Major Influences on the Particle-Size–Transformation-Temperature Relation in Al2O3–ZrO2 Composites

The energetics of martensitic transformation in ZrO₂ is studied using a thermodynamic approach, with particular reference to Al₂O₃–ZrO₂ composites. The different characters of three types of transformation-toughened ceramics are analyzed, and several factors affecting the t → m transformation in Al₂O₃–ZrO₂ composites are discussed. The expression of transformation temperature dependence on particle size is derived and has good agreement with experimental results. The energetics concerned with nucleation of martensitic transformation is also discussed.     

Properties of (Y)ZrO2–Al2O3 and (Y)ZrO2–Al2O3–(Ti or Si)C Composites

The effect of Al₂O₃ and (Ti or Si)C additions on various properties of a (Y)TZP (yttria-stabilized tetragonal zirconia polycrystal)–Al₂O₃–(Ti or Si)C ternary composite ceramic were investigated for developing a zirconia-based ceramic stronger than SiC at high temperatures. Adding Al₂O₃ to (Y)TZP improved transverse rupture strength and hardness but decreased fracture toughness. This binary composite ceramic revealed a rapid loss of strength with increasing temperature. Adding TiC to the binary ceramic suppressed the decrease in strength at temperatures above 1573 K. The residual tensile stress induced by the differential thermal expansion between ZrO₂ and TiC therefore must have inhibited the t - → m -ZrO₂ martensitic transformation. It was concluded that a continuous skeleton of TiC prevented grain-boundary sliding between ZrO₂ and Al₂O₃. In contrast, for the ternary material containing β-SiC in place of TiC, the strength decreased substantially with increasing temperature because of incomplete formation of the SiC skeleton.     

Fabrication and Microstructure of Al2O3–SiC–YAG Hybrid Composites Prepared by Particulate Dispersion

Stable Al₂O₃–SiC–YAG hybrid composites were successfully fabricated by reaction of Al₂O₃ and Y₂O₃ and incorporation of SiC. The hot-pressed bodies consisted of uniformly dispersed grains of microsized YAG particulates and nanosized SiC particulates in an Al₂O₃ matrix. Although the grain size of monolithic A1₂O₃ increases markedly with increased temperature, the grain size of the Al₂O₃–SiC–YAG hybrid composites was effectively restrained due to grain-boundary pinning by the particulates.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Electroconductive Al2O3–NbN Composites

Electroconductive Al₂O₃–NbN ceramic composites were prepared by hot pressing. Dense sintered bodies of ball-milled Al₂O₃–NbN composite powders were obtained at 1550°C and 30 MPa for 1 h under a nitrogen atmosphere. The bending strength and fracture toughness of the composites were enhanced by incorporating niobium nitride (NbN) particles into the Al₂O₃ matrix. The electrical resistivity of the composites decreased with increasing amount of NbN phase. For a 25 vol% NbN–Al₂O₃ composite, the values of bending strength, fracture toughness, Vickers hardness, and electrical resistivity were 444.2 MPa, 4.59 MPa·m^1/2, 16.62 GPa, and 1.72 × 10⁻²Ω·cm, respectively, making the composite suitable for electrical discharge machining.     

Fabrication and Characterization of ZrB2-Based Ceramic Using Synthesized ZrB2–LaB6 Powder

ZrB₂–LaB₆ powder was obtained by reactive synthesis using ZrO₂, La₂O₃, B₄C, and carbon powders. Then ZrB₂–20 vol% SiC–10 vol% LaB₆ (ZSL) ceramics were prepared from commercially available SiC and the synthesized ZrB₂–LaB₆ powder via hot pressing at 2000°C. The phase composition, microstructure, and mechanical properties were characterized. Results showed that both LaB₆ and SiC were uniformly distributed in the ZrB₂ matrix. The hardness and bending strength of ZSL were 17.06±0.52 GPa and 505.8±17.9 MPa, respectively. Fracture toughness was 5.7±0.39 MPa·m^1/2, which is significantly higher than that reported for ZrB₂–20 vol% SiC ceramics, due to enhanced crack deflection and crack bridging near SiC particles.     

Tape Casting of Al2O3/ZrO2 Laminated Composites

Fracture toughness of ZrO₂-toughened alumina could he increased by macroscopic interfaces, such as those existing in laminated composites. In this work, tape casting was used to produce A/A or A/B laminates, where A and B can be Al₂O₃, Al₂O₃/5 vol% ZrO₂, and Al₂O₃/l0 vol% ZrO₂. An increase of toughness is observed, even in the Al₂O₃/Al₂O₃ laminates.     

Influence of the Y2O3 Content and Temperature on the Mechanical Properties of Melt-Grown Al2O3–ZrO2 Eutectics

The effect of Y₂O₃ content on the flexure strength of melt-grown Al₂O₃–ZrO₂ eutectics was studied in a temperature range of 25°–1427°C. The processing conditions were carefully controlled to obtain a constant microstructure independent of Y₂O₃ content. The rod microstructure was made up of alternating bands of fine and coarse dispersions of irregular ZrO₂ platelets oriented along the growth axis and embedded in the continuous Al₂O₃ matrix. The highest flexure strength at ambient temperature was found in the material with 3 mol% Y₂O₃ in relation to ZrO₂(Y₂O₃). Higher Y₂O₃ content did not substantially modify the mechanical response; however, materials with 0.5 mol% presented a significant degradation in the flexure strength because of the presence of large defects. They were nucleated at the Al₂O₃–ZrO₂ interface during the martensitic transformation of ZrO₂ on cooling and propagated into the Al₂O₃ matrix driven by the tensile residual stresses generated by the transformation. The material with 3 mol% Y₂O₃ retained 80% of the flexure strength at 1427°C, whereas the mechanical properties of the eutectic with 0.5 mol% Y₂O₃ dropped rapidly with temperature as a result of extensive microcracking.     

Homogeneous ZrO2–Al2O3 Composite Prepared by Nano-ZrO2 Particle Multilayer-Coated Al2O3 Particles

ZrO₂–Al₂O₃ nanocomposite particles were synthesized by coating nano-ZrO₂ particles on the surface of Al₂O₃ particles via the layer-by-layer (LBL) method. Polyacrylic acid (PAA) adsorption successfully modified the Al₂O₃ surface charge. Multilayer coating was successfully implemented, which was characterized by ξ potential, particle size. X-ray diffraction patterns showed that the content of ZrO₂ in the final powders could be well controlled by the LBL method. The powders coated with three layers of nano-ZrO₂ particles, which contained about 12 wt% ZrO₂, were compacted by dry press and cold isostatically pressed methods. After sintering the compact at 1450°C for 2 h under atmosphere, a sintered body with a low pore microstructure was obtained. Scanning electron microscopy micrographs of the sintered body indicated that ZrO₂ was well dispersed in the Al₂O₃ matrix.     

Al2O3–ZrO2–SiO2 Ternary Glasses for Molybdenum Oxidation Barriers

The wettability of binary and ternary glasses belonging to SiO₂–Al₂O₃–ZrO₂ diagram has been studied using the sessile drop technique at 1750° and 1800°C. The ternary SiO₂–Al₂O₃–ZrO₂ (90–5–5 wt%) glass has proved to be well appropriated as a molybdenum oxidation barrier coating. The addition of 5 wt% of MoO₂ slightly improves its wettablity at higher temperatures without affecting its oxidation barrier properties. The Mo comes into the glass network as a mixture of Mo⁵⁺, Mo⁴⁺, and Mo⁶⁺. After oxidation at 1000°C in oxygen atmosphere, the molybdenum remains in the glass network as Mo⁶⁺.     

Oxidation of ZrB2–SiC: Influence of SiC Content on Solid and Liquid Oxide Phase Formation

The effect of SiC concentration on the liquid and solid oxide phases formed during oxidation of ZrB₂–SiC composites is investigated. Oxide-scale features called convection cells are formed from liquid and solid oxide reaction products upon oxidation of the ZrB₂–SiC composites. These convection cells form in the outermost borosilicate oxide film of the oxide scale formed on the ZrB₂–SiC during oxidation at high temperatures (≥1500°C). In this study, three ZrB₂–SiC composites with different amounts of SiC were tested at 1550°C for various durations of time to study the effect of the SiC concentration particularly on the formation of the convection cell features. A calculated ternary phase diagram of a ZrO₂–SiO₂–B₂O₃ (BSZ) system was used for interpretation of the results. The convection cells formed during oxidation were fewer and less uniformly distributed for composites with a higher SiC concentration. This is because the convection cells are formed from ZrO₂ precipitates from a BSZ oxide liquid that forms upon oxidation of the composite at 1550°C. Higher SiC-containing composites will have less dissolved ZrO₂ because they have less B₂O₃, which results in a smaller amount of precipitated ZrO₂ and consequently fewer convection cells.     

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.     

Zirconium Aluminum Carbides: New Precursors for Synthesizing ZrO2–Al2O3 Composites

ZrO₂–Al₂O₃ nanocrystalline powders have been synthesized by oxidizing ternary Zr₂Al₃C₄ powders. The simultaneous oxidation of Al and Zr in Zr₂Al₃C₄ results in homogeneous mixture of ZrO₂ and Al₂O₃ at nanoscale. Bulk nano- and submicro-composites were prepared by hot-pressing as-oxidized powders at 1100°–1500°C. The composition and microstructure evolution during sintering was investigated by XRD, Raman spectroscopy, SEM, and TEM. The crystallite size of ZrO₂ in the composites increased from 7.5 nm for as-oxidized powders to about 0.5 μm at 1500°C, while the tetragonal polymorph gradually converted to monolithic one with increasing crystallite size. The Al₂O₃ in the composites transformed from an amorphous phase in as oxidized powders to θ phase at 1100°C and α phase at higher temperatures. The hardness of the composite increased from 2.0 GPa at 1100°C to 13.5 GPa at 1400°C due to the increase of density.     

Al2O3–Ni Composites with High Strength and Fracture Toughness

Al₂O₃–Ni composites were prepared by the reactive hot pressing of Al and NiO. The composites had a two-phase, interpenetrating microstructure and contained ∼35 vol% Ni. They exhibited an impressively high combination of strength and toughness at room temperature; the four-point bending strength was in excess of 600 MPa with a fracture toughness of more than 12 MPa·m^1/2. Examination of fracture surfaces showed that Ni ligaments underwent ductile deformation during fracture. SEM analysis revealed knife-edged Ni ligaments with a limited amount of debonding around their periphery (i.e., at the Ni–Al₂O₃ interface), indicating a strong Ni–Al₂O₃ bond.     

Effect of Processing Parameters on the Mechanical and Microstructural Behavior of Ultra-Fine Al2O3– (ZrO2+8%Mol Y2O3) Bioceramic, Densified By High-Frequency Induction Heat Sintering

High-frequency induction heat sintering (HFIHS) is a comparatively new technique that consolidates metals and ceramics very rapidly to full density. In this work, superfast densification behavior and the attendant microstructural features of Al₂O₃–(ZrO₂+8% mol Y₂O₃) composites processed by HFIHS were investigated. The effects of processing parameters such as sintering temperatures, pressures, and heating rate, on the mechanical and microstructural properties were studied. The results indicated that HFIHS was effective in the preparation of fine-grained, nearly fully dense Al₂O₃–8YSZ ceramics from the powder with a smaller particle size by optimizing the overall processing parameters.     

Fracture Strength–Fracture Resistance Response and Damage Resistance of Sintered Al2O3–ZrO2 (12 mol% CeO2) Composites

The fracture strengths of sintered Al₂O₃ containing 20 and 40 vol% ZrO₂(12 mol% CeO₂)—zirconia-toughened alumina (ZTA)—composites along with the fracture resistance can be increased (e.g., to ∼900 MPa and >12 Mpa·m^1/2, respectively), by increasing the mean grain size of the t -ZrO₂ (and the Al₂O₃) from ∼0.5 μm to ∼3 μm. At these lower t -ZrO₂ contents, the fracture strength-fracture resistance curves show a continuous rise as opposed to the strength maxima observed in polycrystalline t -ZrO₂(12 mol% CeO₂), CeTZP, and ZrO₂(12 mol% CeO₂) ceramics containing ≤20 vol% Al₂O₃. The toughened composites also exhibit excellent damage resistance with fracture strengths of 500 MPa retained with surfaces containing ∼150- N Vickers indentations which produce cracks of ∼160-μm radius. Greater damage resistance correlates with an increase in the apparent R -curve response of these composites.     

Critical Microstructures for Microcracking in Al2O3-ZrO2 Composites

The internal strains asSociated with the martensitic phase transformation of zirconia were used to introduce microcracks into Al₂O₃/ZrO₂ composites. The degree of transformation was found to be dependent on the volume fraction of ZrO₂ and its size, the latter of which could be controlled by suitable heat treatments. The microstructural changes that occurred during the heat treatments were studied using quantitative microscopy and X-ray diffraction. For materials containing more than 7.5 vol% Zr0₂, the ZrO₂ particles were found to pin the Al₂O₃ grain boundaries, thus limiting the Al₂O₃ grain growth. The limiting grain size was found to be dependent on size and volume fraction of ZrO₂. Heat treatments for the higher volume fraction materials (>7.5 vol% ZrO₂) caused micro-structural changes which resulted in increased amounts of monoclinic ZrO₂ at room temperature; elastic modulus measurements indicated that this was occurring concurrently with microcracking. By combining the ZrO₂ grain-size distributions with the X-ray analysis it was possible to calculate the critical ZrO₂ size required for the transformation. The critical size was found to decrease with increasing amounts of ZrO₂. Hardness and indentation fracture toughness were measured on the composites. Grain fragmentation was observed at the edge of the indentations and microcracks were observed directly, using an AgNO₃ decoration technique, near the indentations.     

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.     

Activity–Composition Relations in FeCr2O4–FeAl2O4 and MnCr2O4–MnAl2O4 Solid Solutions at 1500° and 1600°C

Activity–composition relations of FeCr₂O₄–FeAl₂O₄ and MnCr₂O₄–MnAl₂O₄ solid solutions were derived from activity–composition relations of Cr₂O₃–Al₂O₃ solid solutions and directions of conjugation lines between coexisting spinel and sesquioxide phases in the systems FeO–Cr₂O₃–Al₂O₃ and MnO–Cr₂O₃–Al₂O₃. Moderate positive deviations from ideality were observed.     

Subsolidus Phase Relationships in the System Fe2O3–Al2O3–TiO2 between 1000° and 1300°C

Subsolidus phase equilibria in the system Fe₂O₃–Al₂O₃–TiO₂ were investigated between 1000° and 1300°C. Quenched samples were examined using powder X-ray diffraction and electron probe microanalytical methods. The main features of the phase relations were: (a) the presence of an M₃O₅ solid solution series between end members Fe₂TiO₅ and Al₂TiO₅, (b) a miscibility gap along the Fe₂O₃–Al₂O₃ binary, (c) an α-M₂O₃( ss ) ternary solid-solution region based on mutual solubility between Fe₂O₃, Al₂O₃, and TiO₂, and (d) an extensive three-phase region characterized by the assemblage M₃O₅+α-M₂O₃( ss ) + Cor( ss ). A comparison of results with previously established phase relations for the Fe₂O₃–Al₂O₃–TiO₂ system shows considerable discrepancy.