Processing of Silicon Carbide-Mullite-Alumina Nanocomposites

Nanocomposite materials in the form of nanometer-sized second-phase particles dispersed in a ceramic matrix have been shown to display enhanced mechanical properties. In spite of this potential, processing methodologies to produce these nanocomposites are not well established. In this paper, we describe a new method for processing SiC-mullite-Al₂O₃ nanocomposites by the reaction sintering of green compacts prepared by colloidal consolidation of a mixture of SiC and Al₂O₃ powders. In this method, the surface of the SiC particles was first oxidized to produce silicon oxide and to reduce the core of the SiC particles to nanometer size. Next, the surface silicon oxide was reacted with alumina to produce mullite. This process results in particles with two kinds of morphologies: nanometer-sized SiC particles that are distributed in the mullite phase and mullite whiskers in the SiC phase. Both particle types are immersed in an Al₂O₃ matrix.     

Dispersing Properties of Copolymers Able to Act as Binders

Macromolecules, containing both charged groups (COO⁻ and SO₃⁻), in order to ensure powder dispersion, and neutral groups (vinyl alcohol and ethyl hydroxyl acrylate), in order to obtain enough strength in the green parts, were synthesized to be used in the dry pressing process. The evaluation and the comparison of the capacity of these synthesized copolymers with disperse alumina particles in aqueous media are considered in this paper. Both COO⁻ and SO₃⁻ ionized groups are responsible for strong adsorption onto alumina surface and can promote sufficient electrostatic repulsive forces to achieve a good state of dispersion. The role of the copolymers in the stabilization of alumina suspensions was found to be greatly affected by the nature and by the fraction of groups in the macromolecular chains. A low concentration of copolymers (0.5 wt% on alumina basis) containing 35% of carboxylic groups and 65% of vinyl alcohol groups (PV35) or containing 55% of carboxylic groups and 45% of hydroxy ethyl acrylate groups (EH2A55) leads to stable alumina suspensions with a low viscosity similar to that obtained with a classical ammonium polymethacrylate (between 10 and 20 mPa·s for 27 vol% alumina suspensions). Copolymers containing sulfonate groups are less efficient.     

Dispersion of Alumina and Silicon Carbide Powders in Alumina Sol

Dispersion of Al₂O₃ and SiC particles in an alumina sol has been investigated through determination of particle-size distribution, zeta potential, and agglomerate morphology. The particle size of Al₂O₃ and SiC (as determined by the particle-size analyzer) is strongly affected by the presence of alumina sol in the solution. The average agglomerate size is decreased by at least 50%. The zeta potential of Al₂O₃ in 1 M alumina sol increases slightly, whereas that of SiC reverses its sign over a wide range of pH values. It is proposed that these effects are caused by AlO₄Al₁₂(OH)₂₄(H₂O)⁷⁺₁₂ sol clusters (1-2 nm in size) that are absorbed on the surface of the large (1-5 µm) ceramic particles. The electrostatic and steric effects of the cluster absorption help to control the dispersion and stabilize the suspension of ceramic particles in the alumina sol during wet processing. It is expected that the alumina-sol clusters can be used as an efficient, clean dispersant for single-phase and composite ceramic powders.     

Coagulation Method of Aqueous Concentrated Alumina Suspensions by Thermal Decomposition of Hydroxyaluminum Diacetate

Consolidation of aqueous concentrated suspensions was used to shape alumina green bodies because it enabled us to obtain complex-shape components with accurate sizes. A high state of alumina particle dispersion was achieved by using (HO)₂C₆H₂(SO₃Na)₂ (Tiron), which allowed us to obtain stable alumina suspensions at pH 9 with a powder concentration higher than 60 vol%. The addition to the suspension of hydroxyaluminum diacetate, (CH₃CO₂)₂AlOH, which decomposed as the temperature increased, permitted us to coagulate an alumina suspension dispersed with Tiron efficiently. Adsorption measurements, electrokinetic mobility, and the rheological behavior of the suspensions provided useful methods to characterize each processing stage. Dense green bodies with sufficient cohesion could be demolded and dried, demonstrating that the dispersant and the flocculant agent chosen permit one to optimize the direct coagulation casting processing of alumina components.     

AI2O3 Coatings as Diffusion Barriers Deposited from Particulate-Containing Sol-Gel Solutions

A procedure for the formation of A1₂O₃ coatings as diffusion barriers between ductile reinforcements (e.g., Nb and Ta) and intermetallic matrices (e.g., MoSi₂ and NiAl) is described. The coating technique involved sol-gel processing of alumina -forming sols with the addition of submicrometer-sized A1₂O₃ particles. Cracking in the coatings, a typical shortcoming of alumina sol-gel coating, was overcome by the addition of the fine particles into the sols. The surface charge of the A1₂O₃ particles was adjusted to be the same as the AIO(OH) colloids in the sols and electrophoresis was used to codeposit A1₂O₃ and AIO(OH) onto the surfaces of the reinforcements. The alumina gel derived from the sols acted as binder for the alumina particles, while the particles reduced the shrinkage of the sol-gel coatings and promoted the formation of dense coatings. The thickness of the coatings could be easily controlled without cracking and the effectiveness of the coatings as diffusion barriers was improved substantially.     

Effect of TiO2 on Initial Sintering of Al2O3

Alpha alumina with additions of TiO₂ sintered more rapidly than "pure" alumina. The rate of initial sintering increased approximately exponentially with titania concentration up to a percentage beyond which the rate of sintering remained approximately constant or decreased slightly with additional titania. The concentration which produces the maximum rate of sintering is thought to be the solubility limit of TiO₂ in Al₂O₃. For alumina particles larger than about 2 μm, the kinetic process was mainly grain-boundary diffusion. With smaller particles, volume diffusion increased. The "solubility limit" increased with decreasing particle size, indicating an excess surface concentration of TiO₂. The data may be interpreted in terms of a region of enhanced diffusion at the grain boundary that increases with TiO₂ concentration. With small alumina particles, this region is large enough to become a significant portion of the volume of the particle, and the small particles appear to sinter by volume diffusion kinetics, but the diffusion coefficient corresponds to an enhanced diffusion coefficient.     

Slow Crack Growth Behavior in Transformation-Toughened Al2O3-ZrO2(Y2O3) Ceramics

Significant increases in the critical fracture toughness (K _IC ) over that of alumina are obtained by the stress-induced phase transformation in partially stabilized ZrO₂ particles which are dispersed in alumina. More importantly, improved slow crack growth resistance is observed in the alumina ceramics containing partially stabilized ZrO₂ particles when the stress-induced phase transformation occurs. Thus, increasing the contribution of the ZrO₂ phase transformation by tailoring the Y₂O₃ stabilizer content not only increases the critical fracture toughness (K_IC) but also the K _Ia to initiate slow crack growth. For example, crack velocities ( v )≥10^–9 m/s are obtained only at K _Ia≥5 MPa.m^1/2 in transformation-toughened ( K _IC=8.5 MPa.m^1/2) composites vs K _Ia≥2.7 MPa.m^1/2 for comparable velocities in composites where the transformation does not occur ( K _IC=4.5 MPa.m^1/2). This behavior is a result of crack-tip shielding by the dissipation of strain energy in the transformation zone surrounding the crack. The stress corrosion parameter n is lower and A greater in these fine-grained composite materials than in fine-grained aluminas. This is a result of the residual tensile stresses associated with larger (≥1 μm) monoclinic ZrO₂ particles which reside along the intergranular crack path.     

Reformulation of an Aqueous Alumina Slip Based on Modification of Particle-Size Distribution and Particle Packing

Six alumina casting slips with particle-size distributions varying from 44 to 0.1 μm were examined. Particle packing was calculated using the approach of Andreasen. Viscosity, green density, and pore-size distribution were measured. It was found that contouring the intermediate size distribution for particles finer than 15 μm provided the most desirable viscosity for slips composed of wide size distributions. For slips containing 50 vol% solids, the lowest viscosity obtained was 196 × 10⁻³ N · s/m² (with a two-component size distribution), and a green density of 2.52 g/cm³ (65% of theoretical) was achieved with a ternary system. These casts had bimodal pore-size distributions centered around approximately 1 and 0.1μm.     

Reactive Laser Ablation Synthesis of Nanosize Alumina Powder

An aluminum (Al) target was laser ablated in an oxygen (O₂) atmosphere, producing nanosize alumina (Al₂O₃) powder. The powder surface area decreased (and the particle size increased) with both increasing oxygen pressure and laser fluence. All powders produced had surface areas between 135 and 250 m²/g, corresponding to primary particle sizes ranging from 7 to 3 nm in radius. Phase evolution with temperature was studied via X-ray diffraction. These powders showed a direct transformation from γ- to α-alumina at approximately 1200°C, bypassing other transition alumina phases, while still maintaining small particle size ( 30 nm). Despite the nanosize particles, green densities equal to 54% of the skeletal density (i.e., true density of the solid phase) were obtained by uniaxial pressing at 40 MPa.     

Ultrafine Alumina Particles Prepared by Mechanochemical/Thermal Processing

Ultrafine alumina particles have been prepared by the mechanical milling and subsequent heat treatment of a mixture of AICI3 and CaO. Heat treatment of the as-milled powder at temperatures above 350°C and washing with water resulted in γ-Al₂O₃ particles 10–20 nm in size. Single phase α-Al₂O₃ was formed in the sample after heat treatment at 1250°C. This study demonstrates a novel process for synthesizing nanoscale alumina particles.     

Tribological Behavior of SiC-Whisker/Al2O3 Composites against Carburized 8620 Steel in Lubricated Sliding

Mineral oil lubricated sliding tests of Sic-whisker (SiC_w,)/A1₂0₃ composites and monolithic alumina against carburized 8620 steel were conducted on a cylinder-on-cylinder machine. The wear rate of the composites was one or two orders of magnitude less than that of pure alumina. Hot-pressed 25 wt% SiC_w,/A1₂0₃ composite had a lower wear rate than sintered and HIPed 7.5 wt% SiC/Al₂O₃ composite under the same conditions. The weight loss of the steel mating ring against the 25 wt% SiC_w, composite was a factor of four lower than against the 7.5 wt% SiC_w, composite, but the former was a factor of 50 to 60 less than that against pure alumina. The composites showed lower friction coefficients than alumina during the run-in stage. The friction coefficients decreased with initial wear. The steady-state friction coefficient decreased with increasing load up to 500 N for hot-pressed 25 wt% SiC,/Al₂0₃ composite. Further, SEM observation showed much less microfracture in composites than in alumina. EDAX analysis revealed less Fe transfer from the steel ring to the composites than to pure alumina. Wear by microfracture and by adhesion in composites was suggested to be suppressed by SIC whiskers. This in turn reduced wear of the steel because of the generation of fewer hard particles.     

Hydrothermal Synthesis of Petal-Like Alumina Flakes

Petal-like alumina flakes were prepared by hydrothermal reaction at 170°C for 6 h with aqua-based precursor materials. The gel particles were calcined at 550°–1200°C. The gel and calcined particles were characterized by differential thermal analysis (DTA), thermogravimetry (TG), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), multipoint Brunauer–Emmett–Teller (BET) surface area, and field emission scanning electron microscopy (FESEM). Crystallization of alumina was confirmed by DTA and XRD studies. XRD results showed that boehmite particles were formed in as-prepared sample while γ-alumina (γ-Al₂O₃) persisted up to 800°C followed by the appearance of θ-alumina (θ-Al₂O₃) at 1000°–1200°C. The characteristics Al–O vibrations in alumina polymorphs were examined by FTIR study. FESEM confirmed the formation of petal-like alumina flakes with the assembly of alumina nanorods.     

Biaxial Strength of a ZrO2/(Ni+Al2O3) Nanocomposite

Previous studies demonstrated that the strength of zirconia (ZrO₂) could be enhanced or reduced by respectively adding micrometer-sized alumina (Al₂O₃) or nickel (Ni) particles. In the present study, 5 vol% micrometer-sized Al₂O₃ particles and 1 vol% nanometer-sized Ni particles are incorporated into the ZrO₂ matrix, which is subsequently densified by pressureless sintering. The biaxial strength of the ZrO₂/(Ni+Al₂O₃) nanocomposite is nearly double that of the monolithic ZrO₂. The increase in strength correlated with a reduction in the critical flaw size and not with any change in toughness, which may be a result of grain boundary strengthening.     

Erosion Damage and Strength Degradation of Zirconia-Toughened Alumina

The erosion wear and posterosion strength properties of Al₂O₃ containing 10 vol% ZrO₂ were determined as a function of the kinetic energy of the impacting sharp particles. Samples were prepared with three different surface treatments to obtain different amounts of tetragonal zirconia on the surface. With all three surface treatments a transformation from tetragonal to monoclinic phase due to the impacting particles was observed. The erosive wear was independent of the initial amount of tetragonal phase at the surface and was not statistically different from that found for commercial alumina. The posterosion strength was relatively insensitive to increasing kineticenergy of the eroding particles, indicating a rising fracture resistance behavior for this zirconia-toughened alumina.     

The Effect of Yttrium on Oxygen Grain-Boundary Transport in Polycrystalline Alumina Measured Using Ni Marker Particles

The grain-boundary transport of oxygen in polycrystalline α-Al₂O₃ (undoped and 500 ppm Y³⁺-doped) was studied in the temperature regime of 1100°–1500°C by monitoring the oxidation of a fine, uniform dispersion of Ni marker particles (0.5 vol%). The annealing treatments were carried out in a high-purity O₂ atmosphere (>99.5%). The Ni particles, which are visibly oxidized to nickel aluminate spinel, were used to determine the depth of oxygen penetration. The thickness of the reaction zone was measured as a function of heat-treatment time and temperature, and a comparison of the oxidation rate constants and activation energies for undoped and Y³⁺-doped alumina was made. The results indicate that the presence of Y³⁺ slows oxygen grain-boundary transport in alumina by a variable factor of from 15 to 3 in the temperature regime of 1100°–1500°C. The values of the activation energy for undoped and Y³⁺-doped alumina were determined to be 430±40 and 497±8 kJ/mol, respectively.     

Alumina/Zirconia Micro/Nanocomposites: A New Material for Biomedical Applications With Superior Sliding Wear Resistance

In the present investigation, the sliding wear behavior is described for Al₂O₃/ZrO₂ micro/nanocomposites and monolithic alumina of similar grain size under defined conditions of a constant sliding speed and different loads (20–150 N). Nano ZrO₂ particles (1.7 vol%) were observed uniformly distributing throughout the composites, and most of them were located within the matrix alumina grains. The wear rate of the alumina and the micro/nanocomposites increased as the contact load increased and a clear transition in friction and wear behavior was observed in both materials. However, the nanocomposite wear resistance at low contact loads was one order of magnitude higher than that of the alumina. In the severe regime, no difference was observed among the materials. The low wear rate (10⁻⁷ mm³·(N·m)⁻¹) along with low pullout indicates higher wear resistance of micro/nanocomposites in the mild regime compared with monolithic alumina. Based on the morphological observation of worn surfaces by scanning electron microscope and on residual stress analysis performed by neutron diffraction, some wear mechanisms of Al₂O₃–ZrO₂ micro/nanocomposites are proposed. The high wear resistance of the nanocomposites is discussed in terms of fracture resistance properties and residual stress. Improvements in mechanical and tribological properties of these composites make them promising candidates for biomedical applications.     

Behavior of Chromium in the System MgA12O4– A12O3

Single crystals of chromium-doped magnesium aluminate spinels with varying amounts of excess alumina have been grown by the flame fusion process. Presumably these crystals contain stoichiometrically significant amounts of defects. When these chromium-doped spinels are annealed at temperatures below their melting point, the spinel structure cannot tolerate such a high concentration of defects and at least some of the excess alumina is exsolved. The chromium ion in magnesium aluminate spinel is pink, whereas in magnesium aluminate spinel containing excess alumina it is green. When exsolution of the alumina occurs during annealing, the aggregate changes to pink. The behavior of the chromium ion is monitored by observing the significant changes in the optical absorption as well as the emission or fluorescence spectra for both single crystals and polycrystalline materials in the system [MgA1₂O₄– A1₂O₃] :Cr.     

Mechanical Properties of Coagulated Wet Particle Networks with Alkali-Swellable Thickeners

Alkali-swellable thickeners (ASTs) such as Acusol 820 and Acusol 830, as well as poly(acrylic acid) homopolymers of various molar mass, have been used as additives in aqueous electrostatically stabilized alumina suspensions. These suspensions have been destabilized by internal enzyme-catalyzed reactions (a direct coagulation casting process) to form viscoelastic solids. The ASTs increase the strength and modulus of the wet green bodies on coagulation. The effect of their molecular architecture on the mechanical properties of wet particulate networks has been studied. At low pH (pH 4.5), ASTs are small insoluble polymer particles that have only minor influence on the low viscosity of the high-solids-loading suspensions. After shifting the pH toward the isoelectric point of α-Al₂O₃, the suspension coagulates and the AST polymer particles swell, thereby increasing the compressive strength and modulus of the alumina-particulate wet green bodies. The presence of small amounts of ASTs (0.4 wt%, based on the solids loading) results in a 10-fold increase in the strength of the wet green bodies. The compressive strength of the wet green bodies that contain ASTs correlates with the size of the expanded AST molecules at pH 9. A possible explanation is that swelling of the AST particles locally decreases the interparticle distance, which leads to increased van der Waals forces between the ceramic particles.     

Melt-Infiltration Processing and Fracture Toughness of Alumina-Glass Dental Composites

Alumina-glass composites were prepared by a melt-infiltration process that is similar to a fabrication method for dental crowns and bridges. Cylindrical alumina samples with green densities ranging from 62% to 72% of theoretical were formed by slip casting followed by sintering at 1100°C for 2 h. A borosilicate glass was infiltrated at 1200°C, resulting in a composite microstructure consisting of fused alumina particles and glass-filled pores. Fracture toughness of the composites, measured by a chevron-notch method with a short rod sample, was ∼3.8 MPa·m^1/2 and was relatively insensitive to the volume fraction of alumina in the range of 0.62 to 0.72.     

Tin(IV) Oxide Coating of Aluminum Borate Whiskers and Alumina Particles by Chemical Vapor Deposition

Aluminum borate whiskers of 0.5–1.0 μ diameter and alumina particles of 10–20 μ diameter were coated with SnO₂ by the reaction of SnCl₄–H₂O–N₂ gas mixtures in a rotary kiln reactor. Prior to coating, the whiskers were slightly etched to ensure adhesion between the SnO₂ layer and the whisker surface. The whiskers were coated at 100°C for 1 h, and then at 300°C for 2 h. This procedure was effective for covering the entire whisker surface with a uniform SnO₂ layer. Precoating was not necessary for the alumina particles. A compressed disk of the coated whiskers had an electrical conductivity of 30–40 S/m.