Processing and Tribological Properties of Si3N4/Carbon Short Fiber Composites

Si₃N₄/carbon fiber composites were fabricated using several types of fiber. All the composites had higher fracture toughness compared with monolithic Si₃N₄ ceramics. Tribological properties were investigated by a ball-on-disk method under unlubricated conditions. The composite containing fibers with a high orientation of graphite layers and high graphite content indicated a low friction coefficient. It was identified, by Raman spectroscopy, that graphite was transferred from the composite to the Si₃N₄ ball of the counterbody during the wear test. This transferred layer was effective for producing the low friction behavior of the composite.     

Comparison of Tribological Behavior Between α-Sialon/Si3N4 and Si3N4/Si3N4 Sliding Pairs in Water Lubrication

We report here the study on tribological behavior of α-Sialon in aqueous medium. The results derived from a wide range of test conditions are briefly discussed. A reduction in friction coefficient from 0.7 to 0.03 and a decrease in wear rate by two orders of magnitude were achieved under low load (9.8 N) and high speed (>0.54 m/s) conditions. The tribological behavior of α-Sialon/Si₃N₄ ceramics was then compared with Si₃N₄/Si₃N₄ tribopairs.     

Tribological Behavior of a Si3N4/Carbon Short Fiber Composite under Water Lubrication

The tribological behavior of monolithic Si₃N₄ and a Si₃N₄/carbon fiber composite has been assessed under high load and low speeds in an aqueous environment. The results showed that the friction coefficient of the Si₃N₄ was not significantly reduced when compared with dry sliding, and this was attributed to the failure to maintain a lubricating layer between the solid–solid surfaces. In the case of the composite, the initial high friction coefficient was reduced shortly after the beginning of the wear test and maintained a low value (about 0.03) throughout. This was attributed to the solid lubricating effect of the composite resulting in lower stress at the contact asperities, preventing the removal of the lubricating layer.     

Friction and Wear Properties of Si3N4/Carbon Fiber Composites with Aligned Microstructure

The friction and wear properties of silicon nitride/carbon fiber composites have been assessed and compared with monolithic Si₃N₄. Three different types of composites have been produced; one in which both the Si₃N₄ grains and the carbon fibers were aligned, one in which only the fibers had alignment, and a third where both the grains and fibers had random orientation. The friction coefficients of all of the composites, following running in, were around 0.2–0.3, typically less than one-third of that of the monolithic material. However there was no significant difference in friction coefficient between the three different types of composite. The specific wear rates of all the materials decreased with sliding distance and those of the composites were lower than the monolithic material. Among the composites, the wear rate of the one with aligned fibers in a randomly oriented Si₃N₄ matrix showed no dependence on sliding direction relative to the fiber alignment, and the specific wear rates of these samples were similar to that of the randomly oriented fiber composite, indicating little effect of fiber alignment alone on the wear properties under the present testing conditions. However, the specific wear rate of the composite with both fiber and grain alignment showed directional dependence. Grain cracking was observed perpendicular to the sliding direction, and the Spara specimen, in which the sliding direction was parallel to the Si₃N₄ grain alignment, showed higher wear rates than the Sperp and N samples of this composite. Such cracks are perpendicular to the major axis of the grains in the Spara sample and are thought to lead to easier removal of grains following their cracking under the tensile stresses induced particularly during the running in period.     

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.     

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.     

Fabrication of TiN/Si3N4 Ceramics by Spark Plasma Sintering of Si3N4 Particles Coated with Nanosized TiN Prepared by Controlled Hydrolysis of Ti(O-i-C3H7)4

TiN-coated Si₃N₄ particles were prepared by depositing TiO₂ on the Si₃N₄ surfaces from Ti(O- i -C₃H₇)₄ solution, the TiO₂ being formed by controlled hydrolysis, then subsequently nitrided with NH₃ gas. A homogeneous TiO₂ coating was achieved by heating a Si₃N₄ suspension containing 1.0 vol% H₂O with the precursor at 40°C. Nitridation successfully produced Si₃N₄ particles coated with 10–20 nm TiN particles. Spark plasma sintering of these TiN/Si₃N₄ particles at 1600°C yielded composite ceramics with a relative density of 96% at 25 vol% TiN and an electrical resistivity of 10⁻³Ω·cm in compositions of 17.5 and 25 vol% TiN/Si₃N₄, making these ceramics suitable for electric discharge machining.     

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.     

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.     

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.     

Fabrication and Mechanical Properties of Si3N4/Carbon Fiber Composites with Aligned Microstructure Produced by a Seeding and Extrusion Method

Si₃N₄/carbon fiber composites have been produced with and without seeding by an extrusion and sintering process. In both cases the carbon fibers were aligned along the direction of extrusion, but the Si₃N₄ grains were only aligned in the seeded material. The mechanical properties of the specimens showed anisotropy with respect to the grain alignment, with both strength and toughness being highest in the direction parallel to the extruding direction. In this direction the seeded specimen, where both the Si₃N₄ grains and the carbon fibers were aligned, showed both higher fracture toughness and higher fracture strength than the nonseeded specimen where only the fibers were aligned.     

Pressureless Sintering of Dense Si3N4 and Si3N4/SiC Composites with Nitrate Additives

The effect of aluminum and yttrium nitrate additives on the densification of monolithic Si₃N₄ and a Si₃N₄/SiC composite by pressureless sintering was compared with that of oxide additives. The surfaces of Si₃N₄ particles milled with aluminum and yttrium nitrates, which were added as methanol solutions, were coated with a different layer containing Al and Y from that of Si₃N₄ particles milled with oxide additives. Monolithic Si₃N₄ could be sintered to 94% of theoretical density (TD) at 1500°C with nitrate additives. The sintering temperature was about 100°C lower than the case with oxide additives. After pressureless sintering at 1750°C for 2 h in N₂, the bulk density of a Si₃N₄/20 wt% SiC composite reached 95% TD with nitrate additives.     

Pressureless Sintering of α-Si3N4 Porous Ceramics Using a H3PO4 Pore-Forming Agent

A new method for preparing high bending strength porous silicon nitride (Si₃N₄) ceramics with controlled porosity has been developed by using pressureless sintering techniques and phosphoric acid (H₃PO₄) as the pore-forming agent. The fabrication process is described in detail and the sintering mechanism of porous ceramics is analyzed by the X-ray diffraction method and thermal analysis. The microstructure and mechanical properties of the porous Si₃N₄ ceramics are investigated, as a function of the content of H₃PO₄. The resultant high porous Si₃N₄ ceramics sintered at 1000°–1200°C show a fine porous structure and a relative high bending strength. The porous structure is caused mainly by the volatilization of the H₃PO₄ and by the continous reaction of SiP₂O₇ binder, which could bond on to the Si₃N₄ grains. Porous Si₃N₄ ceramics with a porosity of 42%–63%, the bending strength of 50–120 MPa are obtained.     

Solubility of Si3N4 in Liquid SiO2

The nitrogen solubility in the SiO₂-rich liquid in the metastable binary SiO₂-Si₃N₄ system has been determined by analytical TEM to be 1%–4% of N/(O + N) at 1973–2223 K. Analysis of the near edge structure of the electron energy loss peak indicates that nitrogen is incorporated into the silicate network rather than being present as molecular N₂. A regular solution model with a positive enthalpy of mixing for the liquid was used to match the data for the metastable solubility of N in the presence of crystalline Si₃N₄ and to adjust the computed phase diagram. The solubility of Si₃N₄ in fused SiO₂ is far less than reported in liquid silicates also containing Al, Mg, and/or Y. Apparently, these cations act as modifiers that break anion bridges in the silicate network and, thereby, allow further incorporation of Si₃N₄ without prohibitive amounts of network cross-linking. Finally, indications emerged regarding the diffuse nature of the Si₃N₄-SiO₂ interface that leads to amorphous regions of higher N content.     

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.     

Lubricated Rolling and Sliding Wear of a SiC-Whisker-Reinforced Si3N4 Composite against M2 Tool Steel

Mineral oil lubricated rolling and sliding wear of SiC whisker (SiC_w) reinforced Si₃N₄ composite and monolithic Si₃N₄ prepared identically against M2 tool steel were investigated using a cylinder-on-cylinder apparatus. Wear of this Si₃N₄ was higher than that of the composite. Wear of the steel against Si₃N₄ was also higher than that against the composite. Relatively larger scale microfracture occurred in the Si₃N₄ than in the composite; more pullout and microchipping of carbide particles were observed in the steel against Si₃N₄ than against the composite. Polishing of the worn surfaces of the steel occurred in both sliding and rolling tests. This was attributed to fine, hard wear debris circulating in the contact area. Spalling was observed in the steel sliding against Si₃N₄ but not in the steel sliding against the composite.     

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.     

Pre-Treatment of Si3N4 Filler Particles for the Improvement of Si3N4filler/Si–C–Nmatrix Particulate-Reinforced Composites

The surface of Si₃N₄ filler particles was modified by heat treatments before the onset of the precursor impregnation and pyrolysis process. The strength, Young's modulus, and hardness of Si₃N_4filler/Si–C–N_matrix particulate-reinforced composites (PRC) were improved up to 50%, 60%, and 71%, respectively, by the treatment. Si was formed at the surface of the Si₃N₄ filler particles by the treatment, which induced a strong bonding between the filler and the Si–C–N matrix during pyrolysis by a carbothermal reaction, thus improving the properties of the PRC.     

Synthesis of Porous Si3N4 Ceramics with Rod-Shaped Pore Structure

Porous Si₃N₄ ceramics were synthesized by pressureless sintering of green compacts prepared using slip casting of slurries containing Si₃N₄, 5 wt% Y₂O₃+2 wt% Al₂O₃, and 0–60% organic whiskers composed of phenol–formaldehyde resin with solids loading up to 60 wt%. Rheological properties of slurries were optimized to achieve a high degree of dispersion with a high solid-volume fraction. Samples were heated at 800°C in air and sintered at 1850°C in a N₂ atmosphere. Porosities ranging from 0% to 45% were obtained by the whisker contents (corresponding to 0–60 vol% whisker). Samples exhibited a uniform pore distribution. Their rod-shaped pore morphology originated from burnout of whiskers, and an extremely dense Si₃N₄ matrix.     

Pressureless Sintering of Si3N4 Ceramic Using AlN and Rare-Earth Oxides

Using intermediate, liquid-forming compositions in the (Y,La)₂O₃-AlN system as additives, fully dense Si₃N₄ ceramics with high strength at high temperature have been obtained by pressureless sintering. The ceramics contain rod-shaped β-Si₃N₄ with M' or K' solid solutions as grain-boundary phases. The strength of these ceramics is 1150 MPa at 1200°C, and the room-temperature toughness is maintained at }7 MPa·m^1/2. Phase relations that are pertinent to the new additive compositions are delineated to rationalize their beneficial effects on sinterability and mechanical properties.