Formation of ZnAl2O4 in the Presence of Cl2

The formation of ZnAl₂O₄ spinel in diffusion couples of Al₂O₃ and ZnO was investigated between 1000° and 1390°C in air and in air containing 4.8 vol% Cl₂ by X-ray diffraction, electron probe microanalysis, and scanning electron microscopy. The rate of formation of a spinel layer obeyed a parabolic rate law and was accelerated remarkably by the presence of Cl₂. The interdiffusion coefficient, , and the activation energy, E, were calculated to be 10⁻⁸ to 10⁻⁹ cm²/s and 123 kcal/mol (514 kJ/mol) in air and 10⁻⁷ cm²/s and 31 kcal/mol (130 kJ/mol) in air containing 4.8 vol% Cl₂, respectively.     

Creep of Polycrystalline MgO-FeO-Fe2O3 Solid Solutions

Steady-state creep experiments were performed on hot-pressed polycrystalline MgO doped with Fe. Dead-load 4-point bend creep tests were conducted at stresses of 26 to 270 kg/cm², at temperatures of 1250° to 1450°C, in O₂ partial pressures of 1 to 10⁻⁹ atm, on specimens with grain sizes of 10 to 65 μm. Viscous steady-state creep was always observed when the grain size was stable. Experiments at variable P _O2's and temperatures were used to identify regimes of high (117 ± 10 kcal/mol) and low (81 ± 5 kcal/mol) activation energy. In the latter, creep rates were nearly independent of Fe dopant concentration and P _O2, whereas in the former creep rates were enhanced by increasing P _O2's and Fe dopant levels. The high- and low-activation-energy regimes were interpreted as diffusional creep controlled primarily by Mg lattice diffusion and O grain-boundary diffusion, respectively.     

Electrical Conduction in Single-Crystal and Polycrystalline Al2O3 at High Temperatures

The electrical conductivity and ion/electron transference numbers in Al₃O₃ were determined in a sample configuration designed to eliminate influences of surface and gas-phase conduction on the bulk behavior. With decreasing O₂ partial pressure over single-crystal Al₂O₃ at 1000° to 1650°C, the conductivity decreased, then remained constant, and finally increased when strongly reducing atmospheres were attained. The intermediate flat region became dominant at the lower temperatures. The emf measurements showed predominantly ionic conduction in the flat region; the electronic conduction state is exhibited in the branches of both ends. In pure O₂ (1 atm) the conductivity above 1400°C was σ≃3×10³ exp (–80 kcal/ RT ) Ω⁻¹ cm⁻¹, which corresponds to electronic conductivity. Below 1400°C, the activation energy was <57 kcal, corresponding to an extrinsic ionic condition. Polycrystalline samples of both undoped hot-pressed Al₂O₃ and MgO-doped Al₂O₃ showed significantly higher conductivity because of additional electronic conduction in the grain boundaries. The gas-phase conduction above 1200°C increased drastically with decreasing O₂ partial pressure (below 10⁻¹⁰ atm).     

Ion-Probe Measurement of Oxygen Self-Diffusion in Single-Crystal Al2O3

Anion self-diffusion coefficients normal to (1102) were obtained for single-crystal Al₂O₃ in a 1.3 × 10 ³ N/m² (10⁻⁵ torr) vacuum at 1585° to 1840°C. Tracer was supplied from an initial 650 to 1300 A Al₂¹⁸O₃ layer produced by the oxidation of vapor-deposited Al metal films in an ¹⁸O₂ atmosphere at 520°C. Concentration gradients extended over depths of 3000 to 5000 A and were measured by mass spectrometry of material sputtered from the samples with a beam of Ar⁺ ions. Crystals which had not been preannealed to remove surface damage displayed enhanced diffusion. Diffusion coefficients from preannealed crystals may be described by D₀ =6.4×10⁵cm²/s, with an activation energy of 188 ± 7 kcal/mol. The diffusion is interpreted as an extrinsic vacancy mechanism.     

Influence of Dopant Concentration on Creep Properties of Nd2O3-Doped Alumina

The microstructural features and tensile creep behavior of Al₂O₃ doped with Nd₂O₃ at levels ranging from 100 to 1000 ppm (Nd:Al atomic ratio) were systematically investigated. Compositional mapping, using both high-resolution scanning transmission electron microscopy and secondary ion mass spectroscopy revealed that, for all of the compositions studied, the Nd³⁺ ions were strongly segregated to the Al₂O₃ grain boundaries. Microstructural observations revealed that the solubility of Nd₂O₃ was between 100 and 350 ppm. Tensile creep tests were conducted over a range of temperatures (1200°–1350°C) and stresses (20–75 MPa). Both the stress and grain-size exponents were analyzed. In selected experiments, controlled grain-growth anneals were used to enable creep testing of samples of the same average grain size but different neodymium concentrations. Independent of dopant level, the neodymium additions decreased the creep rate by 2–3 orders of magnitude, compared with that of undoped Al₂O₃. The value of the apparent creep activation energy increased with increased dopant concentration and then saturated at dopant levels exceeding the solubility limit. Overall, the results of the present study were consistent with a creep-inhibition mechanism whereby oversized segregant ions reduce grain-boundary diffusivity by a site-blocking mechanism.     

Preparation of Porous Cr3C2 Grains with Cr2O3

Porous Cr₃C₂ grains (∼300 to 500 μm) with ∼10 wt% of Cr₂O₃ were prepared by heating a mixture of MgCr₂O₄ grains and graphite powder at 1450° to 1650°C for 2 h in an Al₂O₃ crucible covered by an Al₂O₃ lid with a hole in the center. The porous Cr₃C₂ grains exhibited a three-dimensional network skeleton structure. The mean open pore diameter and the specific surface area of the porous grains formed at 1600°C for 2 h were ∼3.5 (μm and ∼6.7 m²/g, respectively. The present work investigated the morphology and the formation conditions of the porous Cr₃C₂ grains, and this paper will discuss the formation mechanism of those grains in terms of chemical thermodynamics.     

Interdiffusion and Association Phenomena in the System NiO-Al2O3

The rate of formation of NiAl₂O₄ by reaction between single crystals of NiO and Al₂O₃ can be described by k = 1.1 × 10⁴ exp (−108,000 ± 5,000/ RT ) cm²/s. In NiO the behavior of D as a function of concentration supports the Lidiard theory of diffusion by impurity-vacancy pairs. A good fit of the theory to the experimental results was obtained by assuming that Al³⁺ ions diffuse as [Al_Ni· V_Ni]'pairs. The diffusion coefficient of pairs, D_p , obeys the equation 6.6 × 10⁻² exp (−54,000 ± 3,000/ RT ) cm²/s. The free energy of association for pairs was calculated to range from 6.5 kcal/mol at 1789°C to 9.0 kcal/mol at 1540°C. The interdiffusion coefficients in the spinel showed a constant small increase with increasing concentration of Al³⁺ dissolved in the spinel.     

Self-Diffusion of Er in Pure and HfO2-Doped Polycrystalline Er2O3

Using a tracer sectioning technique, the self-diffusion of Er in pure and HfO₂-doped polycrystalline Er₂O₃ was measured at 1614° to 1900°C. Up to ≊ 10 mol% HfO₂ dopant level, the Er self-diffusion coefficients followed a relation based on cation vacancies as the principal mobile defects present and available for cation diffusion. Above 10 mol% HfO₂, deviation from this relation occurred, apparently due to clustering of cation vacancies and oxygen interstitials around the dopant hafnium ions. The activation energy for the self-diffusion of Er in pure Er₂O₃ was 82.2 kcal/mol and increased with the HfO₂ dopant level present.     

Interdiffusion in the System MgO-MgAl2O4

Interdiffusion coefficients in single-crystal MgO were determined using an MgO-MgAl₂O₄ diffusion couple. For a concentration of 1 mol% Al₂O₃ in MgO, the interdiffusion coefficient can be expressed as D =2.0±0.2 exp (−76,000±3,000/ RT ) for the MgO-MgAl₂O₄ couple. This relation compares well with previous measurements in the MgO-Al₂O₃ system. The interdiffusion coefficients, which increased with the mol fraction of cation vacancies, were in the range of 10⁻⁸ to 10⁻¹⁰ cm²s⁻¹ for the concentrations and temperatures studied. Diffusion was enhanced below 1640°C if powdered MgAl₂O₄ was used. Self-diffusion coefficients for Al³⁺ ions in MgO were calculated; Al³⁺ diffuses faster than Cr³⁺ in MgO.     

Strength Degradation and Crack Propagation in Thermally Shocked Al2O3

Strength degradation and crack propagation in Al₂O₃ are shown to depend on the initial strength and grain size of the material. The strengths of single-crystal sapphire and polycrystalline Al₂O₃ specimens with grain sizes of 10, 34, and 40 μ m decreased discontinuously at the critical quenching temperature. In contrast, the strength of polycrystalline Al₂O₃ with a grain size of 85 μm decreased gradually as the quenching temperature increased. The strength retained after thermal shock and the extent of crack propagation decrease with increasing initial strength and grain size, respectively, in Al₂O₃.     

Crack-Healing Behavior of Al2O3 Toughened by SiC Whiskers

Al₂O₃ reinforced by SiC whiskers (Al₂O₃/SiC-W) was hot-pressed to investigate the crack-healing behavior. Semielliptical surface cracks of 100 μm in surface length were introduced using a Vickers indenter. The specimens containing precracks were crack-healed at temperatures between 1000° and 1300°C for 1 h in air, and their strengths were measured by three-point bending tests at room temperature and elevated temperatures between 400° and 1300°C. The results show that Al₂O₃/SiC-W possesses considerable crack-healing ability. The surface cracks with length of 2 c = 100 μm could be healed by crack-healing at 1200° or 1300°C for 1 h in air. Fracture toughness of the material was also determined. As expected, the SiC whiskers made their Al₂O₃ tougher.     

Creep of Polycrystalline MgO and MgO-Fe2O3 Solid Solutions at High Temperatures

Polycrystalline MgO and MgO-Fe₂O₃ solid solutions (0.10 to 8.08 wt% Fe₂O₃) were fabricated to almost theoretical density by vacuum hot-pressing. Specimens were creep-tested in air under four-point dead-load conditions between 1000° and 1400°C at stresses between 50 and 550 kg/cm². Steady-state creep was never achieved in the experiments, which sometimes lasted more than 50 h. The strain rate vs time ( t ) data were described by an equation of the form = c₁/(t+C₂)^p , which is consistent with the assumptions that creep occurs at least in part by a "viscous" mechanism and that grain growth occurs simultaneously. Doping MgO with Fe₂O₃ enhanced the viscous contributions to creep and inhibited the nonviscous ones. Creep rates in these specimens increased with increasing Fe₂O₃ additions. The occurrence of simultaneous grain growth during the high-temperature creep of magnesiowustite (i.e. MgO-Fe₂O₃ solid solutions) was used in establishing the strain rate vs grain size dependence. The results of this study are consistent with a transition between grain boundary and lattice diffusion mechanisms as the grain size increases (4 to 44 μan). The creep of polycrystalline MgO is a mixed process in that viscous and nonviscous (dislocation) contributions are present.     

Fabrication and Microstructure Characterization of Continuous Porous TiO2/Al2O3 Composite Membrane

Using a multipass extrusion process, continuous porous Al₂O₃ body (∼41% porosity) was produced and used as a substrate to fabricate continuous porous TiO₂/Al₂O₃ composite membrane. The diameter of the continuous pores of the porous Al₂O₃ body was about 150 μm. The TiO₂ nanopowders dip coated on the continuous pore-surface Al₂O₃ body existed as rutile and anatase phases after calcination at 520°C in air. However, after aging of the fabricated continuous porous TiO₂/Al₂O₃ composite membrane in 20% NaOH at 60°C for 24 h, a large number of TiO₂ fibers frequently observed on the pore surface. The diameter of the TiO₂ fibers was about 150 nm having a high specific surface area. However, after 48-h aging period, the diameter of the TiO₂ fibers increased, which was about 3 μm. Most of the TiO₂ fibers had polycrystalline structure having nanosized rutile and anatase crystals of about 20 nm.     

Thermal Expansion of 12CaO°7Al2O3

Literature data for the 12CaO°7Al₂O₃ phase show certain discrepancies in the structure, thermal stability, and mean linear thermal expansion obtained by different techniques. Phase-pure, cubic, polycrystallin I2CaO°7Al₂O₃ was synthesized by annealing a stoichiometric melt in air. Infrared spectrophotometry indicated stabilization by moisture. Differential thermal analysis and thermogravimetric analysis showed the cubic phase to be stable up to at least 1200° C. High-temperature X-ray diffraction analysis of a polycrystalline sample and dilatometric measurement of sintered pellets indicated a linear thermal expansion of 41 × 10^-7 to 43X10^-7/°C in the temperature range 200° to 800°C.     

Mechanical Properties of CoAl Materials with the Combined Additions of ZrO2(3Y) and Al2O3

Intermetallic CoAl powder has been prepared via self-propagating high-temperature synthesis (SHS). Dense CoAl materials (99.6% of theoretical) with the combined additions of ZrO₂(3Y) and Al₂O₃ have been fabricated via spark plasma sintering (SPS) for 10 min at 1300°C and 30 MPa. The microstructures are such that tetragonal ZrO₂ (0.3 μm) and Al₂O₃ (0.5 μm) particles are located at the grain boundaries of the CoAl (8.5 μm) matrix. Improved mechanical properties are obtained; especially the fracture toughness and the bending strength of the materials with ZrO₂(3Y)/Al₂O₃= 16/4 mol% are 3.87 MPa·m^1/2 and 1080 MPa, respectively, and high strength (>600 MPa) can be retained up to 1000°C.     

Thermal Grooving of MgO and Al2O3

High-purity polycrystalline MgO and Al₂O₃ were thermally grooved at 1500° and 1600°C. Accurate techniques were developed for following the growth of a single groove. For high-purity samples growth kinetics were essentially similar to those reported in the literature but were determined to be controlled by volume diffusion. Specimens for thermal grooving were prepared from Al₂O₃ to which transition metal oxides (Fe₂O₃₉, MnO, and TiO₂), which are known to accelerate shrinkage and sintering of Al₂O₃ powder compacts, had been added; the rate of groove growth was increased remarkably by minor amounts of these additives. Control of partial pressure indicated that Fe²⁺ and Ti⁴⁺ are the species active in promoting groove growth. Substantial evidence was found for volume diffusion as the mechanism controlling groove formation.     

High-Temperature Creep of Y2O3-Stabilized ZrO2

The compression creep behavior of Y₂O₃-stabilized ZrO₂ (YSZ) was studied at temperatures to 2000 ° C. The function of Y₂O₃ content and grain size was tested in specimens with various impurity concentrations and porosity distributions. For relatively fine-grained specimens, creep rates increased with the 1.5 power of the applied stress at low stresses and with the third power at high stresses. The results for coarse-grained specimens can, in general, be fit by the cube dependence. The 1.5 power can be reduced to a linear dependence by correcting for an apparent threshold stress, which decreases with increasing temperature. Creep activation energies for YSZ are 128 ± 10 kcal/mol, independent of Y₂O₃ content, impurity level, grain size, and porosity distribution. In addition, over a broad range of temperatures and stresses the absolute values of the steady-state creep rates are influenced only by grain size and O₂ partial pressure.     

Synthesis-Fabrication of an Al2O3-Tungsten Carbide Composite

A composite of 70 vol% Al₂O₃ and 30 vol% tungsten carbide was formed by hot-pressing. Simultaneously carbon reacts with an intimate mixture of WO₃ and Al₂O₃ to form a dense body. The composite approached theoretical density; a 1- to -10-μm carbide phase was uniformly dispersed in a 2-μm Al₂O₃ matrix. Maximum density and fine-grained microstructure were obtained when pressure was applied during heating from 1200° to 1600°C and temperature and pressure were then maintained for 20 min. At an initial ratio of 2.8 and 2.9 mol C/mol WO₃, the tungsten appeared as free W, WC, and W₂C. For C/WO₃=3.0 to 3.6, mixtures of W₂C and WC were present, whereas for C/WO₃>3.6, free C appeared with WC. The effects of the hot-pressing parameters are discussed.     

High-Temperature Elastic Properties of Polycrystalline MgO and Al2O3

Adiabatic bulk modulus, B_s , of polycrystalline MgO and Al₂O₃ was measured from 298° to 1473°K using the resonance technique. The Grüneisen constant, calculated from the measured bulk modulus, was constant over the whole temperature range (1.53 for MgO and 1.34 for Al₂O₃). Another important parameter,     , is constant at high temperature and is 3.1 for MgO and 3.6 for Al₂O₃. The Poisson's ratio increases linearly with temperature for MgO and Al₂O₃. To describe the change of bulk modulus with temperature a theoretical equation was verified by using the foregoing constants. A practical form of this theoretical equation is where B_s⁰ is the adiabatic bulk modulus at 0°K, δ is the quantity     , γ is the Grüneisen constant, H is the enthalpy. The experimental data are described very well by this equation, which is equivalent to the empirical equation suggested by Wachtman et al., B_s^T= B_s⁰ - CT exp (-T_c/T) , where C and T_c are empirical constants.     

Toughening and Strengthening of NiAl with Al2O3 by the Addition of ZrO2(3Y)

NiAl/10-mol%-ZrO₂(3Y) composites of almost full density have been fabricated via spark plasma sintering (SPS) for 10 min at 1300°C and 30 MPa. The former intermetallic compound, which contains a trace amount of Al₂O₃, has been prepared via self-propagating high-temperature synthesis. The composite microstructures are such that tetragonal ZrO₂ (∼0.2 μm) and Al₂O₃ (∼0.5 μm) particles are located at the grain boundaries of the NiAl (∼46 μm) matrix. Improved mechanical properties are obtained: the fracture toughness and bending strength are 8.8 MPa·m^1/2 and 1045 MPa, respectively, and high strength (>800 MPa) can be retained up to 800°C.