Effect of Yttrium and Erbium Ions on Epitaxial Phase Transformations in Alumina

The effect of low concentrations of Y, Er, and Cr solutes on the amorphous-to-γ transformation and on the γ-to-α transformation in aluminum oxide has been studied in situ by time-resolved reflectivity. The activation energies of the two transformations with these dopants are the same as in undoped alumina, being 4.1 ± 0.1 and 5.2 ± eV, respectively. Although not affecting the activation energies, Y, Er, and Cr do affect the transformation kinetics. Y and Cr ions decrease the γ-to-α transformation velocity and, over the limited range studied, do so in proportion to their concentration. Concentrations of Er as low as ∼6 ppm retard the γ-to-α transformation and concentrations of 32 ppm essentially stop the transformation occurring within the times and temperatures accessible within the present experiment, thereby preventing quantification of the effect of Er on the α-phase transformation. Erbium also retards the amorphous-to-γ transformation relative to undoped alumina whereas yttrium and chromium accelerate it.     

Physical Stabilization of the β→γ Transformation in Dicalcium Silicate

It has been shown that the monoclinic β -phase of dicalcium silicate (Ca₂SiO₄) can be stabilized against transformation to the orthorhombic γ -phase by physical rather than chemical factors. Stabilization was studied in different types of microstructures fabricated under various processing conditions such as different powder or grain sizes, chemical additives, cooling kinetics, or high-temperature annealing treatments. The observations can be explained in terms of a critical particle size effect controlling nucleation of the transformation. Rapid quenching through the high-temperature hexagonal ( α ) to orthorhombic ( a' _H) transformation at 1425°C, which is accompanied by a −4.7% volume decrease, causes periodic fracture of β -twins due to accumulated strains. Chemical doping with K₂O or Al₂O₃ promotes the formation of amorphous phases which mold themselves around β -Ca₂SiO₄ grains. Annealing treatments cause crystallization of the glass and subsequent transformation to the γ -phase.     

Controlled Gelation and Sintering of Monolithic Gels Prepared from γ-Alumina Fume Powder

The gelation, phase transformation, and densification of a colloidal monolithic gel made from γ-Al₂O₃ fume powder are investigated. Among the six gelation agents that we use, formamide and urea are quick in causing gelation and easy to burn off. The densification rate of this gel decreases rapidly after the γ-to-α phase transformation. TiO₂ is an effective sintering aid to overcome this bottleneck of densification because (1) it enhances the phase transformation rate so that the sintering of α-alumina occurs at a lower temperature, and (2) it promotes sintering rates at the initial and intermediate stages after phase transformation. On the other hand, MgO has an inappreciable effect on gel sintering. The effect of MgO at the final sintering stage is obstructed by this densification barrier after transformation. The titania-doped gel monoliths can be sintered to high density and fine microstructure at 1400°C.     

Duplex α,β-Sialon Ceramics Stabilized by Dysprosium and Samarium

Duplex αβ,-sialon ceramics with a minimum volume fraction of residual intergranular glass have been prepared using Dy or Sm as the α-sialon stabilizing element. These microstructures contained high aspect ratio β-sialon grains homogeneously distributed in an α-sialon matrix. A number of the larger α-sialon grains contained dislocations and showed a core/shell structure. Dy gave an α-sialon which was stable over a wide temperature range (1350–1800°C) for long holding times, while the use of Sm resulted in less stable α-sialon structures at medium temperatures (1450°C) and the formation of melilite, R₂Si_3−xAl_xO_3+xN_4−x, β-sialon, and the 21R sialon polytype during prolonged heating. High α-phase contents gave a very high hardness ( H _V10 is approximately 22 GPa) but a comparatively low indentation fracture toughness (around 4.4 MPam^1/2). Duplex sialons fabricated from powder mixtures corresponding to an α-to-β sialon ratio of around 50:50 resulted in a sialon material with a favorable combination of high hardness (around 22 GPa) and increased toughness (to around 5.5 MPam^1/2).     

Thermal Hysteresis for the α'L↫β Transformations in Strontium Oxide-Doped Dicalcium Silicates

A series of Sr-bearing Ca₂SiO₄ solid solutions (C₂S( ss )), (Sr _x Ca_1−x)₂SiO₄ with 0 ≤ x ≤ 0.12, was prepared. They were examined by high-temperature powder X-ray diffractome-try to determine the start and finish temperatures of the α'_L-to-β and β-to-α'_L martensitic transformations. The thermal hysteresis was positive with x < 0.045, nearly equal to zero at x = 0.045, and negative with x > 0.045. The zero and negative hysteresis were consistent with the thermoelasticity of the transformations. With increasing x from 0.02 to 0.08, the hysteresis decreased steadily from positive to negative, suggesting a continuous increment in the stored elastic energy.     

Preparation Method of Submicrometer-Sized α-Alumina by Surface Modification of γ-Alumina with Alumina Sol

A method is introduced to prepare almost-spherical submicrometer-sized α-alumina via surface modification of γ-alumina with an alumina sol. Milled γ-alumina, in the presence of 3 wt% of α-alumina with a median particle size ( d ₅₀) of 0.32 μm (AKP-30), produced irregularly shaped α-alumina with d ₅₀∼0.3 μm after heat treatment at 1100°C for 1 h. γ-alumina that had been surface-modified by milling in the presence of 3 wt% of the alumina sol resulted in almost-monosized, spherical α-alumina ∼0.3 μm in size after heat treatment at 1100°C for 1 h. Furthermore, almost-spherical α-alumina 0.1—0.2 μm in size was obtained by milling γ-alumina with 3 wt% of AKP-30 alumina in the presence of 3 wt% of the alumina sol, followed by heat treatment at 1100°C for 1 h. The alumina sol that has been introduced in this work seems to act as a dispersant, in addition to helping to form a spherical shape.     

High-Temperature Oxidation Behavior of High-Purity α-, β-, and Mixed Silicon Nitride Ceramics

High-temperature oxidation behavior, microstructural evolution, and oxidation kinetics of additive-free α-, β-, and mixed silicon nitride ceramics is investigated. The oxidation rate of the ceramics depends on the allotropic ratio; best oxidation resistance is achieved for ceramics rich in α-phase. Variations in the oxidation kinetics are directly related to average grain size and glass distribution in the oxidation scale. The oxygen contents incorporated into the Si₃N₄ phase before its dissolution at the oxidation front affects the local glass composition and thereby yields nucleation and growth rates of SiO₂ crystallites within the glass phase and a final oxidation scale microstructure, which depend on the incorporated oxygen contents. For the α-polymorph, the dynamic oxygen solubility is found to remain negligible; therefore, a nitrogen-rich glass forms at the oxidation front, which promotes devitrification and yields a scale with small grain size and thin intergranular glass films. β-Si₃N₄ is observed to form oxygen-rich solid solutions on oxidation, which are in contact with silicon oxynitride or oxygen-rich glass. Nucleation of cristobalite in the latter is sluggish, yielding coarse-grained oxidation scales with thick intergranular glass film.     

Effects of Amorphous and Crystalline SiO2 Additives on γ-Al2O3-to-alpha-Al2O3 Phase Transitions

This paper focused on the effects of various phases of SiO₂ additives on the γ-Al₂O₃-to-α-Al₂O₃ phase transition. In the differential thermal analysis, the exothermic peak temperature that corresponded to the theta-to-α phase transition was elevated by adding amorphous SiO₂, such as fumed silica and silica gel obtained from the hydrolysis of tetraethyl orthosilicate. In contrast, the peak temperature was reduced by adding crystalline SiO₂, such as quartz and cristobalite. Amorphous SiO₂ was considered to retard the γ-to-α phase transition by preventing γ-Al₂O₃ particles from coming into contact and suppressing heterogeneous nucleation on the γ-Al₂O₃ surface. On the other hand, crystalline SiO₂ accelerated the α-Al₂O₃ transition; thus, this SiO₂ may be considered to act as heterogeneous nucleation sites. The structural difference among the various SiO₂ additives, especially amorphous and crystalline phases, largely influenced the temperature of γ-Al₂O₃-to-α-Al₂O₃ phase transition.     

β→α Transformation in Polycrystalline SiC: I, Microstructural Aspects

The effects of annealing conventionally sintered, hot-pressed, and reaction-sintered Sic have been investigated by optical and transmission electron microscopy. In conventionally sintered and hot-pressed bodies, "composite" grains consisting of α-SiC plates sandwiched between recrystallized β-SiC envelopes grow rapidly into the fie-grained β matrix; thickening of these α plates within the p envelopes is relatively sluggish. The existence of the composite plates can be explained by the extreme anisot-ropy of the interfacial energy between β- and α-Sic: {111)β(000l)_α interfaces have energies several orders of magnitude lower than random β/α interfaces. In reaction-sintered Sic, this anisotropy is manifested by rapid growth of α seeds along their basal planes into the epitaxial β reaction product; slow growth occurs perpendicular to the basal planes.     

Liquid-Phase-Assisted Transformation of Seeded γ-Alumina

α-Al₂O₃-seeded, boehmite-derived γ-Al₂O₃ was transformed in the presence of V₂O₅, resulting in a 205°C decrease in the α-Al₂O₃ transformation temperature and a 74% reduction in the apparent activation energy for the γ- to α-Al₂O₃ transformation at temperatures greater than 850°C. These changes are attributed to the lowered energy barrier for nucleation by seeding and the lowered activation energy for material transport through the liquid relative to the unseeded, solid-state transformation. Growth of the transforming alumina yielded fine-grained α-Al₂O₃ particles which exhibited a highly faceted morphology. It is proposed that the combined control of both nucleation and growth during liquid-phase-assisted transformation provides a potentially powerful technique for tailoring powder characteristics in many material systems which undergo nucleation and growth processes.     

29Si MASNMR Spin-Lattice Relaxation Study of α-, β-, and Amorphous Silicon Nitride

The spin-lattice relaxation times, T ₁, in α-, β-, and amorphous Si₃N₄ have been obtained for the first time, using a multiple-pulse saturation recovery method. The saturation recovery of the ²⁹Si magnetization follows exponential behavior under magic-angle spinning conditions, within the limits of experimental error. A rather wide dispersion of T ₁ values is observed for the phases of Si₃N₄: 284 ± 29 min (–46.686 ppm) and 260 ± 23 min (–48.812 ppm) for the α-phase, 36 ± 4 min for the β-phase, and 11 ± 1 min for the amorphous phase, assuming an exponential recovery. The values obtained for the exponent in the power-law fitting are 0.599(9) (–46.686 ppm) and 0.61(1) (–48.812 ppm) for the α-phase, 0.52(2) for the β-phase, and 0.53(3) for the amorphous phase.     

Effect of Initial α-Phase Content on Microstructure and Mechanical Properties of Sintered Silicon Carbide

By using α- and β-SiC starting powders with similar particle sizes, the effects of initial α-phase content on the microstructure and the mechanical properties of the liquid-phase-sintered and subsequently annealed materials were investigated. The microstructures developed were analyzed by image analysis. When β-SiC powder was used, the grains became elongated. The average diameter decreased with increasing α-SiC content and the aspect ratio showed a maximum at 10%α-SiC and decreased with increasing α-SiC content in the starting powder. Such results suggest that microstructure can be controlled by changing α-phase content in starting powders. The strength increased with increasing α-SiC content in the starting powder while the fracture toughness decreased with increasing α-SiC content. There may be a trade-off in improving both the strength and toughness in SiC ceramics sintered with oxide additives.     

Electron Microscopy of Defects in Epitaxical β-SiC Thin Films Grown on Silicon and Carbon {0001} Faces of α-SiC Substrates

Defects present in β-SiC thin films epitaxically grown on hexagonal 6 H α-SiC substrates via chemical vapor deposition have been characterized by transmission electron microscopy. These defects are different from those previously observed in β-SiC films grown on (100) silicon, which were predominantly stacking faults and microtwins. The most common defects in the films grown on α-SiC were large domains rotated 60° with respect to each other and were identified as double positioning boundaries. These boundaries are a special type of incoherent twin boundary. Differences observed in films grown on either the silicon or carbon face of the {0001}α-SiC are characterized as a function of the mechanism of formation of the defects and type of substrate used for growth.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

β→α Transformation in Polycrystalline Sic: II, Interfacial Energetics

The β→α transformation in polycrystalline Sic occurs by the rapid growth of composite grains consisting of α-SiC plates "sandwiched" between grains of recrystallizedp-SiC. Growth of these composite grains into the fine-grained β matrix occurs much more rapidly than thickening of the α plates into their β"envelopes." A phenomenological analysis of the energetics of these several growth processes is presented and it is shown that the observations can be explained by the extreme anisotropy of the interfacial energy between β− and α−SiC; {lll}_β(0001)^α interfaces have much lower energies than random, β/α interfaces. In reaction-sintered Sic, this anisotropy is manifested by rapid growth of a seeds along their basal planes into the epitaxial β reaction product; slow growth occurs perpendicular to the basal planes.     

Synthesis of Nanosize-Necked Structure α- and γ-Fe2O3 and its Photocatalytic Activity

Highly dispersed nanometer-sized α-Fe₂O₃ (hematite) and γ-Fe₂O₃ (maghemite) iron oxide particles were synthesized by the combustion method. Ferric nitrate was used as a precursor. X-ray diffractometer study revealed the phase purity of α- and γ-Fe₂O₃. Both the products were characterized using field emission scanning electron microscope and transmission electron microscope for particle size and morphology. Necked structure particle morphology was observed for the first time in both the iron oxides. The particle size was observed in the range of 25–55 nm. Photodecomposition of H₂S for hydrogen generation was performed using α- and γ-Fe₂O₃. Good photocatalytic activity was obtained using α- and γ-Fe₂O₃ as photocatalysts under visible light irradiation.     

Effect of Monovalent Cation Additives on the γ-Al2O3-to-α-Al2O3 Phase Transition

The effect of monovalent cation addition on the γ-Al₂O₃-to-α-Al₂O₃ phase transition was investigated by differential thermal analysis, powder X-ray diffractometry, and specific-surface-area measurements. The cations Li⁺, Na⁺, Ag⁺, K⁺, Rb⁺, and Cs⁺ were added by an impregnation method, using the appropriate nitrate solution. β-Al₂O₃ was the crystalline aluminate phase that formed by reaction between these additives and Al₂O₃ in the vicinity of the γ-to-α-Al₂O₃ transition temperature, with the exception of Li⁺. The transition temperature increased as the ionic radii of the additive increased. The change in specific surface area of these samples after heat treatment showed a trend similar to that of the phase-transition temperature. Thus, Cs⁺ was concluded to be the most effective of the present monovalent additives for enhancing the thermal stability of γ-Al₂O₃. Because the order of the phase-transition temperature coincided with that of the formation temperature of β-Al₂O₃ in these samples, suppression of ionic diffusion in γ-Al₂O₃ by the amorphous phase containing the added cations must have played an important role in retarding the transition to α-Al₂O₃. Larger cations suppressed the diffusion reaction more effectively.     

Seeding with γ-Alumina for Transformation and Microstructure Control in Boehmite-Derived α-Alumina

The dehydration, transformation, and densification of boehmite (γ-AlOOH) are enhanced by addition of γ-Al₂O₃ seed particles. α-Al₂O₃ microstructures with uniform 1- to 2-μm grain size and sintered densities 98% of theoretical are achieved at 1300°C Thermal analysis shows that γ-Al₂O₃ seed particles transform to α-Al₂O₃ before the matrix, thus controllably nucleating the transformation of θ-AI₂O₃ to α-Al₂O₃.     

Microstructural Development During Gas-Pressure Sintering of α-Silicon Nitride

Gas-pressure sintering of α-Si₃N₄ was carried out at 1850 ° to 2000°C in 980-kPa N₂. The diameters and aspect ratios of hexagonal grains in the sintered materials were measured on polished and etched surfaces. The materials have a bimodal distribution of grain diameters. The average aspect ratio in the materials from α-Si₃N₄ powder was similar to that in the materials from β-Si₃N₄ powder. The aspect ratio of large and elongated grains was larger than that of the average for all grains. The development of elongated grains was related to the formation of large nuclei during the α-to-β phase transformation. The fracture toughness of gaspressure-sintered materials was not related to the α content in the starting powder or the aspect ratio of the grains, but to the diameter of the large grains. Crack bridging was the main toughening mechanism in gas-pressure-sintered Si₃N₄ ceramics.     

Mechanism of Grain Growth and α-β'Transformation During Liquid-Phase Sintering of β'-Sialon

The rates of grain coarsening and α-β'transformation during the liquid-phase sintering of Si₃N₄-β'₆₀-YAG sialon have been measured at varying liquid fractions and z values in order to determine the rate-controlling mechanism. The average β'-grain size after sintering for 16 h at 1650°C shows no variation with the liquid-matrix fraction if the z value is fixed and a marked increase with the z value if the liquid fraction is fixed. Similarly, the amount of untransformed α-phase after sintering for 2.5 or 3.5 min at 1600°C shows no variation with the liquid-matrix fraction if the z value is fixed and a marked decrease with the z value if the liquid fraction is fixed. These results show that the grain coarsening and the α-β'transformation are controlled by the interface reaction. This conclusion is consistent with the observations in carbide-Co systems and with the theoretical predictions that the growth of faceted grains is controlled by interface reaction and that of spherical grains by diffusion. A general rule between the shape and the growth mechanism of grains in a liquid matrix is thus proposed.