Hot Isostatic Processing of Shocked Si3N4 Powder

To enhance the sinter ability of Si₃N₄, powders mixed with 0, 2, and 5 wt% Y₂O₃ were explosively shock-treated. Compacts of these powders were encapsulated in 96% silica glass containers and isostatically hot-pressed. The shocked Si₃N₄ with 5 wt% Y₂O₃ was pressed to a density of 3.09 g/cm³ (95.4% of theoretical) at 1400°C under 430 MPa for 3 h, whereas the unshocked material attained only 82.4% of theoretical density under the same hot isostatic pressing conditions.     

Microstructure and Property Characterization of Sintered Si3N4, SiC, and SiAlON

Commercially produced pressureless sintered Si₃N₄, SiC, and SiAlON were characterized with respect to density, phases present, bend strength, and oxidation resistance. The room-temperature bend strengths of sintered Si₃N₄, SiC, and SiAlON are comparable. However, the room-temperature strengths are much lower (=40 to 50%) than the room-temperature strength of hot–pressed Si₃N₄ (NC-132). The strength loss in Si₃N₄ and SiAlON materials at high temperature was attributed to a viscous grain-boundary phase retained during cooling from the sintering temperature. The oxidation resistance of sintered a-SiC was the best of any materials tested.     

Microstructural Observations on Hot-Pressed Si3N4

The development of microstructure in hot-pressed Si_aN₄ was studiehd for a typical Si₃N₄ powder with and without BeSiN₂ as a densification aid. The effect of hot-pressing temperature on density, α- to β-Si₃N₄ conversion and specific surface area showed that BeSiN₂ appears to increase the mobility of the system by enhancing densification, α- to β-Si₃N₄ transformation, and grain growth at temperatures between 1450° and 1800°. These processes appear to occur in the presence of a liquid phase.     

Microstructure and Creep Behavior of a Si3N4–SiC Micronanocomposite

The microstructure and its influence on the creep behaviour of carbon derived Si₃N₄-SiC micro/nanocomposite tested in bending at temperatures from 1200° to 1400°C in air has been studied. No phase and microstructure change after creep test implied that material is stable at tested temperature range. After creep test only partial crystallization of glassy intergranular phase has been observed. Creep parameters n close to 1, apparent activation energy around 350 kJ/mol together with TEM observation indicated that the main creep mechanisms is solution precipitation controlled by interface reaction in combination with grain boundary sliding caused by the amorphous intergranular phases present in microstructure. However, the grain boundary sliding is hindered by local SiC particles interlocking neighboring Si₃N₄ grains.     

Relation Between Strength, Fracture Energy, and Microstructure of Hot-Pressed Si3N4

A fracture mechanics approach was used to investigate the high strength of hot-pressed Si₃N₄. Room-temperature flexural strengths, fracture energies, and elastic moduli were determined for material fabricated from α- and β-phase Si₃N₄ powders. When the proper powder preparation technique was used, α-phase powder resulted in a high fracture energy (69,000 ergs/cm²), a high flexural strength (95,000 psi), and an elongated (fiberlike) grain morphology, whereas β-phase powder produced a low fracture energy (16,000 ergs/cm²), a relatively low strength (55,000 psi), and an equiaxed grain morphology. It was hypothesized that the high strength of Si₃N₄ hot-pressed from α-phase powder results from its high fracture energy, which is attributed to the elongated grains. High-strength Si₃N₄ has directional properties caused, in part, by the elongated grain structure, which is oriented preferentially with respect to the hot-pressing direction.     

Na2SO4-lnduced Corrosion of Si3N4 Coated with Chemically Vapor Deposited Ta2O5

Hot isostatically pressed Si₃N₄ was coated with chemically vapor-deposited Ta₂O₅, and subjected to oxidative and corrosive environments to determine the feasibility of using a Ta₂O₅ coating for protecting Si₃N₄ from hot corrosion. The coated structure was relatively stable at 1000^deg;C in pure O₂. However, the Ta₂O₅-Si₃N₄ system became unstable in an environment containing Na₂SO₄ and O₂ at 1000^deg;C because (1) Ta₂O₅ and Na₂SO₄ reacted rapidly to form NaTaO₃ and (2) subsequently NaTaO₃ interacted destructively with the underlying Si₃N₄ substrate to form a molten phase.     

High-Temperature Failure Mechanisms of Hot-Pressed Si3N4 and Si3N4/Si3N4-Whisker-Reinforced Composites

The high-temperature flexural strength of hot-pressed silicon nitride (Si₃N₄) and Si₃N₄-whisker-reinforced Si₃N₄-matrix composites has been measured at a crosshead speed of 1.27 mm/min and temperatures up to 1400°C in a nitrogen atmosphere. Load–displacement curves for whisker-reinforced composites showed nonelastic fracture behavior at 1400°C. In contrast, such behavior was not observed for monolithic Si₃N₄. Microstructures of both materials have been examined by scanning and transmission electron microscopy. The results indicate that grain-boundary sliding could be responsible for strength degradation in both monolithic Si₃N₄ and its whisker composites. The origin of the nonelastic failure behavior of Si₃N₄-whisker composite at 1400°C was not positively identified but several possibilities are discussed.     

Compressive Creep and Oxidation Resistance of an Si3N4 Material Fabricated in the System Si3N4-Si2N2O-Y2Si2O7

The compressive creep behavior and oxidation resistance of an Si₃N₄/Y₂Si₂O₇ material (0.85Si₃N₄+0.10SiO₂+0.05Y₂O₃) were determined at 1400°C. Creep re sistance was superior to that of other Si₃N₄ materials and was significantly in creased by a preoxidation treatment (1600°C /120 h). An apparent parabolic rate constant of 4.2 × 10⁻¹¹ kg²·m-⁴·s⁻¹ indicates excellent oxidation resistance.     

Mechanical Properties of Si3N4-SiC Three-Layer Composite Materials

The effects of microstructure and residual stress on the mechanical properties of Si₃N₄-based three-layer composite materials were investigated. The microstructure of each layer was controlled by the addition of two differently sized silicon carbides: fine SiC nanoparticles (∼200 nm) or relatively large SiC platelets (∼20 µm). When the SiC nanoparticles were added, the average grain size of Si₃N₄ was reduced because of the inhibition of grain growth by the particles. On the other hand, when the SiC platelets were added, the microstructure of Si₃N₄ was not much changed because of the large size of the platelets. Three-layer composites were fabricated by placing the Si₃N₄/SiC-nanoparticle layers on the surface of the Si₃N₄/SiC-platelet layer. The residual stress was controlled by varying the amount of SiC added. The mechanical properties of three-layer composites with various combinations of microstructure and residual stress level were investigated.     

Role of Si2N2O in the Passive Oxidation of Chemically-Vapor-Deposited Si3N4

The results of two-step oxidation experiments on chemically-vapor-deposited Si₃N₄ and SiC at 1350°C show that a correlation exists between the presence of a Si₂N₂O interphase and the strong oxidation resistance of Si₃N₄. During normal oxidation, k _p for SiC was 15 times higher than that for Si₃N₄, and the oxide scale on Si₃N₄ was found by SEM and TEM to contain a prominent Si₂N₂O inner layer. However, when oxidized samples are annealed in Ar for 1.5 h at 1500°C and reoxidized at 1350°C as before, three things happen: the oxidation k _p increases over 55-fold for Si₃N₄, and 3.5-fold for SiC; the Si₃N₄ and SiC oxidize with nearly equal k _p's; and, most significant, the oxide scale on Si₃N₄ is found to be lacking an inner Si₂N₂O layer. The implications of this correlation for the competing models of Si₃N₄ oxidation are discussed.     

Hot-Pressing Behavior of Si3N4

The densification behavior of Si₃N₄ containing MgO was studied in detail. It was concluded that MgO forms a liquid phase (most likely a magnesium silicate). This liquid wets and allows atomic transfer of Si₃N₄. Evidence of a second-phase material between the Si₃N₄ grains was obtained through etching studies. Transformation of α- to β-Si₃N₄ during hot-pressing is not necessary for densification.     

Carbothermic Synthesis of Monodispersed Spherical Si3N4/SiC Nanocomposite Powder

The synthesis and structure of a monodispersed spherical Si₃N₄/SiC nanocomposite powder have been studied. The Si₃N₄/SiC nanocomposite powder was synthesized by heating under argon a spherical Si₃N₄/C powder. The spherical Si₃N₄/C powder was prepared by heating a spherical organosilica powder in a nitrogen atmosphere and was composed of a mixture of nanosized Si₃N₄ and free carbon particles. During the heat treatment at 1450°C, the Si₃N₄/C powder became a Si₃N₄/SiC composite powder and finally a SiC powder after 8 h, while retaining its spherical shape. The composition of the Si₃N₄/SiC composite powder changed with the duration of the heat treatment. The results of TEM, SEM, and selected area electron diffraction showed that the Si₃N₄/SiC composite powder was composed of homogeneously distributed nanosized Si₃N₄ and SiC particles.     

Mechanical Behavior of MoSi2 Reinforced–Si3N4Matrix Composites

The mechanical behavior of MoSi₂ reinforced–Si₃N₄ matrix composites was investigated as a function of MoSi₂ phase content, MoSi₂ phase size, and amount of MgO densification aid for the Si₃N₄ phase. Coarse-phase MoSi₂-Si₃N₄ composites exhibited higher room-temperature fracture toughness than fine-phase composites, reaching values >8 MP·am^1/2. Composite fracture toughness levels increased at elevated temperature. Fine-phase composites were stronger and more creep resistant than coarse phase composites. Room-temperature strengths >1000 MPa and impression creep rates of ∼10⁻⁸ s⁻¹ at 1200°C were observed. Increased MgO levels generally were deleterious to MoSi₂-Si₃N₄ mechanical properties. Internal stresses due to MoSi₂ and Si₃N₄ thermal expansion coefficient mismatch appeared to contribute to fracture toughening in MoSi₂-Si₃N₄ composites.     

Strength of Hot Isostatically Pressed Si3N4 After Heat Treatment in Ar-O2 and H2-H2O

The effects of heat treatment in Ar-O₂ and H₂-H₂O atmospheres on the flexural strength of hot isostatically pressed Si₃N₄ were investigated. Increases in room-temperature strength, to values significantly above that of the aspolished material, were observed when the Si₃N₄ was exposed at 1400°C to (1) H₂ with water vapor pressure ( P _H2O) greater than 1 × 10⁻⁴ MPa or (2) Ar with oxygen partial pressure ( P _O2) of between 7 × 10⁻⁶ and 1.5 × 10⁻⁵ MPa. However, the strength of the material was degraded when the P _H2O in H₂ was lower than 1 × 10⁻⁴ MPa, and essentially unaffected when the P _O2 in Ar was higher than 1.5 × 10⁻⁵ MPa. We suggest that the observed strength increases are the result of strength-limiting surface flaws being healed by a Y₂Si₂O₇ layer formed during exposure.     

Oxidation and Strength Retention of Monolithic Si3N4 and Nanocomposite Si3N4-SiC with Yb2O3 as a Sintering Aid

The oxidation behaviors of monolithic Si₃N₄ and nanocomposite Si₃N₄-SiC with Yb₂O₃ as a sintering aid were investigated. The specimens were exposed to air at temperatures between 1200° and 1500°C for up to 200 h. Parabolic weight gains with respect to exposure time were observed for both specimens. The oxidation products formed on the surface also were similar, i.e., a mixture of crystalline Yb₂Si₂O₇ and SiO₂ (cristobalite). However, strength retention after oxidation was much higher for the nanocomposite Si₃N₄-SiC compared to the monolithic Si₃N₄. The SiC particles of the nanocomposite at the grain boundary were effective in suppressing the migration of Yb³⁺ ions from the bulk grain-boundary region to the surface during the oxidation process. As a result, depletion of yttribium ions, which led to the formation of a damaged zone beneath the oxide layer, was prevented.     

Properties of Si3N4 Produced by Nitriding Slip-Cast Si Containing Si3N4 Grog Additions

The properties of Si₃N₄ compositions produced by nitriding slip-cast Si bodies containing up to 16% Si₃N₄ grog were determined. The introduction of grog consistently lowered the densities, the room- and high-temperature strengths, and the resistance to oxidation. The open structure of the grog-containing mixes favored low-temperature gas-phase reactions leading to α-Si₃N₄ formation. In higher-density compositions containing predominantly Si, gas-liquid-solid reactions at higher temperatures produced a relatively greater content of the β phase.     

Chemical Degradation of Si3N4-Bonded SiC Sidelining Materials in Aluminum Electrolysis Cells

A thorough analysis of a silicon nitride (Si₃N₄)-bonded SiC sidelining material from a Hall-Heroult electrolysis cell is reported. Phase composition before and after chemical degradation of the material is obtained by quantitative analysis using Rietveld refinement of X-ray diffraction data and chemical analysis. The main degradation products as a result of the oxidation of Si₃N₄ binder phase are Si₂ON₂ in the upper part and Na₂SiO₃ in the lower part of the sidelining. The microstructure of α-Si₃N₄ (needle) and β-Si₃N₄ (shell) as well as the degradation products Si₂ON₂ (fiber) and Na₂SiO₃ (flake) were revealed by electron microprobe analysis. Chemical reactions and degradation mechanisms are proposed based on the presented findings. The degradation in the lower part is more severe than that in the upper part because Na diffusion from the cathode enhances the oxidation of Si₃N₄. The degradation changes the physical properties of Si₃N₄-bonded SiC such as density and porosity.     

Sintering of Si3N4-Y2O3 Under Nitrogen Pressure

This study shows that the amount ofAl₂O₃ needed to form high density Si₃N₄-15Y₂-O₃ samples can be reduced by using high surface area Si₃N₄ powder and high N₂ overpressure (high sintering temperatures) during the sintering process. The reduction in AI₂O₃ content results in improved oxidation resistance of the sintered samples.     

Reaction-Bonding Preparation of Si3N4/MoSi2 and Si3N4/WSi2 Composites from Elemental Powders

Si₃N₄/MoSi₂ and Si₃N₄/WSi₂ composites were prepared by reaction-bonding processes using as starting materials powder mixtures of Si-Mo and Si-W, respectively. A presintering step in an At-base atmosphere was used before nitriding for the formation of MoSi₂ and WSi₂; the nitridation in a N₂-base atmosphere was followed after presintering with the total stepwise cycle of 1350°C × 20 h +1400°C × 20 h +1450°C × 2 h. The final phases obtained in the two different composites were Si₃N₄ and MoSi₂ or WSi₂; no free elemental Si and Mo or W were detected by X-ray diffraction.     

Impurity Phases in Hot-Pressed Si3N4

Impurity phases in commercial hot-pressed Si₃N₄ were investigated using transmission electron microscopy. In addition to the dominant, β-Si₃N₄ phase, small amounts of Si₂N₂O, SiC, and WC were found. Significantly, a continuous grain-boundary phase was observed in the ∼ 25 high-angle boundaries examined. This film is ∼ 10 Å thick between, β-Si₃N₄ grains and ∼ 30 Å thick between Si₂N₂O and β-Si₃N₄ grains.