Reactive Hot Pressing of Alumina-Silicon Carbide Nanocomposites

A dense alumina-silicon carbide (Al₂O₃–SiC) nanocomposite was synthesized in situ from the reaction of mullite, aluminum, and carbon by reactive hot pressing (RHP). Transmission electron microscopy investigation showed that in situ -formed, nanometer-sized SiC particles were mainly entrapped in the matrix grains, whereas submicrometer-sized particles were located at the grain boundaries or triple points of the Al₂O₃. In addition, no amorphous phase was observed at the interfaces of the Al₂O₃ and SiC grains, which indicated strong direct bonding. Fracture-surface analysis by scanning electron microscopy revealed an intrafracture mode. The bending strength of the nanocomposite RHP-treated at 1800°C was 795 ± 160 MPa, and the fracture toughness, measured by the indentation method, was 3.1 MPa·m^1/2.     

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.     

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.     

Use of Mixed-Rare-Earth Oxide in the Preparation of Reaction-Bonded Mullite at ≤1300°C

A process for production of near-net-shape mullite-matrix ceramic composites at ≤1300°C has been achieved by reaction-bonding Al₂O₃, silicon, mullite seeds, and eutectics of Al₂O₃–SiO₂–mixed-rare-earth oxide. The fusion temperature of the eutectic composition utilized is 1175°C. This liquid phase facilitates silicon oxidation, mullitization, and sintering. Mullite phase develops with low residual Al₂O₃ when 7.5 wt% mixed-rare-earth oxide and 5 wt% mullite seeds are used. The final sinter is >90% of theoretical density, >90% mullite (by quantitative XRD), and suffers 2.2% sintering shrinkage.     

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.     

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.     

Novel Low-Temperature Processing Route of Dense Mullite Ceramics by Reaction Sintering of Amorphous SiO2-Coated γ-Al2O3 Particle Nanocomposites

Dense mullite ceramics were successfully produced at temperatures below 1300°C from amorphous SiO₂-coated gamma-Al₂O₃ particle nanocomposites (AS-gammaA). This method reduces processing temperatures by similar/congruent300°C or more with respect to amorphous SiO₂-coated alpha-Al₂O₃ particle microcomposites (AS-alphaA) and to other Al₂O₃-SiO₂ reaction couples. The good densification behavior and the relatively low mullite formation temperature make AS-gammaA nanocomposites an excellent matrix raw material for polycrystalline aluminosilicate fiber-reinforced mullite composites.     

Contact Damage of Silicon Carbide/Boron Nitride Nanocomposites

To investigate the deformation mechanism of silicon carbide (SiC)/boron nitride (BN) nanocomposites, Hertzian contact tests were performed on monolithic SiC, and nanocomposite and microcomposite SiC/BN. Monolithic SiC had the typical microstructure of hot-pressed SiC with Y₂O₃ and Al₂O₃ additives, composed of slightly large grains in small matrix grains. The microcomposite comprised large BN grains dispersed along the grain boundaries of elongated SiC grains, while the nanocomposite showed a finer microstructure with fine BN particles and small matrix grains. These microstructural differences led to differences in the mechanism of contact damage. The damage of the monolithic SiC and the SiC/BN microcomposite exhibited classical Hertzian cone fracture and many large cracks, whereas the damage observed in the nanocomposites appeared to be quasi-plastic deformation.     

Evidence for Bulk Residual Stress Strengthening in Al2O3/SiC Nanocomposites

The fracture behavior of Al₂O₃/SiC nanocomposites has been studied as a function of the SiC volume fraction and compared to that of the pure Al₂O₃ matrix. A pronounced strengthening effect was only observed for materials with low SiC content (i.e., ≤10 vol%) although no evidence of concurrent toughening was found. Assessment of near-tip crack opening displacement (COD) could not experimentally substantiate significant occurrence of an elastic crack-bridging mechanism, in contrast with a recently proposed literature model. Quantitative fractography analysis indicated that transgranular crack propagation in Al₂O₃/SiC nanocomposites depends on the location of the SiC dispersoids within the matrix texture; the higher the fraction of transgranularly located dispersoids, the more transgranular the fracture mode. Experimental evidence of remarkably high residual stresses arising from thermal dilatation mismatch (upon cooling) between Al₂O₃ and SiC phases were obtained by fluorescence and Raman spectroscopy. A strengthening mechanism is invoked which merely arises from residual stress through strengthening of Al₂O₃ grain boundaries.     

Microstructural Studies in Alkoxide-Derived Mullite/Zirconia/Silicon Carbide-Whisker Composites

Mullite composites toughened with ZrO₂ (with or without a MgO or Y₂O₃ stabilizer) and/or SiC whiskers (SiC( w )) were fabricated by hot-pressing powders prepared from Al, Si, Zr, and Mg(Y) alkoxide precursors by a sol–gel process. Micro-structures were studied by using XRD. SEM, and analytical STEM. Pure mullite samples contained prismatic, preferentially oriented mullite grains. However, the addition of ZrO₂, as well as the hot-pressing temperature, affected the morphology and grain size in the composites; a fine, uniform, equiaxed microstructure was obtained. The effect of SiC( W ) was less pronounced than that of ZrO₂. Glassy phases were present in mullite and mullite/SiC( W ) composites, but were rarely observed in Al₂O₃-rich or ZrO₂-containing samples. The formation of zircon due to the reaction between ZrO₂ and SiO₂ and the considerable solid solution of SiO₂ in ZrO₂ prevented the formation of the glassy phase, whereas the reaction between Al₂O₃ and MgO in MgO-containing samples formed a spinel phase and also deprived the ZrO₂ phase of the stabilizer. Intergranular ZrO₂ particles were either monoclinic or tetragonal, depending on size and stabilizer content; small intragranular ZrO₂ inclusions were usually tetragonal in structure.     

Homogeneous Fabrication of Al2O3–ZrO2–SiC Whisker Composite by Surface-Induced Coating

Al₂O₃–ZrO₂–SiC whisker composites were prepared by surface-induced coating of the precursor for the ZrO₂ phase on the kinetically stable colloid particles of Al₂O₃ and SiC whisker. The fabricated composites were characterized by a uniform spatial distribution of ZrO₂ and SiC whisker phases throughout the Al₂O₃ matrix. The fracture toughness values of the Al₂O₃–15 vol% ZrO₂–20 vol% SiC whisker composites (∼12 MPa.m^1/2) are substantially greater than those of comparable Al₂O₃–SiC whisker composites, indicating that both the toughening resulting from the process zone mechanism and that caused by the reinforced SiC whiskers work simultaneously in hot-pressed composites.     

Densification of Alumina-Silicon Carbide Powder Composites: I, Effects of a Polymer Coating on Silicon Carbide Particles

One possible approach to improving the densification of powder composites containing a major crystalline phase which densifies (e.g., Al₂O₃) and a difficult-to-sinter phase (e.g., SiC) is to accommodate the matrix volume shrinkage with a "disappearing" polymer coating. A polymer coating prevents contact between the nonsinterable particles and the surrounding matrix. The coating can be burned off before sintering, allowing the matrix phase to "shrink-fit" around the nonsinterable particles during sintering. The effects of a polymer coating on the densification of a two-phase particle system were tested using SiC powder dispersed in an Al₂O₃ matrix. The composites processed with a polymer coating showed more densification during equivalent firing cycles than did those processed without a polymer coating. Densification during sintering was approximately proportional to the amount of polymer adsorbed on SiC, suggesting that the Al₂O₃ matrix did shrink-fit into the gaps between the SiC particles and the surrounding Al₂O₃ matrix. Differences in the pore-size distributions of polymercoated green compacts and uncoated compacts indicated a perturbation of the green microstructure by the gaps. The estimated average thickness of the gap is approximately 20 nm, ∼8% of the average radius of the SiC powder used in this study.     

Corrosion of Mullite by Molten Salts

The interaction of molten salts of different Na₂O activities and mullite is examined with furnace and burner tests. The more-acidic molten salts form small amounts of Al₂O₃; the more-basic molten salts form various Na₂O–Al₂O₃–SiO₂ compounds. The results are interpreted using the Na₂O–Al₂O₃–SiO₂ ternary phase diagram, and some possible diffusion paths are discussed. The generally higher melting points of Na₂O–Al₂O₃–SiO₂ compounds lead to better behavior of mullite in molten salts, as compared to SiO₂-protected ceramics such as SiC. Mullite-coated SiC is discussed, and the corrosion behavior is evaluated.     

Reaction Bonding and Mechanical Properties of Mullite/Silicon Carbide Composites

Based on the RBAO technology, low-shrinkage mullite/SiC/ Al₂O₃/ZrO₂ composites were fabricated. A powder mixture of 40 vol% Al, 30 vol% A1₂O₃ and 30 vol% SiC was attrition milled in acetone with TZP balls which introduced a substantial ZrO₂ wear debris into the mixture. The precursor powder was isopressed at 300–900 MPa and heattreated in air by two different cycles resulting in various phase ratios in the final products. During heating, Al oxidizes to Al₂O₃ completely, while SiC oxidizes to SiO₂ only on its surface. Fast densification (at >1300°C) and mullite formation (at 1400°C) prevent further oxidation of the SiC particles. Because of the volume expansion associated with the oxidation of Al (28%), SiC (108%), and the mullitization (4.2%), sintering shrinkage is effectively compensated. The reaction-bonded composites exhibit low linear shrinkages and high strengths: shrinkages of 7.2%, 4.8%, and 3%, and strengths of 610, 580, and 490 MPa, corresponding to compaction pressure of 300, 600, and 900 MPa, respectively, were achieved in samples containing 49–55 vol% mullite. HIPing improved significantly the mechanical properties: a fracture strength of 490 MPa and a toughness of 4.1 MPa^.m^1/2 increased to 890 MPa and 6 MPa^.m^1/2, respectively.     

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.     

Thermal Evolution and Sintering Behavior of a 2:1 Mullite Gel

The thermal evolution of a mullite gel of composition 2Al₂O₃·SiO₂ has been investigated. The gel crystallized at 1300°C into an alumina-rich mullite and corundum, instead of single-phase 2Al₂O₃·SiO₂ mullite. The amount of Al₂O₃ that dissolved in the mullite structure has been determined in the 1300–1780°C temperature range by measuring the mullite lattice parameters. A maximum limit for the amount of Al₂O₃ in solid solution has been observed. Densification of the gel powders has been analyzed up to temperatures of 1780°C. The microstructure of dense materials always showed the presence of residual Al₂O₃ particles.     

Fabrication of Silicon Carbide-Mullite Composite by Melt Infiltration

The melt infiltration method was used to fabricate a SiC-mullite composite at high temperature. Mullite was successfully obtained from a SiO₂ and Al₂O₃ powder mixture by melting above 1830°C in a BN crucible with a lid. When infiltrated into a porous SiC preform, the mullite significantly reacted with SiC to form gaseous SiO and CO, even at the lowest investigated temperature of 1830°C, consuming SiO₂ and leaving Al₂O₃ and silicon phases in the sample. The relevant reactions were studied in detail. A closed system was adopted to suppress the reaction, and a dense composite was successfully obtained.     

Solid Solution Range and Microstructures of Melt-Grown Mullite

The solid solution range of melt-grown mullite was examined by crystal-chemical methods. The maximum Al₂O₃ content as determined by EDX was ∼83.6 wt%, 75 mol%, or the nominal composition 3Al₂O₃.SiO₂. For samples of overall composition 81 to 83 wt% Al₂O₃, extra lines indicating crystallographic superstructure appeared in Guinier X-ray patterns. The corresponding TEM microstructure consisted of a mullite matrix finely twinned on (001), the twins being 0.02 to 0.10 μm wide, with oriented exsolution of α-A1₂O₃, often twinned, also being present. The analogy between mullite superstructure and that of plagioclase feldspars, as well as the relevance of these findings to the SiO₂-Al₂O₃ metastable phase equilibria are discussed.     

Effect of Milling Conditions on the Strength of Alumina–Silicon Carbide Nanocomposites

Processing effects of wet ball-milling on the microstructure and fracture strength of Al₂O₃/5 vol% SiC nanocomposites were investigated. Homogeneous microstructure and a high fracture strength of 1200 MPa could be achieved under the milling condition of relatively low wear contents of Al₂O₃ grinding media, maintaining the homogeneity of the ball-milled powders. The fracture strength decreased with increasing wear content. Degradation of fracture strength was caused by abnormal grain growth related to wear particles from the Al₂O₃ balls.     

Intermediate Phases in Mullite Synthesis Via Aluminum- and Alumina-Filled Polymethylsiloxane

Active filler pyrolysis of polymethylsiloxane/aluminum (PMS/Al) mixtures leads to the formation of mullite at 1400°C, and by 1700°C mullite is the only crystalline phase in an amorphous matrix. These mixtures show a complex series of oxidation and reduction reactions prior to the formation of mullite. Initial oxidation of PMS at low temperatures results in the formation of an amorphous product before any significant oxidation of the Al. After melting of the Al phase, redox reactions lead to the formation of elemental Si and SiC as intermediate crystalline phases along with Al₂O₃ both as the crystalline α-phase and dissolved in the amorphous matrix. Mullite formation occurs by precipitation from the matrix at temperatures above 1400°C. In contrast, PMS/Al₂O₃ mixtures did not show mullite formation until heat treatment at 1700°C. In this case no significant intermediate crystalline phases occur, except for some limited cristobalite crystallization from the matrix.