Microstructure and Mechanical Properties of the in situβ-Si3N4/α'-SiAlON Composite

The in situ β-Si₃N₄/α'-SiAlON composite was studied along the Si₃N₄–Y₂O₃: 9 AlN composition line. This two phase composite was fully densified at 1780°C by hot pressing Densification curves and phase developments of the β-Si₃N₄/α'-SiAlON composite were found to vary with composition. Because of the cooperative formation of α'-Si AlON and β-Si₃N₄ during its phase development, this composite had equiaxed α'-SiAlON (∼0.2 μm) and elongated β-Si₃N₄ fine grains. The optimum mechanical properties of this two-phase composite were in the sample with 30–40%α', which had a flexural strength of 1100 MPa at 25°C 800 MPa at 1400°C in air, and a fracture toughness 6 Mpa·m^1/2. α'-SiAlON grains were equiaxed under a sintering condition at 1780°C or lower temperatures. Morphologies of the α°-SiAlON grains were affected by the sintering conditions.     

Microstructure and Properties of Self-Reinforced Silicon Nitride

Problems associated with manufacturing Si₃N₄/SiC-whisker composites have been overcome by developing selfreinforced Si₃N₄ with elongated β-Si₃N₄ grains formed in situ from oxynitride glass. This Si₃N₄–Y₂O₃–MgO–SiO₂–CaO-based material has a flexure strength >1000 MPa and fracture toughness >8 MPa·m^½. The optimum combination of mechanical properties has been obtained with Y₂O₃:MgO ratios ranging from 3:1 to 1:2, CaO contents ranging from 0.1 to 0.5 wt%, and Si₃N₄ contents between 90 and 96 wt%.     

Fabrication and Mechanical Properties of Silicon Carbide-Silicon Nitride Composites with Oxynitride Glass

A microstructure that consisted of uniformly distributed, elongated β-Si₃N₄ grains, equiaxed β-SiC grains, and an amorphous grain-boundary phase was developed by using β-SiC and alpha-Si₃N₄ powders. By hot pressing, elongated β-Si₃N₄ grains were grown via alpha right arrow β phase transformation and equiaxed β-SiC grains were formed because of inhibited grain growth. The strength and fracture toughness of SiC have been improved by adding Si₃N₄ particles, because of the reduced defect size and the enhanced bridging and crack deflection by the elongated β-Si₃N₄ grains. Typical flexural-strength and fracture-toughness values of SiC-35-wt%-Si₃N₄ composites were 1020 MPa and 5.1 MPam^1/2, respectively.     

Effect of Grain Growth of β-Silicon Nitride on Strength, Weibull Modulus, and Fracture Toughness

β-Si₃N₄ powder containing 1 mol% of equimolar Y₂O₃–Nd₂O₃ was gas-pressure sintered at 2000°C for 2 h (SN2), 4 h (SN4), and 8 h (SN8) in 30-MPa nitrogen gas. These materials had a microstructure of " in-situ composites" as a result of exaggerated grain growth of some β Si₃N₄ grains during firing. Growth of elongated grains was controlled by the sintering time, so that the desired microstructures were obtained. SN2 had a Weibull modulus as high as 53 because of the uniform size and spatial distribution of its large grains. SN4 had a fracture toughness of 10.3 MPa-m^1/2 because of toughening provided by the bridging of elongated grains, whereas SN8 showed a lower fracture toughness, possibly caused by extensive microcracking resulting from excessively large grains. Gas-pressure sintering of β-Si₃N₄ powder was shown to be effective in fostering selective grain growth for obtaining the desired composite microstructure.     

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.     

Microstructural Control of a 70% Silicon Nitride– 30% Barium Aluminum Silicate Self-Reinforced Composite

The processing response of a 70% silicon nitride–30% barium aluminum silicate (70%-Si₃N₄–30%-BAS) ceramic-matrix composite was studied using pressureless sintering, at temperatures ranging from 1740°C, which is below the melting point of BAS, to 1950°C. The relationship between the processing parameters and the microstructural constituents, such as morphology of the β-Si₃N₄ whisker and crystallization of the BAS matrix, was evaluated. The mechanical response of this array of microstructures was characterized for flexural strength, as well as fracture behavior, at test temperatures up to 1300°C. The indentation method was used to estimate the fracture resistance, and R -curves were obtained from modified compact-tension samples of selected microstructures at room temperature.     

Design, Fabrication, and Characterization of Silicon Nitride Particle-Reinforced Silicon Nitride Matrix Composites by Chemical Vapor Infiltration

Silicon nitride particle-reinforced silicon nitride matrix composites were fabricated by chemical vapor infiltration (CVI). The particle preforms with a bimodal pore size distribution were favorable for the subsequent CVI process, which included intraagglomerate pores (0.1–4 μm) and interagglomerate pores (20–300 μm). X-ray fluorescence results showed that the main elements of the composites are Si, N, and O. The composite is composed of α-Si₃N₄, amorphous Si₃N₄, amorphous SiO₂, and a small amount of β-Si₃N₄ and free silicon. The α-Si₃N₄ transformed into β-Si₃N₄ after heat treatment at 1600°C for 2 h. The flexural strength, dielectric constant, and dielectric loss of the Si₃N_4(p)/Si₃N₄ composites increased with increasing infiltration time; however, the pore ratios decreased with increasing infiltration time. The maximum value of the flexural strength was 114.07 MPa. The dielectric constant and dielectric loss of the composites were 4.47 and 4.25 × 10⁻³, respectively. The present Si₃N_4(p)/Si₃N₄ composite is a good candidate for high-temperature radomes.     

Fabrication of Si3N4/SiC Composite by Reaction-Bonding and Gas-Pressure Sintering

Si₃N₄/SiC composite materials have been fabricated by reaction-sintering and postsintering steps. The green body containing Si metal and SiC particles was reaction-sintered at 1370°C in a flowing N₂/H₂ gas mixture. The initial reaction product was dominated by alpha-Si₃N₄. However, as the reaction processed there was a gradual increase in the proportion of β-Si₃N₄. The reaction-bonded composite consisting of alpha-Si₃N₄, β-Si₃N₄, and SiC was heat-treated again at 2000°C for 150 min under 7-MPa N₂ gas pressure. The addition of SiC enhanced the reaction-sintering process and resulted in a fine microstructure, which in turn improved fracture strength to as high as 1220 MPa. The high value in flexural strength is attributed to the formation of uniformly elongated β-Si₃N₄ grains as well as small size of the grains (length = 2 μm, thickness = 0.5 μm). The reaction mechanism of the reaction sintering and the mechanical properties of the composite are discussed in terms of the development of microstructures.     

Influence of Phase Formation on Dielectric Properties of Si3N4 Ceramics

The influence of phase formation on the dielectric properties of silicon nitride (Si₃N₄) ceramics, which were produced by pressureless sintering with additives in MgO–Al₂O₃–SiO₂ system, was investigated. It seems that the difference in the dielectric properties of Si₃N₄ ceramics sintered at different temperatures was mainly due to the difference of the relative content of α-Si₃N₄, β-Si₃N₄, and the intermediate product (Si₂N₂O) in the samples. Compared with α-Si₃N₄ and Si₂N₂O, β-Si₃N₄ is believed to be a major factor influencing the dielectric constant. The high-dielectric constant of β-Si₃N₄ could be attributed to the ionic relaxation polarization.     

Texture Development in Silicon Nitride–Silicon Oxynitride In Situ Composites via Superplastic Deformation

Silicon nitride–silicon oxynitride (Si₃N₄–Si₂N₂O) in situ composites have been fabricated via either the annealing or the superplastic deformation of sintered Si₃N₄ that has been doped with a silica-containing additive. In this study, quantitative texture measurements, including pole figures and X-ray diffraction patterns, are used in conjunction with scanning electron microscopy and transmission electron microscopy techniques to examine the degree of preferred orientation and texture-development mechanisms in these materials. The results indicate that (i) only superplastic deformation can produce strong textures in the β-Si₃N₄ matrix, as well as Si₂N₂O grains that are formed in situ ; (ii) texture development in the β-Si₃N₄ matrix mainly results from grain rotation via grain-boundary sliding; and (iii) for Si₂N₂O, a very strong strain-dependent texture occurs in two stages, namely, preferred nucleation and anisotropic grain growth.     

Fracture Energies of Tape-Cast Silicon Nitride with β-Si3N4 Seed Addition

The fracture energies of the tape-cast silicon nitride with and without 3 wt% rod-like β-Si₃N₄ seed addition were investigated by a chevron-notched-beam technique. The material was doped with Lu₂O₃–SiO₂ as sintering additives for giving rigid grain boundaries and good heat resistance. The seeded and tape-cast silicon nitride has anisotropic microstructure, where the fibrous grains grown from seeds were preferentially aligned parallel to the casting direction. When a stress was applied parallel to the fibrous grain alignment direction, the strength measured at 1500°C was 738 MPa, which was almost the same as room temperature strength 739 MPa. The fracture energy of the tape-cast Si₃N₄ without seed addition was 109 and 454 J/m² at room temperature and 1500°C, respectively. On the contrary, the fracture energy of the seeded and tape-cast Si₃N₄ was 301 and 781 J/m² at room temperature and 1500°C, respectively, when a stress was applied parallel to the fibrous gain alignment. The large fracture energies were attributable primarily to the unidirectional alignment fibrous Si₃N₄ grains.     

Superplastic Deformation in Silicon Nitride–Silicon Oxynitride In Situ Composites

Starting with a mixture of ultrafine β-Si₃N₄ and a SiO₂-containing additive, a superplastic Si₃N₄-based composite was developed, using the concept of a transient liquid phase. Significant deformation-induced phase and microstructure evolutions occurred in the nonequilibrium, fine-grained Si₃N₄ material, which led to the in situ development of a Si₃N₄–22-vol%-Si₂N₂O composite and strong texture formation. The unusual ductility of the composites with elongated Si₂N₂O grains was attributed to the fine-grained microstructure, the presence of a transient liquid phase, and the alignment of the elongated Si₂N₂O grains. The mechanical properties of the resultant composite were enhanced rather than impaired by superplastic deformation and subsequent heat treatment; the resultant composite exhibited both high strength (957 MPa) and high fracture toughness (4.8 MPa·m^1/2).     

Effect of Sintering Additives on Microstructure and Mechanical Properties of Porous Silicon Nitride Ceramics

Porous silicon nitride (Si₃N₄) ceramics with about 50% porosity were fabricated by pressureless sintering of α-Si₃N₄ powder with 5 wt% sintering additive. Four types of sintering aids were chosen to study their effect on the microstructure and mechanical properties of porous Si₃N₄ ceramics. XRD analysis proved the complete formation of a single β-Si₃N₄ phase. Microstructural evolution and mechanical properties were dependent mostly on the type of sintering additive. SEM analysis revealed the resultant porous Si₃N₄ ceramics as having high aspect ratio, a rod-like microstructure, and a uniform pore structure. The sintered sample with Lu₂O₃ sintering additive, having a porosity of about 50%, showed a high flexural strength of 188 MPa, a high fracture toughness of 3.1 MPa·m^1/2, due to fine β-Si₃N₄ grains, and some large elongated grains.     

Residual α–Si3N4 in O' Crystals in CeO2-Doped O'+β' SiAlON Ceramics

The microstructure of a pressureless sintered (1605°C, 90 min) O'+β' SiAlON ceramic with CeO₂ doping has been investigated. It is duplex in nature, consisting of very large, slablike elongated O' grains (20–30 μm long), and a continuous matrix of small rodlike β' grains (< 1.0 μm in length). Many α-Si₃N₄ inclusions (0.1–0.5 μm in size) were found in the large O' grains. CeO₂-doping and its high doping level as well as the high Al₂O₃ concentration were thought to be the main reasons for accelerating the reaction between the α-Si₃N₄ and the Si-Al-O-N liquid to precipitate O'–SiAlON. This caused the supergrowth of O' grains. The rapid growth of O' crystals isolated the remnant α–Si₃N₄ from the reacting liquid, resulting in a delay in the α→β-Si₃N₄ transformation. The large O' grains and the α-Si₃N₄ inclusions have a pronounced effect on the strength degradation of O'+β' ceramics.     

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.     

Combustion Synthesis of Si3N4–SiC Composite Powders

Fine Si₃N₄-SiC composite powders were synthesized in various SiC compositions to 46 vol% by nitriding combustion of silicon and carbon. The powders were composed of α-Si₃N₄, β-Si₃N₄, and β-SiC. The reaction analysis suggested that the SiC formation is assisted by the high reaction heat of Si nitridation. The sintered bodies consisted of uniformly dispersed grains of β-Si₃N₄, β-SiC, and a few Si₂N₂O.     

Barium Aluminosilicate Reinforced In Situ with Silicon Nitride

Advanced ceramic composite materials that exhibit high strength and toughness with good thermal shock resistance are needed for emerging high-temperature engineering applications. A recently developed in situ reinforced barium aluminosilicate glass-ceramic shows promise of meeting many of the requirements for these types of applications with the added benefit of low-cost fabrication through densification by pressureless sintering. The material is toughened through in situ growth of rodlike β-Si₃N₄ grains resulting from the α–β silicon nitride phase transformation. Microstructural development and material properties for temperatures up to 1400°C are discussed. When compared to monolithic barium aluminosilicate, barium aluminosilicate reinforced with 70% by volume of Si₃N₄ shows a significant increase in flexural strength (from 80 to 565 MPa) and fracture toughness (from 1.8 to 5.74 MPa·m^1/2) with a high resistance to thermal shock.     

Bimodal Microstructure in Silicon Nitride–Barium Aluminum Silicate Ceramic-Matrix Composites by Pressureless Sintering

A distinct bimodal microstructure has been obtained in a Si₃N₄–BAS (barium aluminum silicate) ceramic-matrix composite by pressureless sintering. It is shown that the addition of coarse β-Si₃N₄ seeds causes abnormal grain growth in this composite, and hence encourages the formation of a bimodal microstructure. This abnormal grain growth is due to the nature of the heterogeneous nucleation mechanism in Si₃N₄α-to-β phase transformation, and is promoted by the transformation. After complete phase transformation, further abnormal grain growth is comparably slow and governed by the Ostwald ripening mechanism. Therefore, a stable bimodal microstructure can be easily achieved by pressureless sintering.     

Electron Microscopy Study of the Effect of Iron in Reaction-Sintered Silicoa Nitride

The microstructure, crystal structure, and chemical composition of reaction-sintered Si₃N₄ containing iron were studied using conventional and scanning transmission electron microscopy. It was found that the grains of β -Si₃N₄ were large and blocklike with well-developed facets, a series of voids along some grain boundaries, a subgrain of iron silicide near the periphery, and penetration of iron silicide into the three-grain junctions and grain boundaries. At some distance from each β -Si₃N₄ grain was a region of small α-Si₃N₄ grains, with no evidence of iron silicide. Between this region and the β -Si₃N₄ grain was a zone containing both α- and β -Si₃N₄ and iron silicide. These observations suggest that the large β -Si₃N₄ grains grow in liquid iron silicide, that the smaller α-Si₃N₄ grains grow from the vapor, and that the latter are converted to the β form by solution in, and reprecipitation from, liquid iron silicide.     

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.