Bimaterial Composites via Colloidal Rolling Techniques: II, Sintering Behavior and Thermal Stresses

Shrinkage behavior and crack formation during firing have been investigated for Al₂O₃/Ce-TZP composites that have been fabricated by colloidal rolling and folding. These composites show improved sinterability and sinter isotropically after repeated rolling. Interface instability in rolling creates corrugated interfaces with large layer waviness; therefore, rolling can substantially alleviate the in-plane sintering constraints, which leads to improved sinterability. A loss of sintering anisotropy also is observed and is directly correlated to the microstructure instability, which is coincident with the laminate-cellular transition. Sintering cracks during heating and thermal cracks during cooling both are limited to the thick Ce-TZP layers in the composites. The critical layer thickness and the normalized crack spacing of the thermal cracks follow the predicted behavior of elasticity theory. Thus, crack-free, high-density Al₂O₃/Ce-TZP composites with either a laminate or cellular microstructure can be obtained, with a layer thickness of 4-60 µm, via pressureless sintering.     

Transformation Plasticity and Toughening in CeO2-Partially-Stabilized Zirconia–Alumina (Ce-TZP/Al2O3) Composites Doped with MnO

Microstructure, phase stability, and mechanical properties of CeO₂-partially-stabilized zirconia (12 mol% Ce-TZP) containing 10 wt% Al₂O₃ and 1.5 wt% MnO were studied in relation to the base Ce-TZP and the Ce-TZP/Al₂O₃ composite without MnO. The MnO reacted with both CeO₂ and Al₂O₃ to form a new phase of approximate composition CeMnAl₁₁O₁₉. The reacted phase had a magnetoplumbite structure and formed elongated, needlelike crystals. The MnO-doped Ce-TZP/Al₂O₃ composites sintered at an optimum temperature of 1550°C exhibited high strength (650 MPa in four-point bending) and rising crack-growth-resistance behavior, with fracture toughness increasing from 7.6 to 10.3 MPa.In¹² in compact tension tests. These improved mechanical properties were associated with relatively high tetragonal-to-monoclinic transformation temperature ( M _s=−42°C) at small grain size (2.5 μm), significant transformation plasticity in mechanical tests (bending, uniaxial tension, and uniaxial compression) and transformation zones at crack tips in compact tension specimens. The transformation yield stress, zone size, and fracture toughness were sensitive to the sintering temperature varied in the range 1500° to 1600°C. Analysis of the transformation zones using Raman microprobe spectroscopy and calculation of zone shielding for the observed zones indicated that a large fraction of the fracture toughness (∼70%) was derived from transformation toughening.     

Local Measurements of Temperature Changes Associated with the Stress-Induced Tetragonal to Monoclinic Transformation in Zirconia

An experimental arrangement capable of monitoring temperature changes from 0.01 to 0.1 K has been successfully tested for registering the temperature evolution occurring during the tetragonal to monoclinic transformation of an alumina/ceria-stabilized tetragonal zirconia polycrystal (Al₂O₃/Ce-TZP). The arrangement is based on a very small thermistor. The data obtained have been used for evaluating the thermal diffusivity of the Al₂O₃/Ce-TZP composites.     

Role of Autocatalytic Transformation in Zone Shape and Toughening of Ceria–Tetragonal-Zirconia–Alumina (Ce-TZP/Al2O3) Composites

Stress–strain behaviors in three-point bending, transformation zones in single-edge-notch-bend specimens, and transformation toughening were studied in two types of Ce-TZP/Al₂O₃ composites. A commercial grade exhibited yield-point behavior triggered by autocatalytic transformation and elongated zones. A new grade of Ce-TZP/Al₂O₃ composite showed monotonic stress–strain behavior and a zone shape close to theoretical prediction based on a shear–dilatation yield criterion. The effects of zone sizes and shapes on fracture toughness of the two ceramic composites are shown to be qualitatively consistent with the predictions of transformation-zone shielding theories.     

In-Situ Formation of Ce-TZP-M-Type Hexaferrite Composites

Composites consisting of a Ce-TZP matrix and in-situ grown particles of La(Fe,Al)₁₂O₁₉ were prepared by the solid-state reaction of Ce-TZP, La(Fe,Al)O₃, and Al₂O₃ powders. The in-situ formation process of La(Fe,Al)₁₂O₁₉ in a Ce-TZP matrix was investigated in relation to the microstructure evolution. The Ce-TZP-La(Fe,Al)₁₂O₁₉ composites had significant magnetic properties and improved mechanical properties. The maximum value of magnetization of the Ce-TZP-La(Fe,Al)₁₂O₁₉ composites was obtained at 90 mol% LaFe₁₂O₁₉ in La(Fe,Al)₁₂O₁₉. The value of the three-point bending strength of Ce-TZP-20 wt% La(Fe,Al)₁₂O₁₉ (90 mol% LaFe₁₂O₁₉) sintered at 1350°C was 780 MPa, compared with 500 MPa of Ce-TZP ceramics. The composite demonstrated crack sensing based upon the change in magnetic gradient.     

Oxidation of SiC/Porous Al2O3 Laminated Ceramic Composites

The oxidation behavior of SiC/porous Al₂O₃ interphase laminated composites was studied using oxidation experiments and mathematical modeling of the reaction/porous diffusion kinetics in this system. Oxidation at 800°C produced both closure of the interlayer porosity at the lateral ends of the laminate and a limited penetration of the oxidation product layer front from the laminate edges to its interior. Oxidation at 800°C resulted in a persistent product layer of nearly uniform thickness that is more suited to test the effects of oxidation on laminate properties. The modeling approach, which explicitly considers the porous microstructure of the interphase and its evolution upon oxidation, reproduces these experimental observations successfully. The model was extended to study the effect that the mixing of SiC grains with Al₂O₃ grains to form a two-phase porous interphase has on pore closure at the interface and oxide product front penetration into the interior of the laminate. Pore closure was found to be accelerated considerably with increasing SiC content, and was not accompanied by any significant decrease in the distance from the laminate edges upto which an oxidation product layer was formed.     

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.     

Phase Transformations in Dicalcium Silicate: I, Fabrication and Phase Stability of Fine-Grained β Phase

Fine-grained β-Ca₂SiO₄ containing small amounts of sodium was fabricated as an analogue to tetragonal zirconia polycrystals (TZP) in order to study the stress-induced β→γ transformation. This avoided the problems associated with the fabrication and evaluation of composites containing β-Ca₂SiO₄. The microstructure of dense β-Ca₂SiO₄ exhibited severe intergranular strains and twin-terminating microcracks as seen by TEM. The β-phase twin widths were quantitatively correlated with grain sizes giving an average ratio of 0.04. Stress-induced transformation was observed on ground surfaces but not on fracture surfaces. The stress–strain behavior and the mechanical properties were consistent with stress-induced microcracking and microcrack coalescence. The elastic modulus of fully dense β phase was estimated to be 123 GPa.     

High-Toughness Ce-TZP/Al2O3 Ceramics with Improved Hardness and Strength

Simulataneous additions of SrO and Al₂O₃ to ZrO₂ (12 mol% CeO₂) lead to the in situ formation of strontium aluminate (SrO · 6Al₂O₃) platelets (∼0.5 μm in width and 5 to 10 μm in length) within the Ce-TZP matrix. These platelet-containing Ce-TZP ceramics have the strength (500 to 700 MPa) and hardness (13 to 14 GPa) of Ce-TZP/Al₂O₃ while maintaining the high toughness (14 to 15 MPa ± m^1/2) of Ce-TZP. Optimum room-temperature properties are obtained at SrO/Al₂O₃ molar ratios between 0.025 and 0.1 for ZrO₂ (12 mol% CeO₂) with starting Al₂O₃ contents ranging between 15 and 60 vol%. The role of various toughening mechanisms is discussed for these composite ceramics.     

Co2+-Substitution Effect in Ce-TZP/La M-type Hexaferrite Composites

A Ce-TZP/platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was synthesized in situ while sintering from a mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO powders. Platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ crystals were grown in a dense Ce-TZP matrix after sintering at temperatures of 1200°–1350°C. The temperature range for sintering Ce-TZP/La(Fe,Al)₁₂O₁₉ composites was expanded widely by substituting Co²⁺ ions for Fe²⁺ ions in its structure. The highest value of the bending strength of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composites was 880 MPa, which was higher than that of the Ce-TZP/La(Fe,Al)₁₂O₁₉ composite (780 MPa) and Ce-TZP (513 MPa). The saturation magnetization of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was a constant value of 7.7 emu/g after the composite was sintered at 1200°–1350°C.     

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.     

Microstructure and Mechanical Properties of ZrB2-Based Composites Reinforced and Toughened by Zirconia

The present work reported the effect of addition of ZrO₂ on the microstructure and mechanical properties of ZrB₂-based ceramic composites by means of hot-pressed sintering. Observation of microstructure and systematic testing results of mechanical properties were carried out. Through X-ray diffraction analysis and calculation of the volume fraction of ZrO₂ phase transformability, the toughening mechanism of the present composites was explored. The phase transformation toughening by ZrO₂ additive played an important role in improving the fracture toughness of ZrB₂-based composites.     

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.     

Cyclic Fatigue of Ce-TZP/AI2O3 Composites: Role of the Degradation of Transformation Zone Shielding

The origin of cyclic fatigue in two Ce-TZP/Al₂O₃ composites was investigated by (a) measurements of residual stresses in the transformation zones and crack-tip stress intensities in in situ loaded compact specimens using microprobe Raman spectroscopy, (b) examination of the crack-tip transformation zones by transmission electron microscopy, and (c) measurements of crack-growth rates in cyclic fatigue and in sustained loading at 400°C, a temperature at which stress-induced transformation of the tetragonal zirconia to the monoclinic polymorph was suppressed. Transformation zones formed during cyclic fatigue consistently showed lower compressive residual stresses and higher crack-tip stress intensities than the zones formed in sustained loading. Transmission electron microscopy revealed monoclinic laths of smaller average twin spacing and of multiple types of lattice correspondence in the transformation zones of the fatigue specimens as compared to the sustained-load specimens. Crack-growth measurements at 400°C indicated a significant suppression of the cyclic fatigue effect in the absence of transformation plasticity. These results in combination pointed to degradation of transformation-zone shielding as an important contributing cause of cyclic fatigue in Ce-TZP/Al₂O, composites. A more efficient accommodation of the transformation strains within the zones appears to be the underlying mechanism of the degradation of zone shielding in cyclic fatigue.     

Zirconia–Mullite Composites Consolidated by Spark Plasma Reaction Sintering from Zircon and Alumina

Mullite–ZrO₂ composites have been fabricated by attrition milling a powder mixture of zircon, alumina, and aluminum metal with MgO or TiO₂ as sintering additives, heating at 1100°C to oxidize the aluminum metal, and consolidation by spark plasma sintering (SPS). The influence of the SPS temperature on the formation of mullite, and the density and the mechanical properties of the resulting composites have been studied. For the mullite–zirconia composites without sintering additives, the mullite formation was accomplished at 1540°C. In contrast, for the composites having MgO and TiO₂, the formation temperature dropped to 1460°C. The composites without sintering additives were almost fully dense (99.9% relative density) and retained a larger amount of tetragonal zirconia. Those materials attained the best mechanical properties ( E =214 GPa and K _{I C} =6 MPa·m^1/2). To highlight the advantages of using the SPS technique, the obtained results have been compared with the characteristics of a mullite–zirconia composite prepared by the conventional reaction-sintering process.     

Translucent Mg-α-Sialon Ceramics Prepared by Spark Plasma Sintering

The translucent Mg-α-sialon ceramics have been prepared by spark plasma sintering (SPS) α-Si₃N₄ powder with AlN and MgO as the additives at 1850°C for 5 min. The sample possesses a uniform, dense microstructure under the rapid densification of SPS process. The translucent Mg-α-sialon ceramics achieve the maximum transmittance of 66.4% for the sample of 0.5 mm in thickness in the medium infrared region, which could be attributed to the equiaxed microstructure and few glassy phase confirmed by the observation of transmission electron microscopy. The material also exhibits good mechanical properties of high hardness (21.4±0.3 GPa) and fracture toughness (6.1±0.1 MPa·m^1/2).     

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.     

Zirconia Particle Coarsening and the Effects of Zirconia Additions on the Mechanical Properties of Certain Commercial Aluminas

The effects of ZrO₂ additions on the mechanical properties of four commercial aluminas have been studied, and the changes in intergranular and intragranular ZrO₂ particle sizes during aging have been determined for one of the aluminas. In this ceramic, the intercranular and intragranular ZrO₂ particles coarsen obeying t ^1/2 and t ^1/3 kinetics, respectively. Changes in strength of the aluminas with additions of ZrO₂ are shown to be related to changes in the Al₂O₃ matrix microstructure. Differences in toughness of the resulting composites are explained in terms of the different size and morphology of the intergranular ZrO₂ particles and the operation of several toughening mechanisms, with transformation toughening a relatively minor contributor.     

Transformation Zone Shape Effects on Crack Shielding in Ceria-Partially-Stabilized Zirconia (Ce-TZP)–Alumina Composites

Crack tip shielding is evaluated for observed transformation zones in Ce-TZP/Al₂O₃ composites, in which the transformation zone sizes were changed significantly by varying the sintering temperature to control the transformation yield stress. The calculated shielding effects are consistent with an observed insensitivity of crack resistance curves to transformation zone size; smaller zones in materials with higher yield stress were associated with larger ratios of wake length to zone width and correspondingly higher normalized shielding stress intensity factors. Shielding due to the dilatational component of the transformation strain accounted for most of the toughening observed in these materials.     

Mechanical Properties of Si3N4-SiC Three-Layer Composite Materials

The effects of microstructure and residual stress on the mechanical properties of Si₃N₄-based three-layer composite materials were investigated. The microstructure of each layer was controlled by the addition of two differently sized silicon carbides: fine SiC nanoparticles (∼200 nm) or relatively large SiC platelets (∼20 µm). When the SiC nanoparticles were added, the average grain size of Si₃N₄ was reduced because of the inhibition of grain growth by the particles. On the other hand, when the SiC platelets were added, the microstructure of Si₃N₄ was not much changed because of the large size of the platelets. Three-layer composites were fabricated by placing the Si₃N₄/SiC-nanoparticle layers on the surface of the Si₃N₄/SiC-platelet layer. The residual stress was controlled by varying the amount of SiC added. The mechanical properties of three-layer composites with various combinations of microstructure and residual stress level were investigated.