Silicon Nitride–Silicon Carbide Nancocomposites Fabricated by Electric-Field-Assisted Sintering

Starting with Si-C-N(-O) amorphous powders, and using the electric field assisted sintering (EFAS) technique, silicon nitride/silicon carbide nanocomposites were fabricated with yttria as an additive. It was found that the material could be sintered in a relatively short time (10 min at 1600°C) to satisfactory densities (2.96–3.09 g/cm³) using 1–8 wt% yttria. With decreasing yttria content, the ratio of SiC to Si₃N₄ increased, whereas the grain size decreased from ∼150 nm to as small as 38 nm. This offers an attractive way to make nano-nanocomposites of silicon nitride and silicon carbide.     

Microstructural Development and Creep Deformation in an Alumina–5% Yttrium Aluminum Garnet Composite

An alumina–5 vol% yttrium aluminum garnet (YAG) composite was obtained through in situ reaction of alumina and yttria during sintering. Analysis of creep experiments together with microstructural data indicated that both pure alumina and alumina–5 vol% YAG composite deform by a Coble grain boundary diffusion creep process. Comparison with other data suggests that at temperatures greater than ∼1650 K, an isolated or interconnected fine-grained YAG phase does not significantly affect creep in alumina. However, an isolated YAG phase retards both static and dynamic grain growth in the composite.     

Low-Temperature Fine-Grained Alumina–Aluminum Titanate Composites Produced from a Titania-Coated Alumina Precursor

A method for the preparation of alumina–aluminum titanate (AT) composites, which can be sintered to high density with a fine-grained microstructure at <1450°C, is reported. The composite precursor is alumina particles coated by sol–gel-derived titania, which reacts during sintering to form AT in situ at temperature as low as 1300°C. The composite can be sintered at 1350°C to 98% density with 1.5–2.0 μm grain size. Other composites containing 5–50 wt% AT are also investigated.     

Highly Creep-Resistant Silicon Nitride/Silicon Carbide Nano–Nano Composites

A high creep resistance at specified temperature and compressive stress was obtained in this investigation in the silicon nitride/silicon carbide composite with a nano–nano structure (nanosized SiC and Si₃N₄ in dual-phase mixture) by a novel synthesis method. Starting from an amorphous Si–C–N powder derived from pyrolysis of a liquid polymer precursor, nanocomposites with varied grain size were achieved. With yttria additive amount decreasing from 8 to 1 wt% and eventually to zero, the structure underwent a transition from micro-nano (nano-sized SiC included in sub-micron Si₃N₄) to nano–nano type. Nanocrystalline silicon nitride/silicon carbide ceramic composite with 30–50 nm grain size was synthesized without using sintering additive.     

Effect of SiC Submicrometer Particle Size and Content on Fracture Toughness of Alumina–SiC "Nanocomposites"

A simple model was developed which describes the effect of SiC submicrometer particles on the fracture toughness of alumina–SiC "nanocomposites." This effect was attributed to the change in the fracture mode observed in alumina on adding SiC submicrometer particles, which was suggested to be a result of both matrix weakening and grain boundary strengthening. The model suggests that the increase in fracture toughness should be obtained only for small additions (less than 5 wt%) of SiC.     

Tensile Creep Behavior of Alumina/Silicon Carbide Nanocomposite

Tensile creep and creep rupture behaviors of alumina/17 vol% silicon carbide nanocomposite and monolithic alumina Were investigated at 1200° to 1300°C and at 50 to 150 MPa. Compared to the monolithic alumina, the nanocomposite exhibited excellent creep resistance. The minimum creep rate of the nanocomposite was about three orders of magnitude lower and the creep life was 10 times longer than those of the monolith. The nanocomposite demonstrated transient creep until failure, while accelerated creep was observed in the monolith. It was revealed that rotating and plunging of intergranular silicon carbide nanoparticles into the alumina matrix increased the creep resistance with grain boundary sliding.     

B6O–c-BN Composites Prepared by High-Pressure Sintering

High-pressure sintering behavior in the B₆O– c -BN system was investigated using in-laboratory-synthesized B₆O and commercially available c -BN powders (with an average grain size of 0.5, 3, or 6 μm). No reaction occurred between the two components under the high-pressure (4–6 GPa) and high-temperature (1500°–1800°C) conditions that have been investigated. Well-dispersed, sintered B₆O– x ( c -BN) composites (where x = 0–60 vol%) of almost-full density were prepared by sintering at a pressure of 6 GPa and temperature of 1800°C for 20 min. The maximum Vickers microhardness (46 GPa) of these composites was attained by adding 40 vol% c -BN with an average grain size of 0.5 μm. The fracture toughness of these composites increased as the c -BN content increased; the maximum fracture toughness (1.5–1.8 MPa^.m^1/2) was observed for x = 40–60 vol%. Crack deflection along the B₆O– c -BN grain boundary contributed to increasing the fracture toughness.     

Reaction sintering of alumina/mullite nanocomposites from nano-sized starting powders

Alumina/mullite ceramic nanocomposites were prepared by the mixtures of nano-sized starting powders of alumina with silica and alumina with silicon carbide. Silica from deliberate addition and as the product of silicon carbide oxidation reacted completely with alumina to form mullite. Silica from direct addition segregated at the grain boundary and intergranular mullite was formed whereas silica from oxidation was surrounded by alumina matrix and intragranular mullite was formed after reaction sintering. The most significant difference was fracture behaviour where intragranular mullite nanoparticles promoted transgranular fracture in alumina matrix due to thermal mismatch around nanoparticles and intergranular mullite nanoparticles gave rise to intergranular fracture similar to pure alumina. Wear resistance of the nanocomposites was better than that of alumina. Pull-out formation in the nanocomposites was less and pull-out size was also smaller. Fracture toughness of the nanocomposites was significantly higher than that of alumina.     

Effects of Additives on the Pressure-Assisted Densification and Properties of Silicon Carbide

The densification of silicon carbide (SiC) was studied using a variety of additives (Al, AlN, Al₂O₃, B₄C, C, Si₃N₄, and Y₂O₃). The onset of densification of SiC with small amounts of additives occurred at temperatures between 1500° and 1900°C with 28 MPa applied pressure. Al, B₄C, and C promoted densification, while N (added as AlN or Si₃N₄) retarded sintering. A 96.75 wt% SiC–2 wt% Al–1 wt% C–0.25 wt% B₄C starting composition yielded the same percent of theoretical density (in the range of 70%–90% theoretical density) 400°C lower than a 95 wt% SiC–5 wt% AlN material. Yttria additions promoted intergranular fracture, which increased the single-edged precracked beam fracture toughness. The appropriate selection and amount of additives allowed for the tailoring of grain size and intergranular fracture, thus controlling the mechanical properties. While oxygen was present in all materials containing aluminum, the incorporation of additional oxygen as alumina resulted in reduced sintering activity compared with Al metal. Corrosion resistance decreased in both HF and NaOH solutions at 80°C for materials containing a grain boundary phase.     

High-Resolution Transmission Electron Microscopy Study of the Microstructural Development of a Silicon Carbonitride Nanocomposite

Nanocrystalline ceramics are expected to possess enhanced superplasticity over their microcrystalline counterparts. In this effort of producing nanocomposites of silicon nitride and silicon carbide, amorphous Si-C-N derived from pyrolysis of a polysilazane precursor was sintered with yttria as an additive. High-pressure sintering at different temperatures resulted in sintered materials ranging from amorphous to nanocrystalline. High-resolution transmission electron microscopy was conducted to characterize the development and grain-boundary features of the nanocrystalline microstructure. The results provide a preliminary understanding of the process of the formation of the nanocrystalline structure from an amorphous matrix, under the condition of high pressure and relatively low temperature. The wide variation in the thickness of grain-boundary phases observed in this material suggests a nonequilibrium state of the grain boundary, which might be related to the processing conditions.     

Densification and Mechanical Behavior of HfC and HfB2 Fabricated by Spark Plasma Sintering

Hafnium diboride (HfB₂)- and hafnium carbide (HfC)-based materials containing MoSi₂ as sintering aid in the volumetric range 1%–9% were densified by spark plasma sintering at temperatures between 1750° and 1950°C. Fully dense samples were obtained with an initial MoSi₂ content of 3 and 9 vol% at 1750°–1800°C. When the doping level was reduced, it was necessary to raise the sintering temperature in order to obtain samples with densities higher than 97%. Undoped powders had to be sintered at 2100°–2200°C. For doped materials, fine microstructures were obtained when the thermal treatment was lower than 1850°C. Silicon carbide formation was observed in both carbide- and boride-based materials. Nanoindentation hardness values were in the range of 25–28 GPa and were independent of the starting composition. The nanoindentation Young's modulus and the fracture toughness of the HfB₂-based materials were higher than those of the HfC-based materials. The flexural strength of the HfB₂-based material with 9 vol% of MoSi₂ was higher at 1500°C than at room temperature.     

Effect of Silicon Substitution on the Sintering and Microstructure of Hydroxyapatite

The substitution of between 0 and 1.6 wt% silicon (Si-HA) in hydroxyapatite (HA) inhibited densification at low temperatures (1000°–1150°C), with these effects being more significant as the level of silicon substitution was increased. For higher sintering temperatures (1200°–1300°C), the sintered densities of HA and Si-HA compositions were comparable. Examination of the ceramic microstructures by scanning electron microscopy (SEM) showed that silicon substitution also inhibited grain growth at higher sintering temperatures (1200°–1300°C). The negative effect of silicon substitution on the sintering of HA at low temperatures (1000°–1150°C) was reflected in the hardness values of the ceramics. However, for higher sintering temperatures, e.g., 1300°C, where sintered densities were comparable, the hardness values of Si-HA compositions were equal to or greater than that of HA, reflecting the smaller grain sizes observed for the former.     

Influence of Microstructure and Temperature on the Interfacial Fracture Energy of Silicon Nitride/Boron Nitride Fibrous Monolithic Ceramics

The microstructure and interfacial fracture energy of silicon nitride/boron nitride fibrous monoliths, Gamma_BN, were determined as a function of starting silicon nitride composition and temperature using the method described by Charalambides. The glassy phase created by the sintering aids added to the silicon nitride cells was shown to migrate into the boron nitride cell boundaries during hot-pressing. The amount of glassy phase in the boron nitride cell boundaries was shown to strongly influence Gamma_BN at room temperature, increasing the fracture energy with increasing amounts of glass. Similar trends in the interfacial fracture energy as a function of temperature were demonstrated by both compositions of fibrous monoliths, with a large peak in Gamma_BN observed over a narrow temperature range. For silicon nitride cells densified with 6 wt% yttria and 2 wt% alumina, the room-temperature interfacial fracture energy was 37 J/m², remaining constant through 950°C. A sharp increase in Gamma_BN, to 60 J/m², was observed between 1000° and 1050°C. This increase was attributed to interactions of the crack tip with the glassy phase in the boron nitride cell boundary. Measurements at 1075°C indicated a marked decrease in Gamma_BN to 39 J/m². The interfacial fracture energy decreased with increasing temperature in the 1200° to 1300°C regime, plateauing between 17 to 20 J/m². A crack propagation model based on linkup of existing microcracks and peeling/cleaving boron nitride has been proposed.     

Effect of Yttria and Yttrium-Aluminum Garnet on Densification and Grain Growth of Alumina At 1200°–1300°C

Densification and grain growth of alumina were studied with yttria or yttrium-aluminum garnet (YAG) additives at the relatively low temperatures of 1200°–1300°C. Yttria doping was found to inhibit densification and grain growth of alumina at 1200°C and, depending on dopant level, had a lesser effect at 1300°C. At 1200°C, yttria inhibits densification more than it hinders grain growth. The rate of grain growth increases faster with temperature than the rate of densification. Alumina-YAG particulate composites were difficult to sinter, yielding relative densities of only 65% and 72% after 100 h at 1200° and 1300°C, respectively. Pure YAG compacts exhibited essentially no densification for times up to 100 h at 1300°C.     

Microstructural and Mechanical Properties of Hydroxyapatite–Zirconia Composites

This work focuses on the improvement of the mechanical properties of hydroxyapatite (HA) through the addition of 3 mol% yttria partially stabilized zirconia (PSZ). Enamel-derived HA (EHA) from freshly extracted human teeth and commercial HA (CHA) were chosen as the matrix. The effects of addition up to 10 wt% of PSZ and of sintering temperature (1000°–1300°C) on the density, microhardness, and compression strength were evaluated. For EHA–PSZ composites, the density and mechanical properties were generally enhanced by adding 5 wt% PSZ, especially after sintering at 1200°C, whereas CHA–PSZ composites showed lower strength values at sintering temperatures of 1200° and 1300°C with respect to EHA–PSZ composites. This may be due to the lower stability of CHA–PSZ composites with higher amounts of calcium zirconate formed over 1100°C when compared with EHA–PSZ composites.     

Grain boundary glasses in silicon nitride: A review of chemistry,properties and crystallisation

Silicon nitride for engineering applications is densified by liquid phase sintering using oxide additives such as yttria and alumina. The oxynitride liquid remains as an intergranular glass. This paper provides a review of microstructural development in silicon nitride, grain boundary oxynitride glasses and effects of chemistry on properties. Nitrogen increases T_g, viscosities, elastic moduli and microhardness. These property changes are compared with known effects of grain boundary glass chemistry in silicon nitride ceramics where significant improvements in fracture resistance of silicon nitride can be achieved by tailoring the intergranular glass chemistry.Crystallisation of the grain boundary Y–Si–Al–O–N glass phase can improve properties. Nucleation and crystallisation of a Y–Si–Al–O–N glass, similar to that found in grain boundaries of silicon nitride densified with yttria and alumina, can be optimised to form different Y-disilicate polymorphs at different temperatures. One solution to provide a single disilicate phase over a range of temperatures is discussed.     

Creep Deformation in an Alumina–Silicon Carbide Composite Produced via a Directed Metal Oxidation Process

Flexural creep studies were conducted in a commercially available alumina matrix composite reinforced with SiC particulates (SiC_p) and aluminum metal at temperatures from 1200° to 1300°C under selected stress levels in air. The alumina composite (5 to 10 μm alumina grain size) containing 48 vol% SiC particulates and 13 vol% aluminum alloy was fabricated via a directed metal oxidation process (DIMOX(tm))† and had an external 15 μm oxide coating. Creep results indicated that the DIMOX Al₂O₃–SiC_p composite exhibited creep rates that were comparable to alumina composites reinforced with 10 vol% (8 (μm grain size) and 50 vol% (1.5 μm grain size) SiC whiskers under the employed test conditions. The DIMOX Al₂O₃–SiC_p composite exhibited a stress exponent of 2 at 1200°C and a higher exponent value (2.6) at ≥ 1260°C, which is associated with the enhanced creep cavitation. The creep mechanism in the DIMOX alumina composite was attributed to grain boundary sliding accommodated by diffusional processes. Creep damage observed in the DIMOX Al₂O₃-SiC_p composite resulted from the cavitation at alumina two-grain facets and multiple-grain junctions where aluminum alloy was present.     

Preparation and Analysis of a Silicon Carbide Composite Membrane

Silicon carbide (SiC) porous substrates, containing alumina (Al₂O₃) dopant levels of 3, 5, and 8 wt%, are prepared by slip casting and sintering in the temperature range of 1450°–1800°C. The linear shrinkage, bulk density, and pore size of the sintered substrate increase as the sintering temperature and the amount of dopant increase. A large amount of β-phase SiC is transformed to α-phase SiC if the dopant concentration is 5 or 8 wt%. The flexural strength of the substrate doped with 8 wt% Al₂O₃ is higher than that of the substrate doped with 3 wt% Al₂O₃; however, the Weibull modulus of the former is lower. SiC composite membranes of improved selectivity and strength are fabricated by coating the porous substrate with layers of lower Al₂O₃ contents at lower sintering temperatures.     

Superplasticity of Silicon Carbide

Nanocrystalline silicon carbide that was doped with boron and carbon (B,C-SiC) and contained 1 wt% boron additive and 3.5 wt% free carbon was fabricated using hot isostatic pressing under an ultrahigh pressure of 980 MPa and a temperature of 1600°C. The average grain size of the material was 200 nm. The tensile deformation behavior of this material at elevated temperature was investigated. The nanocrystalline B,C-SiC exhibited superplastic elongation of >140% at a temperature of 1800°C. High-resolution transmission electron microscopy observation and electron energy-loss spectroscopy analysis revealed that this nanocrystalline SiC did not have a secondary glassy phase at the grain boundary and the grain boundary had a strong covalent nature, which means that an intergranular glassy phase was not necessary to obtain superplasticity of covalent materials.     

Microstructural Characterization of Porous Silicon Carbide Membrane Support With and Without Alumina Additive

Porous silicon carbide (SiC) membrane supports sintered at 1500°–1800°C were prepared by cold isostatic pressing (CIP) under different pressures and using different amounts of alumina additive (0%–4%). The relationship between processing factors and pore size and microstructure was examined. Varying the sintering temperature, the CIP pressure and the amount of additive used were found to be effective for controlling pore size and microstructure. The pore size and particle size of the membrane support prepared without alumina were found to increase with increasing sintering temperature. This was attributed to surface diffusion. Densification of the undoped support did not occur, however, because of concurrent pore development. In the SiC membrane support containing 4% alumina, small particles and a pore size of around 100 nm were retained. This was because of the formation of a limited amount of SiO₂–Al₂O₃ liquid phase during sintering.