Alumina Sol-Assisted Sintering of SiC—Al2O3 Composites

The composite sol—gel (CSG) technology has been utilized to process SiC—Al₂O₃ ceramic/ceramic particulate reinforced composites with a high content of SiC (up to 50 vol%). Alumina sol, resulting from hydrolysis of aluminum isopropoxide, has been utilized as a dispersant and sintering additive. Microstructures of the composites (investigated using TEM) show the sol-originating phase present at grain boundaries, in particular at triple junctions, irrespective of the type of grain (i.e., SiC or Al₂O₃). It is hypothesized that the alumina film originating from the alumina sol reacts with SiO₂ film on the surface of SiC grains to form mullite or alumina-rich mullite-glass mixed phase. Effectively, SiC particles interconnect through this phase, facilitating formation of a dense body even at very high SiC content. Comparative sinterability studies were performed on similar SiC—Al₂O₃ compositions free of alumina sol. It appears that in these systems the large fraction of directly contacting SiC—SiC grains prevents full densification of the composite. The microhardness of SiC—Al₂O₃ sol—gel composites has been measured as a function of the content of SiC and sintering temperature. The highest microhardness of 22.9 GPa has been obtained for the composition 50 vol% SiC—50 vol% Al₂O₃, sintered at 1850°C.     

Alumina/Silicon Carbide Nanocomposites by Hybrid Polymer/Powder Processing: Microstructures and Mechanical Properties

Nanocomposites with fine, coarse, and bimodal silicon carbide (SiC) particle-size distributions were hot pressed and examined by transmission electron microscopy, scanning electron microscopy, and optical microscopy, as well as by four-point-bend and indentation tests. The finer SiC nanophase was introduced homogeneously by coating a silicon-containing polymer onto the alumina (Al₂O₃) powder, followed by a pyrolysis procedure; for the coarser SiC, nanophase conventional powder processing was used. Powder- and polymer-processed nanocomposites both had their maximum strengths at 5 vol% of SiC. High-strength nanocomposites that contained a higher volume fraction of SiC could be fabricated when the two methods were combined in a hybrid processing route. The SiC phase in the resulting hybrid materials originated from both the polymer and the SiC powder. The mechanical properties of these materials could be correlated with the fabrication route. Processing-flaw populations and calculated Griffith-flaw sizes were not only smaller, but they were also significantly different in the nanocomposites, in comparison to those in Al₂O₃ ceramics; this may explain the strength increase in Al₂O₃/SiC nanocomposite materials.     

Strengthening of Porous Alumina by Pulse Electric Current Sintering and Nanocomposite Processing

Porous Al₂O₃ and SiC–dispersed-Al₂O₃ (Al₂O₃/SiC) nanocomposites with improved mechanical properties were fabricated using pulse electric current sintering (PECS). Microstructures with fine grains and enhanced neck growth, as well as high fracture strength, could be achieved via PECS of Al₂O₃. The incorporation of fine SiC particles into an Al₂O₃ matrix significantly increased the fracture strength of porous Al₂O₃. Based on microstructural observations, it was revealed that the refinement of Al₂O₃ grains and neck growth occurred by PECS and nanocomposite processing.     

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.     

Growth of Tabular α-Al2O3 Grains on Porous Alumina Substrate

Gradient, porous alumina ceramics were prepared with the characteristics of microsized tabular α-Al₂O₃ grains grown on a surface with a fine interlocking feature. The samples were formed by spin-coating diphasic aluminosilicate sol on porous alumina substrates. The sol consisted of nano-sized pseudo-boehmite (AlOOH) and hydrolyzed tetraethyl orthosilicate [Si(OC₂H₅)₄]. After drying and sintering at 1150°–1450°C, the crystallographic and chemical properties of the porous structures were investigated by analytical electron microscopy. The results show that the formation of tabular α-Al₂O₃ grains is controlled by the dissolution of fine Al₂O₃ in the diphasic material at the interface. The nucleation and growth of tabular α-Al₂O₃ grains proceeds heterogeneously at the Al₂O₃/glass interface by ripening nano-sized Al₂O₃ particles.     

THIS ARTICLE HAS BEEN RETRACTEDEffect of Silica Sol on the Properties of Alumina-Based Duplex Ceramic Cores

A series of alumina-based ceramic cores sintered at 1300°C, 1400°C, and 1500°C for 5 h were prepared, and the phases and microstructures were characterized by X-ray diffraction and scanning electron microscopy. The effect of colloidal silica sols on the properties of ceramic core was discussed. The properties of these materials were determined. The results indicated that the microstructure of the core is characterized by the presence of substantially unreacted Al₂O₃ particles having a polycrystalline composition consisting essentially of in situ synthesized 3Al₂O₃·2SiO₂ on the surface of the Al₂O₃ particles. The colloidal silica sol contents do not have an appreciable effect on the densification and shrinkage of the alumina ceramic core. The ceramic cores of 5 wt% colloidal silica sol contents sintered at 1500°C for 5 h showed the smallest creep deformation in the present research.     

Polishing Behavior and Surface Quality of Alumina and Alumina/Silicon Carbide Nanocomposites

The response of Al₂O₃ and Al₂O₃/SiC nanocomposites to lapping and polishing after initial grinding was investigated in terms of changes in surface quality with time for various grit sizes. The surface quality was quantified by surface roughness ( R _a ) and by the relative areas of smooth polished surfaces as opposed to rough as-ground areas. Polishing behavior of the materials was discussed in terms of SiC content and grain size. It was concluded that nanocomposites are more resistant to surface damage than Al₂O₃, and this behavior does not depend on the amount of SiC in the range 1–5 vol%. SiC addition ≥1 vol% is enough to produce a noticeable improvement in surface quality during lapping and polishing.     

Microstructure of Alumina Composites Containing Niobium and Niobium Aluminides

The microstructures of niobium-based alumina composites prepared by pressureless sintering of compacts of attrition milled Al₂O₃, Nb, and Al powder mixtures were studied. The addition of a small amount of Al is assumed to assist in rapid sintering. X-ray diffraction analyses show that Al₂O₃, Nb, NbO, and the intermetallics AlNb₂ and AlNb₃ are present in the composites. Electron microscopy studies confirm the existence of these phases and reveal dense, fine-grained (≤500 nm) composites. Al₂O₃ and Nb grains form the matrix. NbO occurs as grains and additionally as small particles within Al₂O₃ grains and at Al₂O₃/Al₂O₃ grain boundaries. The intermetallic AlNb₂ and AlNb₃ phases do not exceed 300 nm in size if they occur at grain boundaries, and possess even smaller dimensions when occluded within Al₂O₃ grains or located at Al₂O₃ triple junctions. While the niobium intermetallics are expected to form during the heating cycle before reaching the sintering temperature, the NbO is assumed to form during the cooling cycle due to precipitation of oxygen dissolved in the niobium.     

Intragranular Particle Residual Stress Strengthening of Al2O3–SiC Nanocomposites

Al₂O₃/SiC ceramic nanocomposites were fabricated from nanocrystalline Al₂O₃ (10 nm in diameter) and SiC (15 nm in diameter) powders, and a theoretical model of intragranular particle residual stress strengthening was investigated. The SiC nanoparticles in the Al₂O₃ grains create a normal compressive stress at the grain boundaries and a tangential tensile stress in the Al₂O₃ grains, resulting in the "strengthening" of the grain boundaries and "weakening" of the grains. The model gives a good explanation of the experimental results of the authors and others which are difficult to be explained by the existing strengthening models, i.e. the maximum strength is normally achieved at about 5 vol% of SiC particles in the Al₂O₃–SiC ceramic nanocomposites. According to the model, there exists an optimum amount of SiC for strengthening, below which the grain boundaries are not fully "strengthened" and the fracture is mainly intergranular, above which the grains are "weakened" too much and the fracture is mainly transgranular, and at which the fracture is a mixture of intergranular and transgranular.     

Performance of Alumina Membranes from New Nanosynthesis in Ultrafiltration and Nanofiltration

Starting from simple inorganic or organic raw materials in aqueous or alcoholic solvents, a synthesis process has been developed for (i) the preparation of sol–gel-derived alumina (Al₂O₃) membranes or (ii) the manufacture of membranes by the deposition of precalcined nanocorundum (α-Al₂O₃) powders. Because of the equiaxed shape of the synthesized constituent particles, the permeability of the membranes is a factor of 3–5 greater than in previous products. In contrast to the case for known porous transitional Al₂O₃, the equiaxed shape of the particles in this case is enabled for any of the transitional phases and for the final corundum by a synthesis method that avoids the intermediate crystallization of platelet-shaped boehmite. By this means, nanoporous Al₂O₃ components with pore sizes of ∼1 nm or up to 5 nm can be derived preferentially by sol–gel processing, whereas both sol–gel and nanopowder techniques are used to manufacture ultrafiltration α-Al₂O₃ membranes with a high chemical and thermal stability and with average pore sizes of 10–60 nm. Compared with the sol–gel approach, powder processing decreases the drying and sintering shrinkage and, thus, the frequency and size of flaws, improving the cutoff characteristics of the membranes. For catalytic applications, the porous ceramic microstructures also can be applied on larger metal substrates.     

Effect of Annealing Environment on the Crack Healing and Mechanical Behavior of Silicon Carbide-Reinforced Alumina Nanocomposites

The crack healing and strength behavior of an alumina-silicon carbide (Al₂O₃-SiC) nanocomposite (Al₂O₃+ 5 vol% 0.2 μm SiC particles) has been studied, as a function of the crack size and the annealing environment. Results show that annealing treatments can significantly increase the indentation strength. The annealing atmosphere has a profound influence on the extent of crack healing and the degree of strength recovery. Annealing in argon results in a strength increase of 50%, whereas annealing in air yields a three-fold improvement in the indentation strength. Scanning electron microscopic observation has shown that healing of indentation cracks occurs in both environments, with the greater degree of healing occurring during annealing in air. Implications of the findings to the strengthening mechanism in Al₂O₃ (SiC) nanocomposites will be discussed.     

Sliding Wear of Alumina/Silicon Carbide Nanocomposites

The wear resistance of four Al₂O₃/SiC nanocomposites that contained SiC particles of varying average size (40, 200, and 800 nm) was studied under dry sliding conditions and compared with the results obtained in unreinforced alumina. The wear rate of the alumina and the nanocomposites of equivalent grain size increased as the contact load increased; however, the nanocomposite wear resistance at high contact loads was better than that of the alumina by a factor of 3–5. The wear resistance of the nanocomposites of submicrometer grain size was fairly independent of the contact load, and their wear resistance at high contact loads was up to two orders of magnitude better than that of the alumina. The mechanisms responsible for these behaviors were discussed in terms of the microscopic wear mechanisms that were observed on the worn surfaces.     

Advanced Alumina Composites Reinforced with Titanium-Based Alloys

New (inter)metallic-ceramic composites for high-temperature structural and functional applications are prepared via high-energy ball milling. During compaction by pressureless sintering, dense Al₂O₃/Ti-based alloy composites are formed that consist of inter-connected networks of the ceramic and the (inter)metallic phases. Ti-Al-V/Al₂O₃ and Ti-Al-Nb/Al₂O₃ composites show enhanced damage tolerance over monolithic Al₂O₃, i.e ., fracture toughnesses up to 5.6 MPa·m^0.5 and bending strengths up to 527 MPa. The resistance against abrasive wear is almost doubled with respect to monolithic Al₂O₃ ceramic. Electrical resistivity scales with the ceramic volume fraction and ranges between 0.3 mΩ·cm and 55.1 mΩ·cm, with only a weak temperature dependence ≤700°C.     

Preparation and Analysis of a Silicon Carbide Composite Membrane

Silicon carbide (SiC) porous substrates, containing alumina (Al₂O₃) dopant levels of 3, 5, and 8 wt%, are prepared by slip casting and sintering in the temperature range of 1450°–1800°C. The linear shrinkage, bulk density, and pore size of the sintered substrate increase as the sintering temperature and the amount of dopant increase. A large amount of β-phase SiC is transformed to α-phase SiC if the dopant concentration is 5 or 8 wt%. The flexural strength of the substrate doped with 8 wt% Al₂O₃ is higher than that of the substrate doped with 3 wt% Al₂O₃; however, the Weibull modulus of the former is lower. SiC composite membranes of improved selectivity and strength are fabricated by coating the porous substrate with layers of lower Al₂O₃ contents at lower sintering temperatures.     

Alumina/Epoxy Interpenetrating Phase Composite Coatings: I, Processing and Microstructural Development

Interpenetrating phase composite (IPC) coatings consisting of continuously connected Al₂O₃ and epoxy phases were fabricated. The ceramic phase was prepared by depositing an aqueous dispersion of Al₂O₃ (0.3 μm) containing orthophosphoric acid, H₃PO₄, (1–9.6 wt%, solid basis) and heating to create phosphate bonds between particles. The resulting ceramic coating was porous, which allowed the infiltration and curing of a second-phase epoxy resin. The effect of dispersion composition and thermal processing conditions on the phosphate bonding and ceramic microstructure was investigated. Reaction between Al₂O₃ and H₃PO₄ generated an aluminum phosphate layer on particle surfaces and between particles; this bonding phase was initially amorphous, but partially crystallized upon heating to 500°C. Flexural modulus measurements verified the formation of bonds between particles. The coating porosity (and hence epoxy content in the final IPC coating) decreased from ∼50% to 30% with increased H₃PO₄ loading. The addition of aluminum chloride, AlCl₃, enhanced bonding at low temperatures but did not change the porosity. Diffuse reflectance FTIR showed that a combination of UV and thermal curing steps was necessary for complete curing of the infiltrated epoxy phase. Al₂O₃/epoxy IPC coatings prepared by this method can range in thickness from 1 to 100 μm and have potential applications in wear resistance.     

"Alumina" Surface Modification of Silicon Nitride for Colloidal Processing

Two different methods are used to coat silicon nitride particles with an alumina precursor to make Si₃N₄ behave like Al₂O₃ in aqueous slurries. The first method involves the precipitation of an aluminum hydroxycarbonate from dissolved Al(NO₃)₃ during the decomposition of urea. In the second method, dry silicon nitride powder is reacted with aluminum tri- sec -butoxide in hexane at room temperature. Both methods produce a coated powder in which the electrophoretic and rheological properties of aqueous slurries mimic those of alumina. When salt is added to slurries consisting of coated Si₃N₄ powder, all rheological evidence suggests the presence of a short-range repulsive potential that produces a weakly attractive particle network similar to that previously reported for Al₂O₃ powder. Although electrophoretic and rheological data showed that the coated powder behaved like Al₂O₃, consolidation data indicated that slurries of coated powder with added salt did not pack to high density. In addition, these bodies were not plastic as found for bodies consolidated from dispersed and salt-added Al₂O₃ slurries.     

Low-Temperature Processing and Mechanical Properties of Zirconia and Zirconia–Alumina Nanoceramics

The 1.5- to 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ (Y-TZP) and Al₂O₃/Y-TZP nanocomposite ceramics with 1 to 5 wt% of alumina were produced by a colloidal technique and low-temperature sintering. The influence of the ceramic processing conditions, resulting density, microstructure, and the alumina content on the hardness and toughness were determined. The densification of the zirconia (Y-TZP) ceramic at low temperatures was possible only when a highly uniform packing of the nanoaggregates was achieved in the green compacts. The bulk nanostructured 3-mol%-yttria-stabilized zirconia ceramic with an average grain size of 112 nm was shown to reach a hardness of 12.2 GPa and a fracture toughness of 9.3 MPa·m^1/2. The addition of alumina allowed the sintering process to be intensified. A nanograined bulk alumina/zirconia composite ceramic with an average grain size of 94 nm was obtained, and the hardness increased to 16.2 GPa. Nanograined tetragonal zirconia ceramics with a reduced yttria-stabilizer content were shown to reach fracture toughnesses between 12.6–14.8 MPa·m^1/2 (2Y-TZP) and 11.9–13.9 MPa·m^1/2 (1.5Y-TZP).     

Equilibrium Amorphous Silicon–Calcium–Oxygen Films at Interfaces in Copper–Alumina Composites Prepared by Melt Infiltration

The microstructure of copper–alumina (Cu-Al₂O₃) composites that have been prepared via the melt infiltration of liquid copper into porous alumina preforms was studied in detail, using various transmission electron microscopy (TEM) techniques. Two different samples—with open pore diameters of 0.2 and 0.8 μm—were investigated. For both specimens, a single crystalline copper network that extended throughout the open porosity of the alumina preform was observed. An amorphous glass phase that contained silicon and calcium was observed at the Al₂O₃/Cu/Al₂O₃ triple junctions. The diameters of these amorphous pockets, which were strongly faceted along the Al₂O₃ grains, were up to 20 and 100 nm for the initial pore sizes of 0.2 and 0.8 μm, respectively. A glass phase that contained silicon and calcium also was present at the Cu/Al₂O₃ interfaces, whereas the Al₂O₃ boundaries remained dry. Detailed high-resolution transmission electron microscopy investigations have shown that the interfacial glass phase at the Cu/Al₂O₃ interfaces exhibited a uniform equilibrium film thickness along the interface region. However, the interfacial film thickness was dependent on the orientation of the Al₂O₃ grain, and its value varied from 0.4 nm for Al₂O₃ rhombohedral-plane termination ((1¯012)) up to 1 nm for Al₂O₃ basal-plane termination ((0001)).     

Creep Deformation in an Alumina–Silicon Carbide Composite Produced via a Directed Metal Oxidation Process

Flexural creep studies were conducted in a commercially available alumina matrix composite reinforced with SiC particulates (SiC_p) and aluminum metal at temperatures from 1200° to 1300°C under selected stress levels in air. The alumina composite (5 to 10 μm alumina grain size) containing 48 vol% SiC particulates and 13 vol% aluminum alloy was fabricated via a directed metal oxidation process (DIMOX(tm))† and had an external 15 μm oxide coating. Creep results indicated that the DIMOX Al₂O₃–SiC_p composite exhibited creep rates that were comparable to alumina composites reinforced with 10 vol% (8 (μm grain size) and 50 vol% (1.5 μm grain size) SiC whiskers under the employed test conditions. The DIMOX Al₂O₃–SiC_p composite exhibited a stress exponent of 2 at 1200°C and a higher exponent value (2.6) at ≥ 1260°C, which is associated with the enhanced creep cavitation. The creep mechanism in the DIMOX alumina composite was attributed to grain boundary sliding accommodated by diffusional processes. Creep damage observed in the DIMOX Al₂O₃-SiC_p composite resulted from the cavitation at alumina two-grain facets and multiple-grain junctions where aluminum alloy was present.     

Corrosion Behavior of Alumina Ceramics in Caustic Alkaline Solutions at High Temperatures

The corrosion rate and changes in the microstructure and fracture strength of alumina ceramics (93.0% Al₂O₃ and 99.5% Al₂O₃) were studied in 0.1 m to 25 m NaOH solutions at 150°C to 200°C, where m = mol/(kg of H₂O). The attack of the caustic alkaline solution started at the grain boundaries. Consequently, the corrosion resistance increased with decreasing SiO₂ content in Al₂O₃ ceramics, and the corrosion resistance of 99.5% pure Al₂O₃ was similar to that of Si₃N₄ ceramics. Since large pits are formed by corrosion, the surface area increased first and the apparent corrosion rate increased with time in the initial stage of the corrosion. The corrosion rate of Al₂O₃ increased linearly with increasing NaOH concentration, and the activation energy was 102 kJ/mol. The fracture strength of corroded Al₂O₃ decreased monotonically as the degree of dissolution of alumina increased.