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)).     

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.     

Orientation and Grain Boundary Microstructure of Alumina in Al/Al2O3 Composites Produced by Reactive Metal Penetration

The orientation and grain boundary microstructure of alumina in reactive metal penetration Al/Al₂O₃ composites are studied using orientation imaging microscopy and the results are compared with those of sintered polycrystalline Al₂O₃. The interconnected Al₂O₃ in the composite material is separated by Σ3 boundaries (twins) with a 60° rotation around the [0001] direction. A high frequency (∼100%) of Σ3 coincidence boundaries in composite alumina is remarkable since only ∼12% of boundaries in a sintered polycrystalline Al₂O₃ are of special nature. The coincidence boundaries in the in situ alumina grow in a coherent and faceted manner.     

Atomistic Structure of Calcium Silicate Intergranular Films in Alumina Studied by Molecular Dynamics Simulations

Molecular dynamics simulations of calcium silicate (CaSiO₃)intergranular films that were formed during the liquid-phase sintering of alumina (Al₂O₃)ceramics were conducted. A constant-pressure algorithm was used in the simulations to accommodate changes in the sample size during heat treatment and tensile tests. A model of the grain boundary that was wetted by glass was created by melting the silicate film between two Al₂O₃surfaces with the basal orientation. Samples with different film thicknesses and CaO contents were studied. The presence of an ordered interface in the atomistic structure of the mostly amorphous films was revealed. Calcium additives segregated preferentially into the ordered SiO₂/Al₂O₃interface regions. Increased addition of calcium further promoted the ordering and increased stability of the films. Tensile strength was evaluated and showed an increase with low calcium additions, followed by strength reduction at higher CaO additions. Two modes of fracture were observed in the simulations.     

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.     

Microstructural Analysis of Sintered High-Conductivity Zirconia with Al203 Additions

Transmission electron microscopy (at 100 and 1000 kV potential) and analytical scanning transmission electron microscopy were used to study α-Al₂0₃ second-phase particles and their interactions with grain boundaries in two high-conductivity Y₂0₃/Yb₂0₃ stabilized zirconia ceramics containing deliberate additions of the alumina as a sintering aid. Most of the Al₂0₃ particles were intragranular and microanalysis showed that they contained inclusions rich in Zr or Si plus Zr. Al₂O₃ particles at grain boundaries were frequently associated with amorphous cusp areas rich in Si and Al. The results suggest that the Al₂0₃ acts as a scavenger for SiO₂, removing it from grain-boundary localities. A model is proposed whereby this process occurs as the boundaries meet the second-phase particles, assisted by rapid grain-boundary diffusion. Such an ZrO₂-Al₂O₃-SiO₂ interaction and partitioning is predicted thermodynamically and offers a possible explanation for the improvements in ionic conductivity brought about by Al₂O₃ additions, as reported in the literature.     

Effect of Yttrium and Lanthanum on the Final-Stage Sintering Behavior of Ultrahigh-Purity Alumina

Final-stage sintering has been investigated in ultrahigh-purity Al₂O₃ and Al₂O₃that has been doped individually with 1000 ppm of yttrium and 1000 ppm of lanthanum. In the undoped and doped materials, the dominant densification mechanism is consistent with grain-boundary diffusion. Doping with yttrium and lanthanum decreases the densification rate by a factor of ˜11 and 21, respectively. It is postulated that these large rare-earth cations, which segregate strongly to the grain boundaries in Al₂O₃, block the diffusion of ions along grain boundaries, leading to reduced grain-boundary diffusivity and decreased densification rate. In addition, doping with yttrium and lanthanum decreases grain growth during sintering. In the undoped Al₂O₃, surface-diffusion-controlled pore drag governs grain growth; in the doped materials, no grain-growth mechanism could be unambiguously identified. Overall, yttrium and lanthanum decreases the coarsening rate, relative to the densification rate, and, hence, shifted the grain-size-density trajectory to higher density for a given grain size. It is believed that the effect of the additives is linked strongly to their segregation to the Al₂O₃grain boundaries.     

Interfaces in Oriented Al2O3-ZrO2 (Y2O3) Eutectics

Oriented samples of Al₂O₃-ZrO₂ (Y₂O₃) eutectics consisting of an alumina matrix with zirconia dispersoids were grown by directional solidification. Preferred growth directions and epitaxial relations were determined from X-ray and electron diffraction analyses. Imaging of interfaces was performed by high-resolution transmission electron microscopy on oriented platelets. Semicoherent interfaces were observed with faceting along crystallographic planes of both phases.     

Effect of Composition on the Oxygen Tracer Diffusion in Transparent Yttrium Aluminium Garnet (YAG) Ceramics

The grain boundary structure and oxygen tracer diffusion in transparent yttrium aluminum garnet (YAG) ceramics varying from 2% excess of Y₂O₃ to 0.5% excess of Al₂O₃ were studied. The characterization of the specimens is as follows: (i) For the Y₂O₃-excess specimen, a second phase (yttrium aluminum perovskite: YAP) containing silicon in the grain boundary was found, (ii) For the Al₂O₃-excess specimen, both aluminum-rich particles (alumina) and a silicon-rich segregant layer were observed in the grain boundary. The volume diffusion of the oxygen tracer is little influenced by the excess composition. In contrast, the grain boundary diffusion of the oxygen tracer is suppressed in the Y₂O₃-excess specimens, compared to Al₂O₃-excess specimens. These differences are thought to result from the chemical reaction between the second phase and the intergranular liquid phase during the sintering.     

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.     

Effect of Alkali Metal Oxide Addition on the Sinterability of MgO–B2O3–Al2O3 Glass–Al2O3 Filler Composites

The sintering of a composite of MgO–B₂O₃–Al₂O₃ glass and Al₂O₃ filler is terminated due to the crystallization of Al₄B₂O₉ in the glass. The densification of a composite of MgO–B₂O₃–Al₂O₃ glass and Al₂O₃ filler using pressureless sintering was accomplished by lowering the sintering temperature of the composite. The sintering temperature was lowered by the addition of small amounts of alkali metal oxides to the MgO–B₂O₃–Al₂O₃ glass system. The resultant composite has a four-point bending strength of 280 MPa, a coefficient of thermal expansion (RT—200°C) of 4.4 × 10⁻⁶ K⁻¹, a dielectric constant of 6.0 at 1 MHz, porosity of approximately 1%, and moisture resistance.     

Segregation of Mg to the (0001) Surface of Single-Crystal Alumina: Quantification of AES Results

The actual atomic concentration of Mg segregated to the basal plane of MgO-doped single-crystal alumina surfaces is calculated using an Auger electron spectroscopy quantification method which takes the backscattering factors and Auger electron escape depth into account. The results suggest that Mg segregates as effectively as Ca to AI₂O₃ interfaces. Plausible reasons why Mg has not been detected previously in the grain boundaries of MgO-doped poly crystalline Al₂O₃, while Ca has always been found instead, are discussed.     

Mechanism of Alumina-Enhanced Sintering of Fine Zirconia Powder: Influence of Alumina Concentration on the Initial Stage Sintering

The isothermal shrinkage behavior of 2.9 mol% Y₂O₃-doped ZrO₂ powders with 0–1 mass% Al₂O₃ was investigated to clarify the effect of Al₂O₃ concentration on the initial sintering stage. The shrinkage of the powder compact was measured at constant temperatures in the range of 950°–1050°C. The Al₂O₃ addition increased the densification rate with increasing temperature. The values of apparent activation energy ( nQ ) and apparent frequency-factor term (β₀ ⁿ ), where n is the order depending on the diffusion mechanism, were estimated at the initial sintering stage by applying a sintering-rate equation to the isothermal shrinkage data. The diffusion mechanism changed from grain-boundary diffusion (GBD) to volume diffusion (VD) by Al₂O₃ addition and both nQ and β₀ ⁿ increased with increasing Al₂O₃ concentration. The kinetic analysis of the sintering mechanism suggested that the increase of densification rate by Al₂O₃ addition largely depends on the increase of β₀ ⁿ , that is, the increases of n with GBD→VD change and β₀ with an increase in Al₂O₃ content, although the nQ also increases with Al₂O₃ addition. This enhanced sintering mechanism is reasonably interpreted by the segregated dissolution of Al₂O₃ at ZrO₂ grain boundaries.     

Effect Of Grain Boundaries on Diffusion-Controlled Processes in Aluminum Oxide

Oxygen ion diffusion coefficients in single-crystal Al₂O₃ are several orders of magnitude less than alminum ion diffusion coefficients in polycrystalline Al₂O₃. In polycrystalline Al₂O₃, oxygen ion diffusion is enhanced by the presence of grain boundaries as in the chloride ion diffusion in the alkali halides. Creep and sintering of polycrystalline Al₂O₃ occur at a faster rate than is possible through control by lattice diffusion of oxygen; the rates are in fair quantitative agreement with cation diffusion. It is tentatively concluded that enhanced oxygen diffusion in regions adjacent to boundaries allows aluminum ion bulk diffusion to be rate controlling for these processes. The electrical conductivity in Al₂O₃ is too high to be related to either anion or cation diffusion and is predominantly electronic.     

Effect of Alumina Addition on the Tetragonal-to-Monoclinic Phase Transformation in Zirconia–3 mol% Yttria

The tetragonal-to-monoclinic martensitic phase transformation in ZrO–3 mol% Y₂O₃ (PSZ) containing 0 to 12 wt% Al₂O₃ was investigated by dilatometry, XRD, and SEM-EDS methods. The propagation of the transformation into the specimen interiors was suppressed by the addition of Al₂O₃. The grain size was independent of the addition of Al₂O₃. Both Y₂O₃ and Al₂O₃ segregated at grain boundaries. From this segregation behavior, it was suggested that a certain compound or phase of Y₂O₃–Al₂O₃ could be formed at grain boundaries, which would presumably prevent the propagation of the transformation into interiors of PSZ-containing Al₂O₃.     

Microstructures of SrTiO3 Internal Boundary Layer Capacitors During and After Processing and Resultant Electrical Properties

The microstructure of strontium titanate internal boundary layer capacitors at various stages in their processing was studied by transmission electron microscopy of rapidly quenched and normally cooled samples. Compositions containing excess TiO₂, Al₂O₃, and SiO₂ have a completely wetting liquid phase at the sintering temperature; during cooling Ti_nO_{2 n −1}, Magneli phases precipitate at multiple grain junctions. Diffused metal oxides and flux (Bi₂O₃, PbO, CuO, and B₂O₃) rapidly penetrate as a liquid phase along boundaries in postsintering heat treatment. This liquid phase disappears during slow cooling.     

Postsintering Hot Isostatic Pressing of Ceria-Doped Tetragonal Zirconia/Alumina Composites in an Argon–Oxygen Gas Atmosphere

Ceria-doped tetragonal zirconia (Ce-TZP)/alumina (Al₂O₃) composites were fabricated by sintering at 1450° to 1600°C in air, followed by hot isostatic pressing (postsintering hot isostatic pressing) at 1450°C and 100 MPa in an 80 vol% Ar–20 vol% O₂ gas atmosphere. Dispersion of Al₂O₃ particles into Ce-TZP was useful in increasing the relative density and suppressing the grain growth of Ce-TZP before hot isostatic pressing, but improvement of the fracture strength and fracture toughness was limited. Postsintering hot isostatic pressing was useful to densify Ce-TZP/Al₂O₃ composites without grain growth and to improve the fracture strength and thermal shock resistance.     

Electric-Field-Induced Crack Growth Behavior in PZT/Al2O3 Composites

Hard lead zirconate titanate (PZT) and PZT/Al₂O₃ composites were prepared and the alternating-electric-field-induced crack growth behavior of a precrack above the coercive field was evaluated via optical and scanning electron microscopy. The crack extension in the 1.0 vol% Al₂O₃ composite was significantly smaller than that in monolithic PZT and the 0.5 vol% Al₂O₃ composite. Secondary-phase Al₂O₃ dispersoids were found both at grain boundaries and within grains in the composites. A large number of dispersoids were observed at the grain boundaries in the 1.0 vol% Al₂O₃ composite. It appears that the Al₂O₃ dispersoids reinforce the grain boundaries of the PZT matrix as well as act as effective pins against microcrack propagation.     

Microstructure and Bending Strength of 3Y-TZP/12Ce-TZP Ceramics Fabricated by Liquid-Phase Sintering at Low Temperature

With the addition of 1 wt% of MgO–Al₂O₃–SiO₂ glass as a sintering aid, 3Y-TZP/12Ce-TZP ceramics (composed from a mixture of 3Y-TZP and 12Ce-TZP powder) have been fabricated via liquid-phase sintering at 1250°–1400°C. In the sintered bodies, the grain growth of Y-TZP is almost unaffected, whereas that of Ce-TZP is inhibited. MgO·Al₂O₃ spinel and an amorphous phase that contains Al₂O₃ and SiO₂ (from the sintering aid) fully fill the grain junctions. The bending strength of 3Y-TZP/12Ce-TZP, when sintered at 1250°–1300°C, is ∼800–900 MPa, which is greater than that of 3Y-TZP ceramics without Ce-TZP particles. Ce-TZP grains and MgO·Al₂O₃ spinel in 3Y-TZP/12Ce-TZP ceramics may impede crack growth, and the bending strength is enhanced.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.