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.     

Effects of Intergranular Phase Chemistry on the Microstructure and Mechanical Properties of Silicon Carbide Ceramics Densified with Rare-Earth Oxide and Alumina Additions

Based on the processing strategy of improving the mechanical properties of liquid-phase-sintered materials by modifying the secondary phase chemistry, four rare-earth oxides (RE₂O₃, RE = La, Nd, Y, and Yb), in combination with alumina, were used as sintering aids for a submicrometer-size β-SiC powder. Doped with 5 vol% RE₂O₃+ Al₂O₃ additives, all specimens were hot-pressed to near full-densities at 1800°C, and they exhibited similar microstructures and grain size distributions. The SiC grains in all specimens revealed a core-rim structure after being plasma-etched, indicating that they were densified via the same solution-reprecipitation mechanism. It was found that a decrease in the cationic radius of the rare-earth oxides was accompanied by an increase in Young's modulus, hardness, and flexural strength of the SiC ceramics, whereas the fracture toughness was improved by incorporating rare-earth oxides of larger cationic radius. The changes in the mechanical properties were attributed to the difference in the chemistry of the intergranular phases in the four ceramics.     

Preparation, Hardness, and Fracture Toughness of Tantalum Oxynitride Ceramics

Tantalum oxynitride powder with a baddeleyite crystal structure was synthesized and densified by hot pressing in Ar and under high pressure using a belt-type high-pressure apparatus. The tantalum oxynitride powder could not be densified completely under hot-pressing conditions at 1400°C. The use of high pressure resulted in dense materials. The samples showed a hardness of 16–17 GPa and a fracture toughness of 3–4 MPa·m^1/2. The hardness is higher compared with that of ZrO₂ and HfO₂ ceramics. The fracture toughness corresponds to the value of fully stabilized ZrO₂ due to the absence of any transformation toughening mechanism.     

Reaction Sintering and Properties of Silicon Oxynitride Densified by Hot Isostatic Pressing

Silicon oxynitride ceramics were reaction sintered and fully densified by hot isostatic pressing in the temperature range 1700°C to 1950°C from an equimolar mixture of silicon nitride and silica powders without additives. Conversion to Si₂N₂O increases steeply from a level around 5% of the crystalline phases at 1700°C to 80% at 1800°C, and increases a few percent further at higher temperatures. α -Si₃N₄ is the major residual crystalline phase below 1900°C. The hardness level for materials containing 85% Si₂N₂O is approximately 19 GPa, comparable with the hardness of Si₃N₄ hot isostatically pressed with 2.5 wt% Y₂O₃, while the fracture toughness level is around 3.1 MPa. m^1/2, being approximately 0.8 MPa.m^1/2 lower. The three-point bending strength increased with HIP temperature from approximately 300 to 500 MPa.     

Processing Temperature Effects on Molybdenum Disilicide

A series of MoSi₂ compacts were fabricated at increasing hot-pressing temperatures to achieve different grain sizes. The materials were evaluated by Vickers indentation fracture to determine room-temperature fracture toughness, hardness, and fracture mode. From 1500° to 1800°C, MoSi₂ had a constant 67% transgranular fracture and linearly increasing grain size from 14 to 21 μm. Above 1800°C, the fracture percentage increased rapidly to 97% transgranular at 1920°C (32-μm grain size). Fracture toughness and hardness decreased slightly with increasing temperature. MoSi₂ processed at 1600°C had the highest fracture toughness and hardness values of 3.6 MPa.m^1/2 and 9.9 GPa, respectively. The effects of SiO₂ formation from oxygen impurities in the MoSi₂ starting powders and MoSi₂–Mo₅Si₃ eutectic liquid formation were studied.     

Heat-Resistant Silicon Carbide with Aluminum Nitride and Erbium Oxide

Fully dense SiC ceramics with high strength at high temperature were obtained by hot-pressing and subsequent annealing under pressure, with AlN and Er₂O₃ as sintering additives. The ceramics had a self-reinforced microstructure consisting of elongated SiC grains and a grain-boundary glassy phase. The strength of these ceramics was ∼550 MPa at 1600°C, and the fracture toughness was ∼6 MPa·m^1/2 at room temperature. The beneficial effect of the new additive composition on high-temperature strength might be attributable to the introduction of aluminum from the liquid composition into the SiC lattice, resulting in a refractive grain-boundary glassy phase.     

Al2O3─SiC Composites from Aluminosilicate Precursors

Al₂O₃ and SiC composite materials have been produced from mixtures of aluminosilicates (both natural minerals and synthetic) and carbon as precursor materials. These composites are produced by heating a mixture of kaolinite (or synthetic aluminosilicates) and carbon in stoichiometric proportion above 1550°C, so that only Al₂O₃ and SiC remain as the major phases. A similar process has also been used for synthesizing other composite powders having mixtures of Al₂O₃, SiC, TiC, and ZrO₂ in different proportions (all compounds together or selective mixtures of some of them), as desired. The microstructure of hot-pressed dense compacts, produced from these powders, revealed that the SiC phase is distributed very homogeneously, even occasionally within Al₂O₃ grains on a nanosize scale. The homogeneous distribution of SiC particles within the system produced high fracture toughness of the hot-pressed material (K_IC∼ 7.0 MPa · m^1/2) and having Vicker's hardness values greater than 2000 kgf/mm².     

Preparation and Properties of Ternary Ti3AlC2 and its Composites from Ti–Al–C Powder Mixtures With Ceramic Particulates

A layered ternary carbide phase, Ti₃AlC₂, was synthesized by hot pressing from the starting materials of Ti, aluminum, and activated carbon at 1400°C for 2 h. Its composites were also fabricated through addition of micro-sized SiC and partially stabilized zirconia particulates to the pulverized Ti₃AlC₂ powders. The polycrystalline Ti₃AlC₂ ceramic obtained has a flexural strength of 172 MPa and a fracture toughness of 4.6 MPa·m^1/2, respectively. This compound is relatively soft (Vikers hardness of 2.7 GPa) and exhibits good electrical conductivity with an electrical resistivity of 8.2 μΩ·m. Both the Ti₃AlC₂/SiC and Ti₃AlC₂/ZrO₂ composites are superior to the monolithic Ti₃AlC₂ ceramic in strength, fracture toughness, and micro-hardness.     

Effect of Additives on the Activation Energy for Sintering of Silicon Carbide

The combined-stage sintering model was used to determine the activation energy, Q , of sintering for selected SiC-based materials. SiC densified with a liquid (1.65 wt% Al) had an activation energy of 842±79 kJ/mol, a value between those for a silicon carbide densified with 1 wt% C and 0.25 wt% B₄C ( Q =643±37 kJ/mol) and one densified with 2.5 wt% AlN ( Q =1022±122 kJ/mol), compositions which have no liquid phase below 1850°C. The SiC with Al additive began densification by 1500°C and the densification curve was offset by approximately 100°C compared with the other two materials below 1850°C. The choice and amount of additives not only affect densification and activation energy, but also influence microstructure and fracture mode, allowing engineering of mechanical properties.     

Carbon Additions to Molybdenum Disilicide: Improved High-Temperature Mechanical Properties

C addition (2 wt%) to MoSi₂ acted as a deoxidant, removing the otherwise ubiquitous siliceous grain boundary phase in hot-pressed samples, and causing formation of SiC and Mo₅Si₃C₁ (a variable-composition Nowotny phase). Both hardness and fracture toughness of the C-containing alloy were higher than those of the C-free (and oxygen-rich) material; more significantly, the fracture toughness of the MoSi₂+ 2% C alloy increased from 5.5 MPa·m^1/2 at 800°C to ∼11.5 MPa·m^1/2 at 1400°C.     

Effect of Interfacial Reaction on the Thermal Conductivity of Al–SiC Composites with SiC Dispersions

The effect of interfacial reactions between Al and SiC on the thermal conductivity of SiC-particle-dispersed Al-matrix composites was investigated by X-ray diffraction and transmission electron microscopy (TEM), and the thermal barrier conductance ( h _c) of the interface in the Al–SiC composites was quantified using a rule of mixture regarding thermal conductivity. Al–SiC composites with a composition of Al (pure Al or Al–11 vol% Si alloy)–66.3 vol% SiC and a variety of SiC particle sizes were used as specimens. The addition of Si to an Al matrix increased the thermal barrier conductance although it decreased overall thermal conductivity. X-ray diffraction showed the formation of Al₄C₃ and Si as byproducts in addition to Al and SiC in some specimens. TEM observation indicated that whiskerlike products, possibly Al₄C₃, were formed at the interface between the SiC particles and the Al matrix. The thermal barrier conductance and the thermal conductivity of the Al–SiC composites decreased with increasing Al₄C₃ content. The role of Si addition to an Al matrix was concluded to be restraining an excessive progress of the interfacial reaction between Al and SiC.     

Densification, Sintering Reactions, and Properties of Titanium Diboride With Titanium Disilicide as a Sintering Aid

In the present investigation, we explore the feasibility of using TiSi₂ as a sintering aid to densify titanium diboride (TiB₂) at a lower sintering temperature (<1700°C). The hot-pressing experiments were conducted in the temperature range of 1400°–1650°C for 1 h in an argon atmosphere and TiSi₂ addition to TiB₂ was restricted up to 10 wt%, with an overall objective to densify the materials with a fine microstructure as well as to assess the feasibility of enhancing the mechanical and electrical properties. When all the materials were hot pressed at 1650°C, the hot-pressed TiB₂– X % TiSi₂ ( X =0, 2.5, 5, 10 wt%) composites were found to be densified to more than 98%ρ_th (theoretical density), except monolithic TiB₂ (∼94%ρ_th). An interesting observation is the formation of a Ti₅Si₃ phase and this phase formation is described by thermodynamically feasible sintering reactions. Our experimental results suggest that the optimal TiB₂–5 wt% TiSi₂ composite can exhibit an excellent combination of properties, including a high hardness of 25 GPa, an elastic modulus of 518 GPa, an indentation toughness of ∼6 MPa·m^1/2, a four-point flexural strength of more than 400 MPa, and an electrical resistivity of 10 μΩ·cm.     

Effects of α-Sic versus β-Sic Starting Powders on Microstructure and Fracture Toughness of Sic Sintered with Al2O3-Y2O3 Additives

Dense Sic ceramics were obtained by pressureless sintering of β-Sic and α-Sic powders as starting materials using Al₂O₃-Y₂O₃ additives. The resulting microstructure depended highly on the polytypes of the starting SiC powders. The microstructure of SiC obtained from α-SiC powder was composed of equiaxed grains, whereas SiC obtained from α-SiC powder was composed of a platelike grain structure resulting from the grain growth associated with the β→α phase transformation of SiC during sintering. The fracture toughness for the sintered SiC using α-SiC powder increased slightly from 4.4 to 5.7 MPa.m^1/2 with holding time, that is, increased grain size. In the case of the sintered SiC using β-SiC powder, fracture toughness increased significantly from 4.5 to 8.3 MPa.m^1/2 with holding time. This improved fracture toughness was attributed to crack bridging and crack deflection by the platelike grains.     

Fabrication and Characterization of ZrB2-Based Ceramic Using Synthesized ZrB2–LaB6 Powder

ZrB₂–LaB₆ powder was obtained by reactive synthesis using ZrO₂, La₂O₃, B₄C, and carbon powders. Then ZrB₂–20 vol% SiC–10 vol% LaB₆ (ZSL) ceramics were prepared from commercially available SiC and the synthesized ZrB₂–LaB₆ powder via hot pressing at 2000°C. The phase composition, microstructure, and mechanical properties were characterized. Results showed that both LaB₆ and SiC were uniformly distributed in the ZrB₂ matrix. The hardness and bending strength of ZSL were 17.06±0.52 GPa and 505.8±17.9 MPa, respectively. Fracture toughness was 5.7±0.39 MPa·m^1/2, which is significantly higher than that reported for ZrB₂–20 vol% SiC ceramics, due to enhanced crack deflection and crack bridging near SiC particles.     

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.     

Electrochemical Chromium(III) Oxide Coatings on Non-oxide Ceramic Substrates

SiC and TiB₂ were electrochemically coated with Cr₂O₃ from a 0.1 M aqueous solution of chromium nitrate hydrate with ethanol additives. On both substrate materials poly-crystalline Cr₂O₃ was formed at current densities from 5 to 50 mA/cm² and deposition durations of 5 to 30 min. The coating weight increased with current density and with deposition time. The as-deposited coatings contained microcracks due to drying shrinkage. Microstructural observations indicate that sintering of the Cr₂O₃ coatings on TiB₂ at 1100°C for 1 n in a reducing atmosphere in a closed graphite crucible causes the densification of the coating via a liquid phase, which forms by oxidation of TiB₂. Under similar conditions, the Cr₂O₃ coatings on SiC may be sintered via an evaporation–condensation mechanism.     

Hot Isostatic Press Sintering and Properties of Silicon Nitride without Additives

Fully densified silicon nitride without additives was fabricated by means of hot isostatic pressing. The sintering process of highly pure powder was investigated with special interest in the evolution of α–β phase transformation, densification, and microstructure development. It was observed that the transformation occurred without a liquid phase below 1730°C, which corresponds to the melting point of SiO₂. Above 1730°C, the densification and β-grain elongation accelerated concurrently because of the appearance of liquid SiO₂. However, full densification was attained at 1950°C together with marked grain growth. Flexural strength, microhardness, fracture toughness, and Young's modulus of sintered bodies were measured as a function of temperature. In the sintered body started from highly pure powder, excellent MOR behavior was found up to 1400°C. Impurity content of a few hundred ppm was found to be sufficient to make densification easy and to degrade high-temperature strength.     

Refractory Diborides of Zirconium and Hafnium

This paper reviews the crystal chemistry, synthesis, densification, microstructure, mechanical properties, and oxidation behavior of zirconium diboride (ZrB₂) and hafnium diboride (HfB₂) ceramics. The refractory diborides exhibit partial or complete solid solution with other transition metal diborides, which allows compositional tailoring of properties such as thermal expansion coefficient and hardness. Carbothermal reduction is the typical synthesis route, but reactive processes, solution methods, and pre-ceramic polymers can also be used. Typically, diborides are densified by hot pressing, but recently solid state and liquid phase sintering routes have been developed. Fine-grained ZrB₂ and HfB₂ have strengths of a few hundred MPa, which can increase to over 1 GPa with the addition of SiC. Pure diborides exhibit parabolic oxidation kinetics at temperatures below 1100°C, but B₂O₃ volatility leads to rapid, linear oxidation kinetics above that temperature. The addition of silica scale formers such as SiC or MoSi₂ improves the oxidation behavior above 1100°C. Based on their unique combination of properties, ZrB₂ and HfB₂ ceramics are candidates for use in the extreme environments associated with hypersonic flight, atmospheric re-entry, and rocket propulsion.     

Microstructural Evolution and Grain Growth Kinetics in ZrB2–SiC Composites During Heat Treatment

This work reported the microstructural evolution and grain growth kinetics of ZrB₂–SiC composites containing 10, 20, and 30 vol% SiC during heat treatment at 2000°C. The coarsening of ZrB₂ occurred in the three systems, whereas the obvious coarsening for SiC appeared only in the composite with 30 vol% SiC. The kinetics analysis showed the ZrB₂ grain growth rate in the ZrB₂–30 vol% SiC was 25 times lower than that for ZrB₂–10 vol% SiC during heat treatment. Furthermore, the grain growth controlling mechanisms of ZrB₂ and SiC were discussed. In addition, it was found that the heat treatment had little effect on Vickers hardness and fracture toughness of ZrB₂–SiC.     

Tribological Properties of Silicon Carbide and Silicon Carbide–Graphite Composite Ceramics in Sliding Contact

A monolithic SiC ceramic and two SiC–C composite ceramics containing 10 and 20 vol% graphite were fully densified with Al₄C₃ and B₄C as additives. The tribological properties of these materials were evaluated by sliding against sintered silicon carbide under dry conditions using two tribometers, block-on-ring and pin-on-disk, where wear occurred under low and high contact stresses, respectively. For all three materials, under low stress, worn surfaces were smooth and wear processes were dominated by tribochemical reaction; under high stress, worn surfaces were rough and wear processes were dominated by fracture and three-body abrasion. A lubricating effect of the graphite particles in the SiC–C composites was observed in all sliding tests. However, while the addition of graphite could concurrently result in a reduction in friction and an increase in wear resistance in the block-on-ring tests, the addition of graphite led to sharply enhanced wear rates despite the lowered coefficients of friction in the pin-on-disk tests. The cause for that difference was attributed to the effect of both the hardness of the materials and the contact stresses.