Kinetics and Microstructural Evolution of Heterogeneous Transformation of θ-Alumina to α-Alumina

Ultrafine (<0.1 μm) high-purity θ-Al₂O₃ powder containing 3–17.5 mol%α-Al₂O₃ seeds was used to investigate the kinetics and microstructural evolution of the θ-Al₂O₃ to α-Al₂O₃ transformation. The transformation and densification of the powder that occurred in sequence from 960° to 1100°C were characterized by quantitative X-ray diffractometry, dilatometry, mercury intrusion porosimetry, and transmission and scanning electron microscopy. The relative bulk density and the fraction of α phase increased with annealing temperature and holding time, but the crystal size of the α phase remained ∼50 nm in all cases at the transformation stage (≤1020°C). The activation energy and the time exponent of the θ to α transformation were 650 ± 50 kJ/mol and 1.5, respectively. The results implied the transformation occurred at the interface via structure rearrangement caused by the diffusion of oxygen ions in the Al₂O₃ lattice. A completely transformed α matrix of uniform porosity was the result of appropriate annealing processes (1020°C for 10 h) that considerably enhanced densification and reduced grain growth in the sintering stage. The Al₂O₃ sample sintered at 1490°C for 1 h had a density of 99.4% of the theoretical density and average grain size of 1.67 μm.     

Densification Behavior in Microwave-Sintered Silicon Nitride at 28 GHz

Si₃N₄ powders were sintered using a 28 GHz gyrotron source, with Y₂O₃, Al₂O₃, and MgO as sintering aids, in an attempt to investigate the effect of microwave radiation on densification behavior. The microwave-sintered samples were compared with identical samples produced by conventional pressureless sintering. The effect of sintering on the microstructural development and grain growth of the samples was assessed using scanning electron microscopy. Phase transformation behavior was assessed using X-ray diffractometry. In the microwave-sintered samples, densification and α→β transformation occurred at temperatures ∼200°C lower than those of the conventionally sintered samples. More importantly, at comparable stages of densification, the microstructures of the microwave-sintered and conventionally sintered samples were significantly different, with the microwave-sintered samples showing the development of elongated β grains at a much earlier stage of the α→β transformation. It was concluded that the effect of microwave radiation on sintering was not simply a decrease in sintering temperatures, but in possibly a different sintering mechanism, clearly related to localized heating within the grain-boundary phase.     

Novel Two-Step Sintering Process to Obtain a Bimodal Microstructure in Silicon Nitride

A two-step sintering process is described in which the first step suppresses densification while allowing the α-to-β phase transformation to proceed, and the second step, at higher temperatures, promotes densification and grain growth. This process allows one to obtain a bimodal microstructure in Si₃N₄ without using β-Si₃N₄ seed crystals. A carbothermal reduction process was used in the first step to modify the densification and transformation rates of the compacts consisting of Si₃N₄, Y₂O₃, Al₂O₃, and a carbon mixture. The carbothermal reduction process reduces the oxygen:nitrogen ratio of the Y-Si-Al-O-N glass that forms, which leads to the precipitation of crystalline oxynitride phases, in particular, the apatite phase. Precipitation of the apatite phase reduces the amount of liquid phase and retards the densification process up to 1750°C; however, the α-to-β phase transformation is not hindered. This results in the distribution of large β-nuclei in a porous fine-grained β-Si₃N₄ matrix. Above 1750°C, liquid formed by the melting of apatite resulted in a rapid increase in densification rates, and the larger β-nuclei also grew rapidly, which promoted the development of a bimodal microstructure.     

In S/Yu-Toughened Silicon Carbide-Titanium Carbide Composites

A process based on liquid-phase sintering and subsequent annealing for grain growth is presented to obtain in situ -toughened SiC-30 wt% TiC composites. Its microstructures consist of uniformly distributed elongated α-SiC grains, matrixlike TiC grains, and yttrium aluminum garnet (YAG) as a grain boundary phase. The composites were fabricated from β-SiC and TiC powders with the liquid forming additives of A1₂O₃ and Y₂O₃ by hot pressing. During the subsequent heat treatment, the β→α phase transformation of SiC led to the in situ growth of elongated α-SiC grains. The fracture toughness of the SiC-30 wt% TiC composites after 6-h annealing was 6.9 MPa-m^1/2, approximately 60% higher than that of as-hot-pressed composites (4.4 MPa-m^1/2). Bridging and crack deflection by the elongated α-SiC grains appear to account for the increased toughness of this new class of composites.     

Nd2O3-Doped Sialons with ZrO2/ZrN Additions Formed by Sintering and Hot Isostatic Pressing

β-sialon and Nd₂O₃-doped α-sialon materials of varying composition were prepared by sintering at 1775° and 1825°C and by glass-encapsulated hot isostatic pressing at 1700°C. Composites were also prepared by adding 2–20 wt% ZrO₂ (3 mol% Nd₂O₃) or 2–20 wt% ZrN to the β-sialon and α-sialon matrix, respectively. Neodymium was found to be a fairly poor α-sialon stabilizer even within the α-phase solid solution area, and addition of ZrN further inhibited the formation of the α-sialon phase. A decrease in Vickers hardness and an increase in toughness with increasing content of ZrO₂(Nd₂O₃) or ZrN were seen in both the HIPed β-sialon/ZrO₂(Nd₂O₃) composites and the HIPed Nd₂O₃-stabiIized α-sialons with ZrN additions.     

Densification and Grain Growth of Al2O3 Nanoceramics During Pressureless Sintering

α - Al₂O₃ nanopowders with mean particle sizes of 10, 15, 48, and 80 nm synthesized by the doped α-Al₂O₃ seed polyacrylamide gel method were used to sinter bulk Al₂O₃ nanoceramics. The relative density of the Al₂O₃ nanoceramics increases with increasing compaction pressure on the green compacts and decreasing mean particle size of the starting α-Al₂O₃ nanopowders. The densification and fast grain growth of the Al₂O₃ nanoceramics occur in different temperature ranges. The Al₂O₃ nanoceramics with an average grain size of 70 nm and a relative density of 95% were obtained by a two-step sintering method. The densification and the suppression of the grain growth are achieved by exploiting the difference in kinetics between grain-boundary diffusion and grain-boundary migration. The densification was realized by the slower grain-boundary diffusion without promoting grain growth in second-step sintering.     

Grain Growth of α-SiAlON in the Calcium-Doped System

Two calcium-doped α-SiAlON compositions (Ca_0.6Si_10.2Al_1.8−O_0.6N_15.4 and Ca_1.8Si_6.6Al_5.4O_1.8N_14.2) were prepared by hot pressing at 1600° and 1500°C, respectively, for complete phase transformation from α-Si₃N₄ to α-SiAlON. Both samples were subsequently fired at different temperatures for different periods of time to study the grain growth of α-SiAlON. Elongated α-SiAlON grains were developed in both samples at high temperatures. The kinetics of grain growth was investigated based on the variations in length and width of the α-SiAlON grains under different sintering conditions. Different growth rates were found between the length and width directions of the α-SiAlON crystals, resulting in anisotropic grain growth in the microstructural development.     

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 α to β (β') Phase Transition on the Sintering of Silicon Nitride Ceramics

By using α-Si₃N₄ and β-Si₃N₄ starting powders with similar particle size and distribution, the effect of α-β (β') phase transition on densification and microstructure is investigated during the liquid-phase sintering of 82Si₃N₄·9Al₂O₃·9Y₂O₃ (wt%) and 80Si₃N₄·13Al₂O₃·5AIN·5AIN·2Y₂O₃. When α-Si₃N₄ powder is used, the grains become elongated, apparently hindering the densification process. Hence, the phase transition does not enhance the densification.     

Densification of Si3N4 with LiYO2 Additive

This paper deals with the densification and phase transformation during pressureless sintering of Si₃N₄ with LiYO₂ as the sintering additive. The dilatometric shrinkage data show that the first Li₂O- rich liquid forms as low as 1250°C, resulting in a significant reduction of sintering temperature. On sintering at 1500°C the bulk density increases to more than 90% of the theoretical density with only minor phase transformation from α-Si₃N₄ to β-Si₃N₄ taking place. At 1600°C the secondary phase has been completely converted into a glassy phase and total conversion of α-Si₃N₄ to β-Si₃N₄ takes place. The grain growth is anisotropic, leading to a microstructure which has potential for enhanced fracture toughness. Li₂O evaporates during sintering. Thus, the liquid phase is transient and the final material might have promising mechanical properties as well as promising high-temperature properties despite the low sintering temperature. The results show that the Li₂O−Y₂O₃ system can provide very effective low-temperature sintering additives for silicon nitride.     

Seeding of the Reaction-Bonded Aluminum Oxide Process

The effect of the initial α-Al₂O₃ particle size in the reaction-bonded aluminum oxide (RBAO) process on the phase transformation of aluminum-derived γ-Al₂O₃ to α-Al₂O₃, and subsequently densification, was investigated. It has been demonstrated that if the initial α-Al₂O₃ particles are fine (∼0.2 μm, i.e., 2.9 × 10¹⁴γ-Al₂O₃ particles/cm³), then they seed the phase transformation. The fine α-Al₂O₃ decreases the transformation temperature to ∼962°C and results in a finer microstructure. The smaller particle size of the seeded RBAO decreases the sintering temperature to as low as ∼1135°C. The results confirm that seeding can be utilized to improve phase transformations and densification and subsequently to tailor final microstructures in RBAO-derived ceramics.     

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.     

Hot Isostatic Press Sintering and Properties of Silicon Nitride without Additives

Fully densified silicon nitride without additives was fabricated by means of hot isostatic pressing. The sintering process of highly pure powder was investigated with special interest in the evolution of α–β phase transformation, densification, and microstructure development. It was observed that the transformation occurred without a liquid phase below 1730°C, which corresponds to the melting point of SiO₂. Above 1730°C, the densification and β-grain elongation accelerated concurrently because of the appearance of liquid SiO₂. However, full densification was attained at 1950°C together with marked grain growth. Flexural strength, microhardness, fracture toughness, and Young's modulus of sintered bodies were measured as a function of temperature. In the sintered body started from highly pure powder, excellent MOR behavior was found up to 1400°C. Impurity content of a few hundred ppm was found to be sufficient to make densification easy and to degrade high-temperature strength.     

Effects of α-Sic versus β-Sic Starting Powders on Microstructure and Fracture Toughness of Sic Sintered with Al2O3-Y2O3 Additives

Dense Sic ceramics were obtained by pressureless sintering of β-Sic and α-Sic powders as starting materials using Al₂O₃-Y₂O₃ additives. The resulting microstructure depended highly on the polytypes of the starting SiC powders. The microstructure of SiC obtained from α-SiC powder was composed of equiaxed grains, whereas SiC obtained from α-SiC powder was composed of a platelike grain structure resulting from the grain growth associated with the β→α phase transformation of SiC during sintering. The fracture toughness for the sintered SiC using α-SiC powder increased slightly from 4.4 to 5.7 MPa.m^1/2 with holding time, that is, increased grain size. In the case of the sintered SiC using β-SiC powder, fracture toughness increased significantly from 4.5 to 8.3 MPa.m^1/2 with holding time. This improved fracture toughness was attributed to crack bridging and crack deflection by the platelike grains.     

SiAION Ceramics

The phase relations in and physical properties of SiAlON ceramics prepared by the hot isostatic pressing technique or by pressureless sintering with a sintering aid are reviewed. The sintering aid used is an AIN and Al₂O₃ mixture either pure or in combination with Y₂O₃ and/or various rare-earth oxides. Special attention is paid to the amount and type of phase(s) formed and to how properties such as hardness (HV10), fracture toughness ( K _IC), and oxidation resistance vary with the sintering aid used for different types of SiAlON materials, i.e., O'-, almost monophasic α-, pure β-, and mixed (α+β)-SiAION Ceramics.     

Effect of Rare Earth Oxide Additives on the Phase Transformation Rates of Si3N4

Fully dense Si₃N₄ sintered with rare-earth (RE=La, Nd, Gd, and Yb) oxide additives were fabricated by hot pressing. They were mainly composed of the α-phase, which enabled the investigation of the α–β transformation kinetics without the effect of porosity. The phase transformation kinetics was found to be linear. The activation energies for the phase transformation were 677, 546, 487, and 424 kJ/mol for RE=La, Nd, Gd, and Yb, respectively, and showed a good correlation with the ionic radii of RE atoms, which was discussed in conjunction with the segregation behaviors of RE atoms at the interface.     

Transformation and Densification of Nanocrystalline θ-Alumina during Sinter Forging

The sinter forging behavior of α-Al₂O₃ seeded and unseeded nanocrystalline θ-Al₂O₃ was investigated as a function of temperature, stress, and strain rate. Seeded samples exhibited the highest degree of plastic deformation during the θ- to α-AI₂O₃ phase transformation. As a result, microstructure control, increased densification, and a higher degree of transformation were obtained. A uniform microstructure of 150 nm α-Al₂O₃ grains developed, reaching 57% relative density after sintering 1.5 wt%α-Al₂O₃ seeded samples for 30 min at 1060°C. When sinter forged at 0.25 mm/min to 63 MPa and 1060°C for 30 min large deformations during the phase transformation increased the relative density to 74%. When the stress was increased to 235 MPa (1060°C, 30 min), 99.7% dense α-Al₂O₃ with a grain size of 230 nm was obtained. By increasing the sinter forging temperature to 1150°C, 99.5% relative density was achieved at 190 MPa for 30 min.     

Effect of Alumina Additions on Microstructural Aspects of the β to α Transformation in Tantalum (V) Oxide

Tantalum (V) oxide (Ta₂O₅) has potential applications as part of an environmental barrier coating system for Si₃N₄-based turbine components. However, at elevated temperatures, Ta₂O₅ undergoes a phase transformation from the orthorhombic (β) phase to the tetragonal phase (α), which is undesirable because of the associated volume change. The purpose of the present work was to study the effect of alumina additions (0–5 wt%) on the β to α transformation temperature, and associated modifications to the Ta₂O₅ microstructure. Sintered microstructures were characterized using SEM (scanning electron microscopy), and XRD (X-ray diffraction) was used to identify the phases present at room temperature. It was found that for undoped Ta₂O₅, transformation of the low-temperature β-phase begins at ∼1300°C, and leads to extensive microcracking of the sintered sample. For samples containing alumina, an increase in the transformation temperature was observed. The solubility limit of alumina in Ta₂O₅ was between 1 and 3 wt%; for samples in which this was exceeded, the AlTaO₄ second and phase particles were seen to be highly effective at inhibiting grain growth.     

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.     

Grain Growth in Sintered ZnO and ZnO-Bi2O3 Ceramics

Grain growth in a high-purity ZnO and for the same ZnO with Bi₂O₃ additions from 0.5 to 4 wt% was studied for sintering from 900° to 1400°C in air. The results are discussed and compared with previous studies in terms of the phenomenological kinetic grain growth expression: G ⁿ— G ⁿ₀= K ₀ t exp(— Q/RT ). For the pure ZnO, the grain growth exponent or n value was observed to be 3 while the apparent activation energy was 224 ± 16 kJ/mol. These parameters substantiate the Gupta and Coble conclusion of a Zn²⁺ lattice diffusion mechanism. Additions of Bi₂O₃ to promote liquidphase sintering increased the ZnO grain size and the grain growth exponent to about 5, but reduced the apparent activation energy to about 150 kJ/mol, independent of Bi₂O₃ content. The preexponential term K ₀ was also independent of Bi₂O₃ content. It is concluded that the grain growth of ZnO in liquid-phase-sintered ZnO-Bi₂O₃ ceramics is controlled by the phase boundary reaction of the solid ZnO grains and the Bi₂O₃-rich liquid phase.