High-Temperature Chemistry and Oxidation of ZrB2 Ceramics Containing SiC, Si3N4, Ta5Si3, and TaSi2

The effect of Si₃N₄, Ta₅Si₃, and TaSi₂ additions on the oxidation behavior of ZrB₂ was characterized at 1200°–1500°C and compared with both ZrB₂ and ZrB₂/SiC. Significantly improved oxidation resistance of all Si-containing compositions relative to ZrB₂ was a result of the formation of a protective layer of borosilicate glass during exposure to the oxidizing environment. Oxidation resistance of the Si₃N₄-modified ceramics increased with increasing Si₃N₄ content and was further improved by the addition of Cr and Ta diborides. Chromium and tantalum oxides induced phase separation in the borosilicate glass, which lead to an increase in liquidus temperature and viscosity and to a decrease in oxygen diffusivity and of boria evaporation from the glass. All tantalum silicide-containing compositions demonstrated phase separation in the borosilicate glass and higher oxidation resistance than pure ZrB₂, with the effect increasing with temperature. The most oxidation-resistant ceramics contained 15 vol% Ta₅Si₃, 30 vol% TaSi₂, 35 vol% Si₃N₄, or 20 vol% Si₃N₄ with 10 mol% CrB₂. These materials exceeded the oxidation resistance of the ZrB₂/SiC ceramics below 1300°–1400°C. However, the ZrB₂/SiC ceramics showed slightly superior oxidation resistance at 1500°C.     

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.     

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.     

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.     

Crack-Healing Behavior of Si3N4/SiC Ceramics under Cyclic Stress and Resultant Fatigue Strength at the Healing Temperature

Si₃N₄/SiC composite ceramics were sintered and subjected to three-point bending. A semi-elliptical surface crack of 100 μm surface length was made on each specimen. The crack-healing behavior under cyclic stress of 5 Hz, and resultant cyclic fatigue strengths at healing temperatures of 1100° and 1200°C, were systematically investigated. The main conclusions are as follows: (1) Si₃N₄/SiC composite ceramics have an excellent ability to heal a crack at 1100° and 1200°C. (2) This sample could heal a crack even under cyclic stress at a frequency of 5 Hz. (3) The crack-healed sample exhibited quite high cyclic fatigue strength at each crack-healing temperature, 1100° and 1200°C.     

Mechanical Properties of Si2N2O/SiC-Whisker Composites

The mechanical and thermal properties of Si₂N₂O/SiC-whisker composites were studied with emphasis on the effect of matrix composition and of whisker content. The fracture toughness of Si₂N₂O was remarkably improved by 90% with a concomitant 70% strength improvement by addition of SiC whiskers of only 10 vol%. Optimum mechanical and thermal properties of Si₂N₂O/SiC-whisker composites were obtained at an equimolar ratio of Si₃N₄/SiO₂, which is the stoichiometric composition for Si₂N₂O. Additional investigation concerning the Si₂N₂O-matrix/SiC-whisker interface by controlling sintering additives is necessary for further improvement of mechanical and thermal properties of Si₂N₂O/SiC-whisker composites.     

Tribological Behavior of Si3N4 and Si3N4/Carbon Fiber Composites Against Stainless Steel Under Water Lubrication for a Thrust-Bearing Application

The tribological behavior of Si₃N₄ ceramics and Si₃N₄/carbon fiber composites sliding against stainless steel under water lubrication was investigated using a thrust-bearing-type test method with normal applied loads varying from 0 to 1000 N in 100 N increments. In the case of the monolithic Si₃N₄, the friction coefficient was found to increase up to 0.4 the first time the applied load was increased from 100 to 200 N, and sudden failure of the ceramic ring specimen occurred. In the case of the Si₃N₄/carbon fiber composite, a low friction coefficient was maintained up to the maximum normal load of 1000 N. The addition of the carbon fibers to the silicon nitride ceramics effectively restricts material transfer from the stainless steel to the Si₃N₄ worn surface due to reduction of solid–solid contact through the solid lubricating effect of the carbon fibers.     

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.     

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.     

Evaluation of Slow Crack Growth Resistance in Ceramics for High-Temperature Applications

The slow (subcritical) crack growth (SCG) resistance of Si₃N₄ and SiC ceramics has been evaluated by a stepwise loading test on bending bars precracked by Vickers indentation. Three highly refractory materials were selected for the evaluation: i.e., (1) high-purity Si₃N₄ sintered by hot isostatic pressing (HIP) without additives and (2,3) α - and β - SiC pressureless sintered with B and C addition. Under the hypothesis of linear elastic behavior at high temperature, which was found satisfied in the present materials, the SCG resistance was expressed in terms of initial stress intensity factor critical for SCG failure within a predetermined lifetime. The present method was found useful in shortening the testing time and consistent with other traditional fatigue tests (e.g., static-fatigue test): It is recommended as a screening test for materials under research and development. Among the materials tested in the present study, the highest SCG resistance up to 1440°C was found in the high-purity Si₃N₄ without additives.     

Si3N4/SiC-Whisker Composites without Sintering Aids: II, Fracture Behavior

The fracture behavior of an Si₃N₄/SiC-whisker composite fabricated without sintering aids is investigated using a double approach based on the examination of R -curve behavior and a statistical analysis of crack propagation. In the composite with 20 vol% whisker, a 30% increase in toughness over the matrix value can be attributed to crack-tip phenomena. Strong interfacial bonding prevents any contribution to toughening by mechanisms operating in the wake region of the crack. Based on experimental observations of microfracture in both SiC whiskers and Si₃N₄ grains, toughening caused by crack-tip phenomena is quantitatively discussed in terms of fracture energy and whisker-distribution parameters.     

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.     

Wear Perfomance of Ceramics in Ring/Cylinder Applications

In support of efforts to apply ceramics to advanced heat engines, a study was performed of the wear mechanisms of ceramics at the ring/cylinder interface. A laboratory apparatus was constructed to reproduce most of the conditions of an actual engine. Ring and cylinder specimens having a simple geometry were used to facilitate their fabrication. Attempts to operate three zirconias, α-SiC, Si₃N₄, and several plasma-sprayed coatings without lubrication were unsuccessful because of high friction and wear rates. The ceramics responded well to liquid lubricants at a temperature of 260°C. Plasma-sprayed coatings of Cr₂O₃ and hypersonic flame-sprayed coatings of Co-bonded WC performed particularly well as ring coatings. Similar performance was obtained with these coatings operating against SiC, Si₃N₄, SiC-whisker-reinforced Al₂O₃, and Cr₂O₃ coatings. The study demonstrated the critical need for lubrication.     

Influence of Rare-Earth Additives on Wear Properties of Hot-Pressed Silicon Nitride Ceramics under Dry Sliding Conditions

The influence of different rare-earth sintering additives (Y, Yb, Lu) on the wear properties of Si₃N₄ ceramics was investigated during sliding contact without lubricant. The kind of rare-earth additives was shown to have a significant effect on the wear behavior for contact sliding under the present testing conditions. Samples sintered with Y₂O₃ as the sintering additive showed evidence of fracture type wear although this was not observed in samples sintered with Yb₂O₃ and Lu₂O₃. These smaller rare earths lead to higher grain boundary bonding strength and superior high-temperature properties and resulted in higher wear resistance. These results showed that the wear properties of Si₃N₄ ceramics could be tailored by judicious selection of the sintering additives.     

Controlled Surface Flaws in Hot-Pressed Si3N4

Surface flaws of controlled size and shape were produced in high-strength hot-pressed Si₃N₄ with a Knoop microhardness indenter. Fracture was initiated at a single suitably oriented flaw on the tensile surface of a 4-point-bend specimen, with attendant reduction in the measured magnitude and scatter of the fracture strength. The stress required to propagate the controlled flaw was used to calculate the critical stress-intensity factor, K _IC, from standard fracture-mechanics formulas for semielliptical surface flaws in bending. After the bend specimen had been annealed, the room-temperature K _IC values for HS-130 Si₃N₄ increased to a level consistent with values obtained from conventional fracture-mechanics tests. It was postulated that annealing reduces the residual stresses produced by the microhardness indentation. The presence of residual stresses may account for the low K _IC, values. Elevated-temperature K_IC values for HS-130 Si₃N₄ were consistent with double-torsion data. Controlled flaws in HS-130 Si₃N₄ exhibited slow crack growth at high temperatures.     

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.     

Abrasive Wear Behavior of a Si3N4-MoSi2 Composite

MoSi₂ particles (20 vol%) have been added to Si₃N₄ to form ceramic matrix-intermetallic composites. Benefits associated with the addition of the MoSi₂ to Si₃N₄ include higher strength, higher fracture toughness, no loss in oxidation resistance, and lower electrical resistivity. However, because the hardness of MoSi₂ is approximately half that of Si₃N₄, a decrease in the specific wear rate of the Si₃N₄-20 vol% MoSi₂ composite is expected to result from the incorporation of the MoSi₂ into the Si₃N₄. In this U.S. Bureau of Mines and Los Alamos National Laboratory study, it is found, however, that the specific wear rate of the composite during two-body abrasion by SiC particles is equivalent in magnitude to the specific wear rate of monolithic Si₃N₄. The specific wear rates of both the Si₃N₄-20 vol% MoSi₂composites and monolithic Si₃N₄ are four to five times less than that of monolithic MoSi₂.     

Effects of Grain Size of Hot-Pressed Silicon Nitride on Contact Damage Morphology and Residual Strength

Effects of the grain size of hot-pressed Si₃N₄ on contact damage morphology and residual strength were studied using the elastic/plastic indentation method with a spherical indenter. The contact damage, initially formed with increasing indentation load, was Hertzian cracks in the Si₃N₄ consisting of fine grains (mean grain size: 0.2 μm). In the coarser-grained Si₃N₄ (mean grain size: 0.8 μm), there was a damage texture, consisting of grain-sized microcracks. The residual strength was degraded at a load slightly higher than the critical load for contact damage formation. The strength degradation was not caused by contact damage but the residual stress formed around the impressions.     

Slip Casting of SiC-Whisker-Reinforced Si3N4

Si₃N₄ composite materials containing up to 20 vol% SiC whiskers were slip cast and pressureless sintered at 1820°C and 0.13 MPa of N₂. Viscosimetry showed no influence of whisker loading on the rheology of the highly concentrated aqueous slips up to 15 vol% whiskers. During casting the whiskers were preferentially aligned parallel to the mold surfaces. Depending on the whisker loading, green densities of 0.64 to 0.69 fractional density could be achieved. Strong anisotropic shrinkage occurred during sintering with a maximum linear shrinkage of 21% perpendicular but only 7% parallel to the whisker plane. With increasing whisker content from 0 to 20 vol% sintered densities decreased from 0.98 to 0.88, respectively.     

Elastic Properties of Al2O3 and Si3N4 Matrix Composites with SiC Whisker Reinforcement

A study of the elastic moduli of Al₂O₃ and Si₃N₄ ceramics reinforced with 0 to 25 wt% SiC whiskers has been performed. The Young's moduli, shear moduli, and longitudinal modulus are compared with calculated predictions for aligned fiber composites by Hill and Hashin and Rosen, and for fibers randomly oriented in three dimensions by Christensen and Waal. The measured values are in excellent quantitative agreement with those derived for the random orientation of the SiC whiskers.