Measurement of Residual Stresses in Oxide–ZrO2 Three-Layer Composites

Al₂O₃–ZrO₂ and MgO–ZrO₂ layered composites were fabricated in such a way that the outer layers of bar-shaped specimens consisted of the oxide (Al₂O₃ or MgO) and unstabilized ZrO₂, while the bulk consisted of the oxide and partially stabilized ZrO₂. During cool-down from the sintering or the annealing temperature, the outer layers expanded because of the tetragonal → monoclinic transition in ZrO₂, thereby creating compressive stresses in the outer layers and tensile stresses in the bulk. Residual stresses were determined using a strain gage technique in which a strain gage was mounted on one face while the opposing face was incrementally ground off. Measurement of the strain as a function of thickness permitted the evaluation of residual stresses using pertinent equations from simple beam theory.     

Constrained Densification of Alumina/Zirconia Hybrid Laminates, II: Viscoelastic Stress Computation

To analyze the inhibited densification during sintering and differential shrinkage during cooling of Al₂O₃/ZrO₂symmetric and asymmetric laminates, viscoelastic formulations, in which the viscosity and elastic modulus vary with time, have been developed. The viscoelastic mismatch stresses have been numerically computed over the entire processing cycle, including the heating period, the isothermal period, and the cooling period. The viscosity and free sintering rates that are needed for stress computation have been obtained by modifying the parameters that are measured for a normal isotropic densifying compact using cyclic loading dilatometry. The modification is based on the available sintering models to account for the effect of strain history on compact viscosity and sintering rates. The stress calculation shows that, with the exception of the initial heating period, the viscoelastic stress is identical to the viscous stress that is calculated solely from the strain rate mismatch. Sintering damage in the laminates is shown to occur during densification under conditions where the differential sintering stress is smaller than the intrinsic sintering pressure. The magnitude of residual stress in hybrid laminates on cooling is dependent on the cooling rate, and slower cooling rates are capable of almost completely relaxing the expansion mismatch stress at temperatures of >1200°C.     

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.     

Laminar Ceramics Utilizing the Zirconia Tetragonal-to-Monoclinic Phase Transformation to Obtain a Threshold Strength

Ceramic laminates have been fabricated with thin layers, containing a mixture of unstabilized zirconia (MZ-ZrO₂) and alumina (Al₂O₃), sandwiched between thicker layers of alumina that contain a small fraction of Y₂O₃-stabilized tetragonal ZrO₂ to inhibit grain growth. The MZ-ZrO₂ undergoes a tetragonal-to-monoclinic phase transformation during cooling to produce biaxial compressive stresses in the thin layers. Cracks that extend within the thicker alumina layers can be arrested by the compressive layers to produce a threshold strength, i.e., a strength below which the probability of failure is zero. Laminates composed of Al₂O₃ layers 315 ± 15 μm thick and Al₂O₃/MZ-ZrO₂ layers 29 ± 3 μm thick exhibit a threshold strength of 507 ± 36 MPa, regardless of the MZ-ZrO₂ content, for volume fractions ≥0.35. These results, piezospectroscopic stress measurements, and microstructural observations suggest that microcracking produced during the transformation reduces the magnitude of the compressive stresses achieved, which in turn limits the magnitude of the threshold strength.     

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.     

Neutron Diffraction Measurements of the Residual Stresses in Al2O3-ZrO2 (CeO2) Ceramic Composites

High-resolution neutron powder diffraction was used to study the residual stresses in Al₂O₃-ZrO₂ (12 mol% CeO₂) ceramic composites containing 10, 20, and 40 vol% ZrO₂ (CeO₂). The diffraction data were analyzed using the Rietveld structure refinement technique. The analysis shows that for all samples, the CeO₂-stabilized tetragonal ZrO₂ particles are in tension and the Al₂O₃ matrix is in compression. For both the ZrO₂ particles and the Al₂O₃ matrix, the average lattice strains are anisotropic and increase approximately linearly with a decrease in the corresponding phase content. It is shown that these features can be qualitatively understood by taking into consideration the thermal expansion mismatch between the ZrO₂ and Al₂O₃ grains. Also, for all composite samples, the diffraction peaks are broader than the instrumental resolution, indicating that the strains in these samples are inhomogeneous. From an analysis of the refined peak shape parameters, the average root-meansquare strain, which describes the distribution of the inhomogeneous strain field, was determined. Finally, the average residual stresses were evaluated from the experimentally determined average lattice strains and compared with recent results of X-ray measurements on similar composites.     

Surface Cracking in Layers Under Biaxial, Residual Compressive Stress

Thin two-phase, Al₂O₃/ t -Zr(3Y)O₂ layers bounded by much thicker Zr(3Y)O₂ layers were fabricated by co-sintering powders. After cooling, cracks were observed along the center of the two-phase, Al₂O₃/ t -Zr(3Y)O₂ layers. Although the Al₂O₃/ t -Zr(3Y)O₂ layers are under residual, biaxial compression far from the surface, tensile stresses, normal to the center line, exist at and near the surface. These highly localized tensile stresses can cause cracks to extend parallel to the layer, to a depth proportional to the layer thickness. A tunneling/edge cracking energy release rate function is developed for these cracks. It shows that for a given residual stress, crack extension will take place only when the layer thickness is greater than a critical value. A value of the critical thickness is computed and compared with an available experimental datum point. In addition, the behavior of the energy release rate function due to elastic mismatch is calculated via the finite element method (FEM). It is also shown how this solution for crack extension can be applied to explain cracking associated with other phenomena, e.g., joining, reaction couples, etc.     

Strengthening of Oxide Ceramics by Transformation-Induced Stress

Alumina-zirconia composites were fabricated by isostatic pressing and sintering of powder mixtures in such a way that bar-shaped specimens consisted of three layers. The outer layers contained A1₂O₃ and unstabilized ZrO₂ while the central layer contained A1₂O₃ and partially stabilized ZrO₂ (with 2 mol% Y₂O₃). When cooled from the sintering temperature, some of the zirconia in the outer layers transformed to the monoclinic form while zirconia in the central layer was retained in the tetragonal form. The transformation of zirconia in the outer layers led to the establishment of surface compressive stresses and balancing tensile stresses in the bulk. The existence of surface compressive stresses was verified by a strain gauge technique and bending strength measurements on samples with varying thickness of the outer layers. The layered composites exhibited greater strength in comparison with monolithic Al₂O₃-ZrO₂ specimens. Further, variation of strength in bending with outer layer thickness (for a fixed total thickness) indicated that failure occurred from internal flaws. Scanning electron microscopy of fracture surfaces revealed that strength-limiting flaws were voids located in the central layer near the interface separating the central and the outer layers.     

Strength Improvement in Transformation-Toughened Alumina by Selective Phase Transformation

A1₂O₃-15 vol% ZrO₂ bar-shaped ceramic specimens were fabricated in the green state in such a way that the near surface regions consisted of A1₂O₃ and unstabilized ZrO₂ while the bulk consisted of A1₂O₃ and partially stabilized ZrO₂. After sintering, specimens had macroscopic residual compressive surface stresses and balancing interior tensile stresses due to the tetragonal-to-monoclinic phase transformation in the outer layers which occurs during cooling. The depth of the surface region was controlled during green forming. Residual surface compressive stresses at room temperature varied between 100 and 400 MPa depending on the outer-layer thickness. The increased strengths of the three-layer specimens were obtained in the as-fired unground condition, demonstrating that the stresses introduced are the result of transformation of tetragonal zirconia into monoclinic polymorph which occurred upon cooling from the sintering temperature. Specimens with residual surface compressive stresses were 200 MPa stronger at 750°C than monolithic specimens, demonstrating the viability of this approach for improving elevated-temperature mechanical properties.     

Processing-Related Fracture Origins: III, Differential Sintering of ZrO2 Agglomerates in Al2O3/ZrO2 Composite

Large, hard ZrO₂ agglomerates remained in an Al₂O₃/ZrO₂ composite suspension after inefficient ball-milling. The ZrO₂ agglomerates shrank away from the consolidated Al₂O₃/ZrO₂ powder matrix during sintering, producing crack-like voids which were responsible for strength degradation.     

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.     

Crack Bifurcation in Laminar Ceramic Composites

Crack bifurcation was observed in laminar ceramic composites when cracks entered thin Al₂O₃ layers sandwiched between thicker layers of Zr(12Ce)O₂. The Al₂O₃ layers contained a biaxial, residual, compressive stress of ∼2 GPa developed due to differential contraction upon cooling from the processing temperature. The Zr(12Ce)O₂ layers were nearly free of residual, tensile stresses because they were much thicker than the Al₂O₃ layers. The ceramic composites were fabricated by a green tape and codensification method. Different specimens were fabricated to examine the effect of the thickness of the Al₂O₃ layer on the bifurcation phenomena. Bar specimens were fractured in four-point bending. When the propagating crack encountered the Al₂O₃ layer, it bifurcated as it approached the Zr(12Ce)O₂/ Al₂O₃ interface. After the crack bifurcated, it continued to propagate close to the center line of the Al₂O₃ layer. Fracture of the laminate continued after the primary crack reinitiated to propagate through the next Zr(12Ce)O₂ layer, where it bifurcated again as it entered the next Al₂O₃ layer. If the loading was stopped during bifurcation, the specimen could be unloaded prior to complete fracture. Although the residual stresses were nearly identical in all Al₂O₃ layers, crack bifurcation was observed only when the layer thickness was greater than ∼70 μm.     

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.     

Conventional and Microwave-Induced Sintering Mechanisms for Reaction-Bonded Aluminum Oxide with Zirconium Oxide Additions

Powder compacts consisting of Al, Al₂O₃, and ZrO₂ were heated by microwave radiation. Tracing the phase evolution during reaction bonding revealed the reaction mechanism. In the case of conventional heating, the compacts expanded slightly at temperatures of <700°C due to Al surface oxidation and expanded sharply at temperatures greater than 700°C as oxidation proceeded from the surface to the interior. Then, the compacts shrank at 1550°C due to sintering. For the case of microwave heating, the compacts expanded at temperatures of <550°C due to the formation of Al₃Zr. This Al₃Zr formation was caused by the preferential heating of ZrO₂ relative to Al and Al₂O₃ by microwave radiation. Then, Al₃Zr was oxidized to form Al₂O₃ and ZrO₂ at temperatures of >1000°C. Finally, the compacts shrank at 1550°C due to sintering, similarly to conventional sintering.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

Consolidation of Alumina—Zirconia Mixtures by a Colloidal Process

The relationship between the dispersion of colloidal powder particles in Al₂O₃–ZrO₂ suspensions and the microstructures of consolidated compacts was examined. Suspensions were prepared from Al₂O₃ powder and ZrO₂ sol with average particle sizes of 390 and 62 nm, respectively. The dispersion was controlled by pH and salt concentration adjustments. The compacts composed of completely separated Al₂O₃ and ZrO₂ layers were obtained from well-dispersed suspensions with pH values below about 4 and salt concentration of 0.0527 M. An increase in pH or salt concentration resulted in macroscopically uniform compacts. The compacts made from suspensions with pH values above about 7, however, were composed of a mixture of Al₂O₃ and ZrO₂ agglomerates, with one acting as a matrix and the other a dispersed phase. Suspensions with a pH value of 4.5 and optimum salt concentrations resulted in compacts with microscopically uniform microstructure. Above or below these salt concentrations, ZrO₂ agglomerates were distributed in an Al₂O₃ matrix. The optimum concentration was dependent on solid content. In addition, the dispersion of mixed suspensions was compared with those of single-component suspensions. The ZrO₂ particles formed three-dimensional networks during agglomeration, which reduced the component separation in suspensions and during consolidation.     

Processing of Tape–Cast Laminates Prepared from Fine Alumina/Zirconia Powders

This paper addresses the effect of thermocompression pressure, shear deformation of green laminates, and postsinter HIPing on the microstructural homogeneity of cast tapes and laminates prepared from fine Al₂O₃, and Al₂O₃/ ZrO₂, powders. Green density increases with increasing thermo–compression pressure. Sintered densities, however, depend more on the macroscopic uniformity in the green tapes. When density gradients develop within the individual green tapes (because of improper drying), sintering is constrained in two dimensions and densities remain low. Postsinter HIPing does not significantly increase the sintered densities because of the retention of open porosity within the individual tape–cast layers. The use of a revised thermocompression process involving shear deformation results in higher sintered densities and complete densification after HIPing. Sintered densities increase with the degree of shear strain during green–state deformation processing. Thus, green-state deformation can improve homogeneity in laminates. A further variation of the shear deformation process has also been developed that allows the formation of complex shapes from tape–cast laminates in the green state, while retaining layer integrity.     

Tensile Ductility in Zirconia-Dispersed Alumina at High Temperatures

High-temperature plastic flow in Al₂O₃-10 wt% ZrO₂ (2.5 mol% Y₂O₃) has been examined at temperatures between 1400° and 1500°C. Al₂O₃-10 wt% ZrO₂ (2.5 mol% Y₂O₃) exhibits much higher flow stress and smaller tensile elongation below about 1450°C than 0.1 wt% MgO-doped single-phase Al₂O₃. The suppression of grain growth with ZrO₂ dispersion into Al₂O₃ is not effective for improving the tensile ductility. The limited ductility in Al₂O₃-10 wt% ZrO₂ (2.5 mol% Y₂O₃) is associated with the increment of flow stress caused by ZrO₂. The ZrO₂ dispersion or segregation in Al₂O₃/Al₂O₃ boundaries suppresses the grain boundary sliding and hence results in the increased flow stress at high temperatures.     

Transformation and Microcrack Toughening as Complementary Processes in ZrO2-Toughened Al2O3

Both tetragonal ( t ) and monoclinic ( m ) ZrO₂ particles in ZrO₂-toughened Al₂O₃ can give rise to toughening. In the stress field of propagating cracks, the t -ZrO₂ particles can undergo the stress-induced t → m transformation, and the residual stresses around already-transformed m -ZrO₂ particles can cause microcracking. The t -ZrO₂ particles transformed in crack tip stress fields do not, however, also cause appreciable microcracking. The toughening increments via these distinct mechanisms are comparable. It appears that optimally fabricated Zr0₂-toughened Al₂O₃'s should contain a mixture of t - and m -ZrO₂.     

Effects of Interfacial Films on Thermal Stresses in Whisker-Reinforced Ceramics

Toughening of whisker-reinforced (or fiber-reinforced) ceramics by whisker pullout requires debonding at the whisker/matrix interface. Compressive clamping stresses, which would inhibit interface debonding and/or pullout, are expected in composites where the matrix has a higher thermal expansion coefficient than the whisker. Because such mismatch in thermomechanical properties can result in brittle composites, it is important to explore approaches to modify the thermal stresses in composites. As a result, the effects of a film at the whisker/matrix interface on the stresses due to thermal contraction mismatch upon cooling are considered in this study. Analysis of various properties of the film are considered for the whisker/matrix systems, in particular for SiC/Al₂O₃, SiC/cordierite, and SiC/mullite composites. Reduction of thermomechanical stresses is shown to occur when the interfacial film has a low Young's modulus. Also, when the whisker has a lower thermal expansion coefficient than the matrix (e.g., SiC/Al₂O₃), the interfacial stresses generated during cooling decrease as the thermal expansion coefficient of the film increases.