Synthesis and Properties of Porous Single-Phase β'-SiAlON Ceramics

Single-phase β'-SiAlON (Si_{6− z} Al _z O _z N_{8− z} , z = 0–4.2) ceramics with porous structure have been prepared by pressureless sintering of powder mixtures of á-Si₃N₄, AlN, and Al₂O₃ of the SiAlON compositions. A solution of AlN and Al₂O₃ into Si₃N₄ resulted in the β'-SiAlON, and full densification was prohibited because no other sintering additives were used. Relative densities ranging from 50%–90% were adjusted with the z -value and sintering temperature. The results of X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses indicated that single-phase β'-SiAlON free from a grain boundary glassy phase could be obtained. Both grain and pore sizes increased with increasing z -value. Low z -value resulted in a relatively high flexural strength.     

High-Temperature Properties of Mixed α'/β'-SiAlON Materials

The mechanical behavior of mixed α'/β'-SiAlON materials was studied at elevated temperatures. Two different α'/β'-SiAlON compositions along the Si₃N₄-Y₂O₃9AlN composition line in the Si₃N₄-Al₂O₃AlN-YN3AlN plane (α'-SiAlON plane) were prepared using three different raw-material mixtures. Six different materials were obtained with significantly lower values in α'-SiAlON than expected. The high-temperature properties of the materials studied were influenced strongly by the chemical composition (α' content and grain-boundary phase) of the SiAlONs. A high content of α'-SiAlON was beneficial in terms of creep behavior of the materials. The same materials, however, were characterized by a considerably degradated fracture behavior at elevated temperatures in air because of a crack-growth process enhanced by the poor oxidation resistance of these materials. It was concluded that, despite some superior features of the materials studied, a long-term application of mixed α'/β'-SiAlON materials at 1400°C in air is problematical. A combination of all properties required for such applications was not observed. For that reason, it is suggested that the real high-temperature potential of these materials in air should be limited to temperatures <1300°C.     

Synthesis and Characterization of β'-SiAlON Ceramics from Organosilicon Polymers

A polycarbosilane has been modified with aluminum alkoxide to obtain a new preceramic compound. The pyrolysis in NH₃ flow of this polyaluminocarbosilane leads to the formation of an amorphous Si-Al-O-N phase. The nitridation process has been followed by IR and ²⁹Si MAS-NMR spectroscopies. A fine-grained β-SiAION ceramic is obtained by firing the amorphous phase at 1500°C. The crystallization process has been studied by XRD, ²⁹Si MAS-NMR, and TEM techniques.     

Nucleation and Growth of α'-SiAlON on α-Si3N4

Morphology, composition, and growth defects of α'-SiAION have been studied in a fine-grained material with an overall composition Y_0.33Si₁₀Al₂O₁N₁₅ prepared from α-Si₃N₄, AlN, Al₂O₃, and Y₂O₃ powders. TEM analysis has shown that fully grown α'-SiAloN grains always contain an α-Si₃N₄ core, implicating heterogeneous nucleation operating in the present system. The growth mode is epitaxial, despite the composition and lattice parameter difference between α-Si₃N₄ and α'-SiAlON. The inversion boundary that separates two domains in the seed crystal is seen to continue in the grown α'-SiAION. Lacking a special growth habit, the growth typically proceeds from more than one site on the seed crystal, and the different growth fronts impinge on each other to give an equiaxed appearance of α'-SiAlON. Misfit dislocations on the α/α'interface are identified as [0001] type ( b = 5.62 Å) and 1/3 [1 2 10] type ( b = 7.75 Å). These nucleation and growth characteristics dictate that microstructural control of α'-SiAlON must rest on the size distribution of the starting α-Si₃N₄ powder.     

Edge-Defined Film-Fed Growth of β-Alumina and Mg-Substituted β-Alumina

High Na vapor pressure, peritectic decomposition, and high reactivity of the melt complicate the growth of α-alumina crystals. These difficulties were overcome by using a high-pressure (300 psig) growth chamber, Na₂O-rich melts, and Ir for all surfaces in contact with the melt. These procedures were combined with the edge-defined film-fed growth technique to produce single-crystal β alumina tubes and ribbons.     

Topotactic Growth of β-Alumina on α-Alumina

Thin foils of polycrystalline α-alumina were reacted with a potassium-rich vapor at ≤900°C. Potassium β-alumina formed along α-alumina grain boundaries and protruded from holes in the foils. Conventional transmission electron microscopy was used to analyze the α-alumina/β-alumina phase boundary for possible orientation relations.     

Phase Relationships and Stability of α'-SiAlON

Phase diagrams on the α'-SiAlON plane have been investigated for ytterbium-, yttrium-, and neodymium-containing systems at different temperatures. Phase relationships between α'-SiAlON, β'-SiAlON, AlN polytypoids, and liquid/grain-boundary phases have been determined. The stability region of the α'-SiAlON phase increases as the temperature increases and the ionic size of the rare-earth cation decreases. Meanwhile, the solubility of aluminum and oxygen in β'-SiAlON varies with the solubility of aluminum and oxygen in α'-SiAlON, which causes migration of all the phase lines on the α'-plane toward the nitrogen-rich side at lower temperatures and with larger modifying cations. These systematic variations of the phase relationships fully explain the occurrence of α'→β' reverse transformations that are sometimes observed in this system.     

Transparent Hafnia-Containing β-Quartz Glass Ceramics: Nucleation and Crystallization Behavior

Heterogeneous nucleation and crystallization of lithium alumosilicate glasses with hafnia-containing nucleation agents was explored. Kinetic, thermodynamic, and structural data were considered to assess nucleation efficiency and to characterize the crystallization process. It is shown how lattice parameters and, particularly, anisotropy of the nuclei phase depend on the amount of ZrO₂–HfO₂ substitution in a specific base glass. For a given crystallization treatment, the size of the derived crystallites of β-quartz structure is used as a measure of nucleation rates. A nonlinear dependence of nucleation efficiency on HfO₂ content was established, with the supposedly most efficient nucleation corresponding to the lowest degree of anisotropy of the nuclei crystallites, i.e., when about 20%–30% of ZrO₂ was substituted by HfO₂. Apparent activation energies and estimates of the Avrami coefficient were determined from nonisothermal crystallization experiments for selected compositions to highlight the differences between hafnia and zirconia. Hafnia can be used alone or in combination with other agents to nucleate nanocrystalline glass ceramics with a low coefficient of thermal expansion.     

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.     

Mechanism of Grain Growth of β-SiAlON

The mechanism for grain growth of β-SiAlON has been investigated by annealing high-density β-SiAlON–YAG materials at 1650°C. An observed decrease in grain growth with increasing weight fraction of liquid confirms a diffusion-controlled growth mechanism in the system. The grain-growth mechanism is further characterized by the development of large elongated grains in addition to smaller grains. After prolonged heating, an equilibrium maximum grain size is developed causing a homogenization of the microstructure.     

Hydration of Sodium β- and β'-Aluminas

The enthalpy and entropy for the hydration of sodium β - and β '-aluminas have been determined by measuring the infrared absorbance of single-crystal samples following equilibration at elevated temperatures in water vapor pressures ranging from 3 to 70 kPa. The equilibrium water concentrations can be varied continuously and reversibly up to saturation concentrations of about 0.9H₂O-Na_1.2AI₁₁O_17.1 for the β-phase and 0.4H₂O.Na_1.67Mg_.67Al_10.33O₁₇ for the β'-phase. The hydration reactions are exothermic; Δ H =−56 ± 2 for sodium β '-aIumina and ΔH =−67 ± 2 kJ/mol for sodium β-alumina. The entropies of hydration are about −143 ± 6 J/(mol-K) for both sodium β - and β '-aIuminas.     

Grain Growth During Gas-Pressure Sintering of β-Silicon Nitride

The microstructures of gas-pressure-sintered materials from β-Si₃N₄ powder were characterized in terms of the diameter and aspect ratio of the grains. The size distributions of diameters in materials fabricated by heating for 1 h at 1850° to 2000°C were nearly constant when they were normalized by average diameters because of normal grain growth. The rate-determining step in the densification and grain growth was expected to be the diffusion of materials through the liquid phase. The activation energy for grain growth was 372 kJ/mol. The average aspect ratio of the grains was 3 to 4, whereas that of large grains was smaller because of shape accommodation. The fracture toughness was about the same as that of material from α-Si₃N₄ powder despite the smaller aspect ratio of the grains     

Thermal Expansion of Synthetic β-Spodumene and β-Spodumene—Silica Solid Solutions

Synthetic β-Spodumene and several β-Spodumene-silica solid solutions were prepared, and their thermal expansion behavior was studied using high-temperature X-ray diffraction techniques. Data indicate that all β-Spodumenes are characterized by a pronounced anisotropy of thermal expansion much the same as that of the silica polymorph keatite. Anisotropy increases slightly and the volume expansion decreases as the compositions become richer in SiO₂. Specimens with more than 80.8 wt% SiO₂ at 130O°C and 1 atm contain P-cristobalite along with β-Spodumene. The lattice parameters of β-Spodumene compositions throughout the solid solution range were determined. The structural aspects of the anisotropy of thermal expansion are discussed.     

Nonequiaxial Grain Growth and Polytype Transformation of Sintered α-Silicon Carbide and β-Silicon Carbide

α(6 H )- and β(3 C )-SiC powders were sintered with the addition of AlB₂ and carbon. α-SiC powder could be densified to ∼98% of the theoretical density over a wide range of temperatures from 1900° to 2150°C and with the additives of 0.67–2.7 mass% of AlB₂ and 2.0 mass% of carbon. Sintering of the β-SiC powder required a temperature of >2000°C for densification with these additives. Grains in the α-SiC specimens grew gradually from spherical-shaped to plate-shaped grains at 2000°C; the 6 H polytype transformed mainly to 4 H . On the other hand, grains in the β-SiC largely grew at >2000°C; the 3 C polytype transformed to 4 H , 6 H , and 15 R . The stacking faults introduced in grains were denser in β-SiC than in α-SiC. The rapid grain growth in the β-SiC specimen was attributed to polytype transformation from the unstable 3 C polytype at the sintering temperature.     

Synthesis of Kelp-Like Crystalline β-SiC Nanobelts and their Apical Growth Mechanism

Novel kelp-like crystalline β-SiC nanobelts have been synthesized through direct pyrolysis of methyltrichlorosilane at 600°C in an autoclave. The products are characterized by X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, electron diffraction, and Raman spectroscopy. On the basis of morphology and structural characterization, an apical growth mechanism is proposed to clarify the formation of as-prepared nanobelts. Also, at 420 nm, a broad peak is observed in the visible photoluminescence emission.     

Growth of Twinned β -Silicon Carbide Whiskers by the Vapor-Liquid-Solid Process

Whiskers of twinned SiC in the cubic form were produced by the vapor-liquid-solid process as a byproduct of the corrosion of silicon nitride. These whiskers were characterized and their properties related to their use in reinforced materials.     

Phase Equilibrium Investigations on Na–K–(β+β")-Alumina

The activities of Na₂O and K₂O dissolved in mixed-alkali Na–K–(β+β")-Al₂O₃ (NKBA) have been determined by using yttria stabilized zirconia (YSZ) as a solid electrolyte in the following galvanic cells: The approach enables to verify in situ the establishment and maintenance of the β/β"-equilibrium, and to characterize it as a function of the phase composition of NKBA. The results can be expressed as follows:      

In Situ Growth of β-SiC Nanowires in Porous SiC Ceramics

Polycarbosilane (PCS) was used as a precursor to prepare porous silicon carbide (SiC) ceramics with in situ growth of β-SiC nanowires. The pore size of the as-prepared porous ceramics was 1.37 μm in average, and had a narrow distribution. The nanowires with diameters ranging from ∼10 to 50 nm existed in the channels of the porous body. Their morphology, microstructure, and composition were characterized by field emission scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy, which confirmed that the nanowires had a single-crystal β-SiC structure with the 〈111〉 growth direction. A vapor–liquid–solid process was discussed as a possible growth mechanism of the β-SiC nanowires.