Diffusion Bonds between a Stainless Steel and Zirconia

Extremely strong diffusion bonds can be made directly between Y₂O₃-stabilized TZP ZrO₂ and Fe─18Cr─8Ni stainless steel above a critical joining temperature of about 1100°C. Fracture initiates at the metal/ceramic interface with plasticity occurring in the metal. Bonding is accompanied by a thin interfacial reaction layer which may possibly lead to local melting during the bonding cycle. This behavior is similar to that observed with Ni─Cr alloys bonded to TZP ZrO₂, but a less vigorous interfacial reaction occurs with stainless steel, and stronger bonds can be made.     

Characterization of Interfacial Reactions Between β-Al2O3 and Y2O3-Partially-Stabilized ZrO2

The interfacial reaction between Y₂O₃-partially-stabilized ZrO₂ and α-Al₂O₃ was studied. It was noted that α-Al₂O₃ forms inside the periphery of the β-Al₂O₃ grains; its formation suggests the loss of Na₂O from the p-Al₂O₃, either by evaporation or by dissolution in the ZrO₂ matrix. The presence of Na₂ZrO₃ is suspected.     

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.     

Mechanism of ZrTiO4 Synthesis by Mechanochemical Processing of TiO2 and ZrO2

High-energy ball milling initiates a solid-state reaction in an equimolar mixture of TiO₂ and ZrO₂. The first stage of ball milling induced the transformation of anatase TiO₂ to high-pressure phase TiO₂ (II), isostructural with ZrTiO₄. The formation of solid solutions monoclinic ZrO₂/TiO₂ and TiO₂ (II)/ZrO₂ was observed in the intermediate stage. Afterward, a nanosized ZrTiO₄ phase was formed in the milled product from the TiO₂ (II)/ZrO₂ solid solution. The sintering of the milled product at a temperature <1100°C was examined in situ by Raman spectroscopy. The full solid-state reaction toward ZrTiO₄ ceramic is completed at a temperature considerably lower than reported in the literature.     

Interfacial Reactions between Sapphire and Silver—Copper—Titanium Thin Film Filler Metal

Wetting and brazing studies of sputtering-deposited, submicrometer thin film filler metal in an Ag—Cu—Ti/Al₂O₃ system were performed. The interfacial reaction layer between the filler metal and Al₂O₃ was investigated. It is possible to make a brazing joint even with a reaction layer of less than 100 nm thickness. Different types of interfacial reaction layers were observed when the Ti content in the filler metal was varied. The Cu—Ti—O system compounds were observed in the samples with high wetting capabilities, but not in the sample with low wetting characteristics. It was found that these compounds are substances that promote effective brazing.     

Microstructure and Short-Term Oxidation of Hot-Pressed Si3N4/ZrO2(+Y2O3) Ceramics

Composite ceramic materials based on Si₃N₄ and ZrO₂ stabilized by 3 mol% Y₂O₃ have been formed using aluminum isopropoxide as a precursor for the Al₂O₃ sintering aid. Densification was carred out by hot-pressing at temperatures in the range 1650° to 1800°C, and the resulting micro-structures were related to mechanical properties as well as to oxidation behavior at 1200°C. Densification at the higher temperatures resulted in a fibrous morphology of the Si₃N₄ matrix with consequent high room-temperature toughness and strength. Decomposition of the ZrO₂ grains below the oxidized surface during oxidation introduced radial stresses in the subscalar region, and from the oxidation experiments it is suggested that the ZrO₂ incorporated some N during densification.     

Transient Thermal Stress Behavior in ZrO2-Toughened Al2O3

The initial strength of (σ_i) and thermal shock resistances (Δ T_c and σ_r/σ_i), as determined by quench tests, of Al₂O₃-ZrO₂ composites are increased by increasing amounts of tetragonal ZrO₂ second phase for contents of up to ∼15 vol%. For composites with ≤9 vol% ZrO₂ the increases in σ_r and Δ T_c reflect the increase in γ_IC with addition of ZrO₂ However, for ZrO₂contents >9 vol%, the thermal shock resistances (Δ T_c and σ_r/σ_i) and σ_i are also affected by machining-induced microcracking in the surface of the samples. For ZrO₂ contents >14 vol%, bulk microcracking can become extensive and result in a degradation of σ_i and Δ T_c .     

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.     

Microstructural Evolution in a ZrO2 Wt% Y2O3 Ceramic

Several unusual microstructural features, i.e., 90° tetragonal ZrO₂ twins containing antiphase domain boundaries, tetragonal ZrO₂ precipitates in a colony morphology, and precipitate-free zones at the perimeter of cubic ZrO₂ grains containing fine tetragonal ZrO₂ precipitates, were observed in a single ZrO₂-12 wt% Y₂O₂ ceramic annealed at 1550°, 1400°, and 1250°C, respectively. The type of phase transformation responsible for each microstructural feature is described.     

Structure of Incoherent ZrO2/Al2O3 Interfaces

High-resolution electron microscopy was used to image incoherent ZrO₂/Al₂O₃ interfaces in ZrO₂-toughened Al₂O₃ containing intragranular ZrO₂. These particles are generally spherical but are sometimes faceted. High-resolution electron micrographs provide atomic-level information on the interfacial structure. For spherical particles, both ledgelike images and misfit dislocation-like images accommodated the lattice misfit, depending on the orientation of the interface, while faceted particles imply at least one low-energy ZrO₂/Al₂O₃ interface.     

Metastable Phase Formation in Plasma-Sprayed ZrO2 (Y2O3)–Al2O3

Rapidly solidified ZrO₂ (Y₂O₃)–Al₂O₃ powders were prepared by melting fine-particle aggregates in a high-enthalpy plasma flame and then rapidly quenching them in cold water or on a copper chill plate. To ensure complete melting and homogenization of all the particles before quenching, the water-quenching treatment was often repeated two or even three times. The resulting melt-quenched powders and splats displayed a variety of metastable structures, depending on composition and cooling rate. ZrO₂-rich material developed an extended solid solution phase, whereas eutectic material formed a nanofibrous or amorphous structure. Under high cooling rate conditions, the ZrO₂-rich material developed a nanocomposite structure ( t -ZrO₂+α-Al₂O) directly by melt-quenching, whereas, more typically, such a structure was developed only after postannealing of the as-quenched metastable material.     

Strength-Toughness Relations in Sintered and Isostatically Hot-Pressed ZrO2-Toughened Al2O3

The fracture toughness of fine-grained undoped ZrO₂-toughened Al₂O₃ (ZTA) was essentially unchanged by postsintering hot isostatic pressing and increased monotonically with ZrO₂ additions up to 25 wt%. The strength of ZTA with 5 to 15 wt% tetragonal ZrO₂, which depended monotonically on the amount of ZrO₂ present before hot isostatic pressing, was increased by pressing but became almost constant between 5 and 15 wt% ZrO₂ addition. The strength appeared to be controlled by pores before pressing and by surface flaws after pressing; the size of flaws after pressing increased with ZrO₂ content. The strength of ZTA containing mostly monoclinic ZrO₂ (20 to 25 wt%) remained almost constant despite the noticeable density increase upon hot isostatic pressing because the strength was controlled by preexisting microcracks whose extent did not change on postsintering pressing. These strength-toughness relations in sintered and isostatically hot-pressed ZTA are explained on the basis of R -curve behavior. The importance of the contribution of microcracks to the toughness of ZTA is emphasized.     

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.     

Al2TiO5-ZrTiO4-ZrO2 Composites: A New Family of Low-Thermal-Expansion Ceramics

The characterization and properties of ceramic composites containing the phases Al₂TiO₅, ZrTiO₄, and ZrO₂ are described. The range of compositions investigated gives very low average thermal expansions (α_24–1000°C as low as −2.0 × 10⁻⁶°C⁻¹) and excellent high-temperature stability. The low thermal expansions are apparently due to a combination of microcracking by the titanate phases and a contractive phase transformation by the ZrO₂. The crystal chemistry and microstructure of the product are processing dependent. Although the composites represent a complex microcracking system, the low thermal expansions and high-temperature stability make them potential candidates for commercial applications requiring thermal shock resistance.     

Crystallization of MgO-Al2O3-SiO2-ZrO2 Glasses

The crystallization of MgO-Al₂O₃-SiO₂-ZrO₂ glasses at 1000°C was studied. Isothermal heat treatments of a cordierite-based glass (2MgO.2Al₂O₃.5SiO₂= Mg₂Al₄Si₅O₁₈) with 7 wt% ZrO₂ produced surface crystallization of α-cordierite and tetragonal ZrO₂ ( t -ZrO₂). These phases advanced into the glass by cocrystallization of t -ZrO₂ rods in an α-cordierite matrix with a well-defined orientation relation. The t -ZrO₂ rods were unstable with respect to diffusional breakup (a Rayleigh instability) and decomposed into rows of aligned ellipsoidal and spheroidal particles. The t -ZrO₂ was very resistant to transformation to monoclinic symmetry. With a similar glass containing 15 wt% ZrO₂, surface crystallization of α-cordierite and t -ZrO₂ was accompanied by internal crystallization of t -ZrO₂ dendrites. Transformation of the dendrites to mono-clinic symmetry was observed under some conditions.     

High-Temperature Strength and Fracture Toughness of Y2O3-Partially-Stabilized ZrO2/Al2O3 Composites

The temperature dependence of bending strength, fracture toughness, and Young's modulus of composite materials fabricated in the ZrO₂ (Y₂O₃)-Al₂O₃ system were examined. The addition of A1203 enhanced the high-temperature strength. Isostatically hot-pressed, 60 wt% ZrO₂ (2 mol% Y₂O₃)/40 wt% Al₂O₃ exhibited an extremely high strength, 1000 MPa, at 1000°C.     

Transformation Kinetics of Ba2Ti9O20 with ZrO2 Additive

Pure Ba₂Ti₉O₂₀ (BT29) was synthesized by a solid-state reaction in one step with various amounts of ZrO₂ powder additive. The transformation kinetics of BT29 were investigated by quantitative X-ray diffractometry (XRD). The results show that stoichiometric powder mixtures transform to the BT29 phase by nucleation and growth mechanism between 1200° and 1300°C with 1.0 mol% ZrO_2. The activation energy of the transformation was found to be 620±60 kJ/mol, but decreases to 515±30 kJ/mol when doped with 1.0 mol% ZrO₂. The addition of ZrO₂ possibly changes the phase transformation mechanism of BT29 from diffusion controlled to interface controlled.     

Modification of αAI2O3 Platelet/ZrO2 Matrix Interface by Epitaxial Growth of β-AI2O3 on the α-AI2O3

An epitaxial β-alumina crystal growth method was used to modify α-AI₂O₃ platelet surfaces before inclusion as a reinforcing phase in partially stabilized zirconia (3Y-TZP). The as-grown surface phase was Na-β"-AI₂O₃. This was converted to Ca-β"-AI₂O₃ by ion exchange, as the latter is more temperature-stable at composite sintering temperatures. The conditions of formation, thermal stability, and chemical compatibility of these interfacial phases were examined. α-AI₂O₃ platelets with Ca-β"-AI₂O₃ film were incorporated into 3Y-TZP. The β"-AI₂O₃/ZrO₂ interface was found to promote platelet debonding and pullout, thus enhancing the α-AI₂O₃ platelet/crack interactions during the fracture process.     

Stability of Ultrafine Tetragonal ZrO2 Coprecipitated with Al2O3 by the Spray-ICP Technique

The transformation of ultrafine powders (particle size, 0.01 to 0.04 μm) of the system ZrO_2–Al₂O₃, prepared by spraying their corresponding nitrate solutions into an inductively coupled plasma (ICP) of ultrahigh temperature, was investigated. The powders were composed of metastable tetragonal ZrO₂ ( mt- ZrO₂) and γ-Al₂O₃. On heating, the mt- ZrO₂ (or tetragonal ZrO₂, t -ZrO₂) was retained up to 1200°C. At 1380°C the transformation to monoclinic ZrO₂ ( m -ZrO₂) occurred and the amount of the m -ZrO₂ decreased with the increase in Al₂O₃ content, thus indicating the stabilization of the t -ZrO₂ by the Al₂O₃, which seems to be explained in terms of the retardation of grain growth.     

Preparation and Properties of Ternary Ti3AlC2 and its Composites from Ti–Al–C Powder Mixtures With Ceramic Particulates

A layered ternary carbide phase, Ti₃AlC₂, was synthesized by hot pressing from the starting materials of Ti, aluminum, and activated carbon at 1400°C for 2 h. Its composites were also fabricated through addition of micro-sized SiC and partially stabilized zirconia particulates to the pulverized Ti₃AlC₂ powders. The polycrystalline Ti₃AlC₂ ceramic obtained has a flexural strength of 172 MPa and a fracture toughness of 4.6 MPa·m^1/2, respectively. This compound is relatively soft (Vikers hardness of 2.7 GPa) and exhibits good electrical conductivity with an electrical resistivity of 8.2 μΩ·m. Both the Ti₃AlC₂/SiC and Ti₃AlC₂/ZrO₂ composites are superior to the monolithic Ti₃AlC₂ ceramic in strength, fracture toughness, and micro-hardness.