Reaction Hot Pressing of α'- and β'- SiAlON Ceramics

Hot pressing kinetics of α-Si₃N₄, AIN, Al₂O₃, and Y₂O₃ powder mixtures forming α'- and β'-SiAlONs have been studied. Densification proceeds in two steps, first by a small shrinkage upon ternary eutectic oxide melting (SiO₂–Al₂O₃–Y₂O₃) at 1340°C, followed by a massive particle rearrangement and further shrinkage at higher temperature when nitride dissolution begins. With better wettability, AIN initially traps the oxide melt and delays densification. In addition, the preferential dissolution of AIN at 1450°C enriches the melt composition in AI, triggering transient precipitation of supersaturated β'-SiAlON. Full densification is readily achieved at 1550°C without complete α-Si₃N₄ conversion.     

Sintering Kinetics at Isothermal Shrinkage: Effect of Specific Surface Area on the Initial Sintering Stage of Fine Zirconia Powder

The isothermal shrinkage behaviors of fine zirconia powders (containing 2.8–2.9 mol% Y₂O₃) with specific surface areas of about 6 and 16 m²/g were investigated to clarify the effect of specific surface area on the initial sintering stage. The shrinkage of powder compact was measured under constant temperatures in the range of 1000°–1100°C. The increase in specific surface area enhanced the densification rate with increasing temperature. The values of activation energy ( Q ) and frequency-factor term (β₀) of diffusion at initial sintering were estimated by applying the sintering-rate equation to the isothermal shrinkage data. The Q of diffusion changes little but the β₀ increases with the increase in specific surface area. It is therefore concluded that the increase in the specific surface area of fine zirconia powder enhances the shrinkage rate because of an increase in the β₀ at the initial stage of sintering.     

Densification of Nanocrystalline Yttria by Low Temperature Spark Plasma Sintering

We investigated the densification of undoped, nanocrystalline yttria (Y₂O₃) powder by spark plasma sintering (SPS) at sintering temperatures between 650°C and 1050°C at a heating rate of 10°C/min and an applied stress of 83 MPa. In spite of the low sinterability of the undoped Y₂O₃, a remarkable densification of the powder started at about 600°C, and a theoretical density of more than 97% was achieved at a sintering temperature of 850°C with a grain size of about 500 nm. The low temperature SPS is effective for fabricating dense Y₂O₃ polycrystals.     

Effect of Additives on the Pressureless Sintering of Aluminum Nitride between 1500° and 1800°C

Combined oxide additives (Y₂O₃, CaO, La₂O₃, CeO₂, SiO₂, TiO₂, and Fe₂O₃) were investigated as AIN sintering aids. AIN can be fully sintered at 1600°C to substantial thermal conductivity (92 W/(m·K)) using a multiple sintering aid of Y₂O₃, CaO, SiO₂, La₂O₃, and CeO₂. This lowtemperature material has small grain size (1 to 3 μm).     

Effect of Calcination on the Sintering of Gel-Derived, Zirconia-Toughened Alumina

The densification behavior of ZrO₂ (+ 3 mol% Y₂O₃)/85 wt% Al₂O₃ powder compacts, prepared by the hydrolysis of metal chlorides, can be characterized by a transition- and an α-alumina densification stage. The sintering behavior is strongly determined by the densification of the transition alumina aggregates. Intra-aggregate porosity, resulting from calcination at 800°C, partly persists during sintering and alumina phase transformation and negatively influences further macroscopic densification. Calcination at 1200°C, however, densifies the transition alumina aggregates prior to sintering and enables densification to almost full density (96%) within 2 h at 1450°C, thus obtaining a microstructure with an alumina and a zirconia grain size of 1 μm and 0.3–0.4 μm, respectively.     

Morphology and Sinterability of Thermally Treated Carbothermally Synthesized Silicon Nitride Powders

Carbothermally produced alpha-Si₃N₄ powder is thermally treated (1400°-1500°C for 4-12 h) in nitrogen-gas to determine the impact of thermal treatment on powder composition, particle size, morphology, and sinterability. Thermal treatment reduces residual carbon and oxygen content and reduces internal porosity (lower surface area), which results in a rounding of the particles. The lower oxygen content of the heat-treated, carbothermally produced alpha-Si₃N₄ powder allows Y₂O₃-Al₂O₃-SiO₂ sintering formulation to be adjusted so that an improvement in the early stage of densification can be achieved.     

A Simple Way to Synthesize Yttrium Aluminum Garnet by Dissolving Yttria Powder in Alumina Sol

A precursor for Y₃Al₅O₁₂ was synthesized as a YAG sol by simply dissolving Y₂O₃ powder in an alumina sol. Phase-pure Y₃Al₅O₁₂ powder was obtained by precipitating the YAG sol with an aqueous dilute ammonia solution followed by calcination at 1100°C. TG/DTA analysis showed an exotherm at 938°C attributed to formation of YAG phase and weight loss of 44% at 1000°C. XRD and FT-IR analysis showed that phase-pure YAG can be formed through noncrystalline and metastable hexagonal YAlO₃ without forming either yttrium or aluminum formate intermediate.     

EELS Study of Oxygen Diffusion in Aluminum Nitride

The oxygen/nitrogen interdiffusion in AIN ceramics was investigated by electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). AL₂O₃/AIN diffusion couples were prepared by oxidation of an AIN ceramic. The samples were annealed for different times in the temperature range from 1500° to 1900°C. The diffusion couples were encapsulated in a tantalum ampoule to guarantee an inert atmosphere. Oxygen concentration profiles across the oxide/nitride interface were measured by EELS. The oxygen/nitrogen interdiffusion coefficient in AIN is given by D = 1.5_–1.2^+6.0× 10^–8 exp[–240 ± 40 (kJ/mol)/( RT )] (cm²/s). The magnitude and temperature dependence of the N/O interdiffusion is comparable to diffusion coefficients reported in the literature for other non-oxide ceramic materials. At standard AIN sintering conditions the O/N interdiffusion is so slow that it cannot provide an effective means for oxygen removal from the AIN grains.     

High-Temperature Environmental Stability of the Compounds in the Al2O3–Y2O3 System

Heat treatments in several environments were performed on a series of compounds in the Al₂O₃ and Y₂O₃ system: Al₂O₃Y₃Al₅O₁₂ eutectic, Y₃Al₅O₁₂, YAlO₃, Y₄Al₂O₉, and Y₂O₃. The yttrium aluminates were found to be stable at high temperatures under vacuum and in air. However, when they were heat-treated under vacuum in proximity to SiC, degradation was observed. This was found to be primarily a result of carbothermal reduction. In a similarly reducing environment without Si, the yttrium aluminates, and Al₂O₃ and Y₂O₃, all exhibited degradation by carbothermal reduction. Based upon the experimental results, a degradation mechanism for yttrium aluminates was proposed.     

Bulk, Dense, Nanocrystalline Yttrium Aluminum Garnet by Consolidation of Amorphous Powders at Low Temperatures and High Pressures

Amorphous Al₂O₃–37.5% Y₂O₃ powders, prepared using spray pyrolysis followed by partial or complete thermal decomposition, were hot-pressed at 315°–640°C and 500 or 750 MPa uniaxial pressure. Hot pressing of fully decomposed amorphous powder at 450°–640°C at pressures up to 750 MPa led to densification (up to 96%) as well as nanocrystallization of yttrium aluminum garnet (YAG). When the pressure was applied during heating, instead of after reaching the final temperature, higher relative densities resulted. Fully crystalline starting powder did not densify. The low true density of the amorphous phase (3.1 g·cm⁻³) was believed to be responsible for the densification through enhanced ionic mobilities.     

Rapid Rate Sintering of Nanocrystalline ZrO2−3 mol% Y2O3

Conventional ramp-and-hold sintering with a wide range of heating rates was conducted on submicrometer and nanocrystalline ZrO₂–3 mol% Y₂O₃ powder compacts. Although rapid heating rates have been reported to produce high density/fine grain size products for many submicrometer and smaller starting powders, the application of this technique to ZrO₂–3 mol% Y₂O₃ produced mixed results. In the case of submicrometer ZrO₂–3 mol% Y₂O₃, neither densification nor grain growth was affected by the heating rate used. In the case of nanocrystalline ZrO₂–3 mol% Y₂O₃, fast heating rates severely retarded densiflcation and had a minimal effect on grain growth. The large adverse effect of fast heating rates on the densification of the nanocrystalline powder was traced to a thermal gradient/differential densification effect. Microstructural evidence suggests that the rate of densification greatly exceeded the rate of heat transfer in this material; consequently, the sample interior was not able to densify before being geometrically constrained by a fully dense shell which formed at the sample exterior. This finding implies that rapid rate sintering will meet severe practical constraints in the manufacture of bulk nanocrystalline ZrO₂–3 mol% Y₂O₃ specimens.     

Sintering of Silicon Nitride with YAIO3 Additive

Sintering of Si₃N₄ powder with the addition of a Y₂O₃+ Al₂O₃ mixture or YAlO₃ as sintering aids was investigated. Sintering was improved in the case of YAlO₃ additive compared to that for the Y₂O₃+ Al₂O₃ mixture. An initial delay in densification was most likely caused by heterogeneity of the liquid phase formed in the case of the separate oxide additions at temperatures above 1700°C.     

Sintering Kinetics at Isothermal Shrinkage: II, Effect of Y2O3 Concentration on the Initial Sintering Stage of Fine Zirconia Powder

The shrinkage behavior of fine zirconia powders containing 2.9 and 7.8 mol% Y₂O₃ was investigated to clarify the effect of Y₂O₃ concentration on the initial sintering stage. The shrinkage of powder compact was measured under both conditions of constant rates of heating (CRH) and constant temperatures. CRH measurements revealed that when the Y₂O₃ concentration of fine zirconia powder increased, the starting temperature of shrinkage shifted to a high temperature. Isothermal shrinkage measurements revealed that the increase in Y₂O₃ concentration causes the shrinkage rate to decrease. The values of activation energy ( Q ) and frequency-factor term (β₀) of diffusion at initial sintering were estimated by applying the sintering-rate equation to the isothermal shrinkage data. When the Y₂O₃ concentration increases, both Q and β₀ of diffusion increase. It is, therefore, concluded that the increase in Y₂O₃ concentration of fine zirconia powder decreases the shrinkage rate because of increasing Q of diffusion at the initial stage of sintering.     

Sintering Kinetics at Constant Rates of Heating: Effect of Al2O3 on the Initial Sintering Stage of Fine Zirconia Powder

The sinterabilities of fine zirconia powders including 5 mass% Y₂O₃ were investigated, with emphasis on the effect of Al₂O₃ at the initial sintering stage. The shrinkage of powder compact was measured under constant rates of heating (CRH). The powder compact including a small amount of Al₂O₃ increased the densification rate with elevating temperature. The activation energies at the initial stage of sintering were determined by analyzing the densification curves. The activation energy of powder compact including Al₂O₃ was lower than that of a powder compact without Al₂O₃. The diffusion mechanisms at the initial sintering stage were determined using the new analytical equation applied for CRH techniques. This analysis exhibited that Al₂O₃ included in a powder compact changed the diffusion mechanism from grain boundary to volume diffusions (VD). Therefore, it is concluded that the effect of Al₂O₃ enhanced the densification rate because of decrease in the activation energy of VD at the initial sintering stage.     

Improvement of Mechanical Properties and Corrosion Resistance of Porous β-SiAlON Ceramics by Low Y2O3 Additions

Addition of Y₂O₃ as a sintering additive to porous β-SiAlON (Si_{6− z} Al _z O _z N_{8− z} , z = 0.5) ceramics has been investigated for improved mechanical properties. Porous SiAlON ceramics with 0.05–0.15 wt% (500–1500 wppm) Y₂O₃ were fabricated by pressureless sintering at temperatures of 1700°, 1800°, and 1850°C. The densification, microstructure, and mechanical properties were compared with those of Y₂O₃-free ceramics of the same chemical composition. Although this level of Y₂O₃ addition did not change the phase formation and grain size, the grain bonding appeared to be promoted, and the densification to be enhanced. There was a significant increase in the flexural strength of the SiAlON ceramics relative to the Y₂O₃-free counterpart. After exposure in 1 M hydrochloric acid solution at 70°C for 120 h, no remarkable weight loss and degradation of the mechanical properties (flexural and compression strength) was observed, which was attributed to the limited grain boundary phase, and with the minor Y₂O₃ addition the supposed formation of Y-α-SiAlON.     

Effect of Heat Treatment on the Microstructure and Properties of Dense AIN Sintered with Y2O3 Additions

The secondary phase constitution in two sintered AIN ceramics (1.8% and 4.2% Y₂O₃ additions) was studied as a function of heat treatment temperatures between 1750° and 1900°C under pure nitrogen atmosphere. The effect of the phase constitution on the physical properties, such as density, thermal conductivity ( K ), and lattice constants, and on the mechanical properties in three-point bending, was also investigated. Y₃Al₅O₁₂ was found to getter dissolved oxygen from the AIN lattice below 1850°C, but evaporated at 1850°C and above. Y₄Al₂O₉ appeared to sublimate below 1850°C in the atmosphere used in this study. Depending on the secondary phase constitution, heat treatment affected thermal conductivity favorably or adversely. Occasionally, samples with similar lattice oxygen contents were found to have different thermal conductivities, suggesting that factors besides dissolved oxygen can also influence K . Lattice parameter measurements indicated that, within the small range of lattice oxygen concentrations in the AIN samples studied, the c-axis was more sensitive than the a -axis to oxygen content.     

Influence of Yttria–Alumina Content on Sintering Behavior and Microstructure of Silicon Nitride Ceramics

The present study investigates the influence of the content of Y₂O₃–Al₂O₃ sintering additive on the sintering behavior and microstructure of Si₃N₄ ceramics. The Y₂O₃:Al₂O₃ ratio was fixed at 5:2, and sintering was conducted at temperatures of 1300°–1900°C. Increased sintering-additive content enhanced densification via particle rearrangement; however, phase transformation and grain growth were unaffected by additive content. After phase transformation was almost complete, a substantial decrease in density was identified, which resulted from the impingement of rodlike β-Si₃N₄ grain growth. Phase transformation and grain growth were concluded to occur through a solution–reprecipitation mechanism that was controlled by the interfacial reaction.     

Effect of Europium Concentration on Densification of Transparent Eu:Y2O3 Scintillator Ceramics Using Hot Pressing

Europium (Eu) was found to act as a solid-state sintering aid in Y₂O₃ optical ceramics by controlling ionic diffusivity, which in turn leads to enhanced optical transparency. Transparent ceramic samples of Eu-doped Y₂O₃, with no additional additives, were sintered by uniaxial vacuum hot pressing under 40 MPa and maximum temperature of 1580°C. Optical attenuation was found to decrease with increasing Eu concentrations between 0 and 5 at% for ceramics processed under the same sintering conditions. In order to study the effect of Eu concentration on ceramic densification, the strain rate and grain size during sintering at constant temperature and varied pressure were measured. A diffusional flow densification model was used to derive instantaneous effective diffusion constants for the densification process. Diffusion constants were found to increase with increasing Eu concentration according to a log–linear relationship. Eu²⁺ was detected in samples after hot pressing through fluorescence spectroscopy, and the extrinsic defect chemistry was found to be dominated by the reduced Eu in solid solution with Y₂O₃. A sintering model with diffusion rate limited by yttrium interstitial transport and controlled by the incorporation of Eu²⁺ onto the cation sublattice was found to be in good agreement with experimental diffusivity data.     

Transparent Cr4+-Doped YAG Ceramics for Tunable Lasers

Transparent Cr⁴⁺:YAG (Y₃Al_SO₁₂) ceramics doped with Ca and Mg as counterions and SiO₂ as a sintering aid were fabricated by a solid-state reaction method using high-purity powders of Al₂O₃, Y₂O₃, and Cr₂O₃. The mixed powder compacts were sintered at 1750°C for 10 h in oxygen, or 1750°C for 10 h under vacuum, and then annealed at 1400°C for 10 h in oxygen. Cr-doped YAG ceramics sintered in oxygen had a brown color and characteristic absorption by Cr⁴⁺ ions, whereas these YAG ceramics sintered under different conditions (vacuum + oxygen) had a green color and absorption at ∼590 and 430 nm by Cr³⁺ ions. The absorption behavior of YAG ceramics sintered in oxygen was almost equivalent to that of Cr⁴⁺:YAG single crystals fabricated by the Czochralski method.     

Field-Assisted Densification of Superhard B6O Materials with Y2O3/Al2O3 Addition

B₆O is a possible candidate of superhard materials with a hardness of 45 GPa measured on single crystals. Up to now, densification of these materials was only possible at high pressure. However, recently it was found that Al₂O₃ can be utilized as an effective sintering additive, similar to the addition of Y₂O₃/Al₂O₃ that was used in this work. The densification behavior of the material as a function of applied pressure, its microstructure evolution, and the resulting mechanical properties were investigated. A strong dependence of the densification with increasing pressure was found. The material revealed characteristic triple junctions filled with amorphous residue composed of B₂O₃, Al₂O₃, and Y₂O₃, while no amorphous grain-boundary films were observed along internal interfaces. Mechanical testing revealed on average a hardness of 33 GPa, a fracture toughness of 4 MPa·m^1/2, and a strength value of 520 MPa.