain state of ZrB₂-SiC ultra-high-temperature ceramics, produced using commercial powders with different impurity levels, was investigated by X-ray diffraction. Upon analysis of ZrB₂ and SiC diffraction lines shift, the level of thermal stresses (strains) of the different phases was determined. An increase of internal stresses in ceramics with rising viscous-brittle transition temperatures, T_ve, was attributed to increased grain boundary strength. Ceramics, for which high T_ve and high level of internal stresses were estimated, exhibited high strength, up to 700 MPa at 1400 °C. A field of compressive thermal stresses in the matrix phase resulted to be necessary for achieving high strength at low-temperatures. On the contrary, the presence of low-melting impurities at the grain boundaries negatively impacted on the stress level in ZrB₂ boundaries in the high temperature regime.     

Factors controlling the mechanical behavior of alumina–magnesia–carbon refractories in air

This work analyzes the mechanical behavior of alumina-magnesia-carbon (AMC) refractories in air up to 1260 °C. AMC refractory bricks are used on sidewalls and bottoms working linings of steel-making ladles. In plant, AMC bricks are exposed to air atmosphere during the periods of time when the ladle is empty, such as preheating. Stress–strain relationships were determined in compression, and the following parameters were calculated from these curves: strength, apparent Young's modulus, fracture strain and yield strength. Young's modulus at room temperature was also determined by the impulse excitation technique. To identify the main determining factors, the tested specimens were analyzed by apparent porosity measurements, X-ray diffraction and scanning electron microscopy coupled with X-ray dispersive energy. Thermodynamic simulations of the AMC refractories were also performed using FactSage software, so as to understand the mineralogical changes that occur in the refractories as temperature increases.     

Wire-electrical discharge machinable alumina zirconia niobium carbide composites – Influence of NbC content

Alumina zirconia (ZTA) ceramics can be made electric discharge machinable by addition of a percolating network of an electrically conductive phase. In this study the influence of NbC content on the mechanical and electrical properties as well as the ED-machinability of ZTA-NbC ceramics containing 17 vol.% zirconia and 24–32 vol.% NbC were investigated. Samples were hot pressed from mixed and milled starting powders. Surface morphology and surface roughness of wire electrical discharge machined surfaces were studied by SEM and perthometry. Cutting speed was determined to benchmark the ED-machinability.Rising NbC contents progressively impede sinterability. Maximum strength, Young’s modulus and hardness were found at intermediate NbC contents. Conductivity evidently rises with NbC content, the cutting performance showed an adverse tendency. The surface quality of the materials was improved by increasing the content of conductive phase. Additional trimming operations can reduce the mean roughness of machined surfaces to 1 μm.