Composition and Properties of Hot-Pressed SiC-AIN Solid Solutions

High-density SiC-AIN compositions were fabricated from powder mixtures by hot-pressing in the 1700° to 2300°C temperature range. At 2100°C, a 2H solid solution was found from =35 to 100 wt% AlN. The single-phase solid solution samples had steep composition gradients of >10%/μm within the grains. Lattice parameters closely followed Vegard's law. For compositions with <35% AIN, multiphase assemblages were found. Increasing grain size was observed for increasing firing temperature for SiC and AIN. Grain size of the solid solutions was significantly smaller than for SiC or AIN fired to the same temperature. Microhardness values decreased linearly in the solid solution region with increasing AIN content. Flexural strengths of SiC and AIN decreased with increasing firing temperature and increasing grain size. The strengths of SiC, AIN, and the solid solutions were low for materials hot-pressed at 2100°C.     

Toughening of Mullite/Cordierite Laminated Composites by Transformation Weakening of β-Cristobalite Interphases

An interesting concept for achieving graceful failure in oxide composites is discussed. It is based on crack deflection in a weak interphase between a matrix and reinforcement (e.g. fiber), around a fibrous core in a fibrous monolith, or in an interphase in a laminated composite. The interphase can be phase transformation weakened by a crystallographic unit cell, volume contraction, and/or shape change. Mullite/cordierite laminates with a β→α-cristobalite, transformation-weakened interphase were investigated for interphase debonding behavior. The laminates were fabricated by stacking alternate, tape-cast, green sheets of chemically doped β-cristobalite, which was synthesized by an organic steric entrapment method, and a mullite/cordierite matrix mixture. The laminate showed fracture behavior depending on a critical particle size effect. The grain size of polycrystalline β-cristobalite was controlled by annealing time at 1300°C. A hot-pressed laminated composite, annealed for 10 h at 1300°C, had an average grain size of ∼4 μm and a 3-point flexure strength of 131 MPa. Its work of fracture was 2.4 kJ/m² but non-catastrophic fracture behavior was demonstrated. The indentation response indicated crack deflection along the cristobalite debonding interphase. With increasing annealing time, the strength decreased due to the formation of internal macrocracks in the cristobalite layer, which occurred spontaneously during thermally induced transformation.     

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.     

Effect of Sintering Atmosphere on Grain Shape and Grain Growth in Liquid-Phase-Sintered Silicon Carbide

We investigated the effects of the sintering atmosphere on the interface structure and grain-growth behavior in 10-vol%-YAG-added SiC. When α-SiC was liquid-phase-sintered in an Ar atmosphere, the grain/matrix interface was faceted, and abnormal grain growth occurred, regardless of the presence of α-seed grains. In contrast, when the same sample was sintered in N₂, the grain interface was defaceted (rough), and no abnormal grain growth occurred, even with an addition of α-seed grains. X-ray diffraction analysis of this sample showed the formation of a 3C (β-SiC) phase, together with a 6H (α-SiC) phase. These results suggest that the nitrogen dissolved in the liquid matrix made the grain interface rough and induced normal grain growth by an α→β reverse phase transformation. Apparently, the growth behavior of SiC grains in a liquid matrix depends on the structure of the grain interface: abnormal growth for a faceted interface and normal growth for a rough interface.     

Phase Transformation and Texture in Hot-Forged or Annealed Liquid-Phase-Sintered Silicon Carbide Ceramics

Starting from three powder mixtures of 80 vol% SiC (100α, 50α/50β, 100β) and 20 vol% YAG, liquid-phase-sintered silicon carbide ceramics were prepared by hot pressing at 1800°C for 1 h under 25 MPa, and then by hot forging or annealing at 1900°C for 4 h under an applied stress of 25 MPa in argon. The phase transformation and texture development in the as-hot-pressed, hot-forged, and annealed SiC ceramics were investigated via X-ray diffraction (XRD) and the pole figure measurements. The 6H → 4H polytypic transformation was observed in samples consisting of both α- and β-SiC phases when subjected to compressive deformation but absent in the case of annealing, suggesting the deformation-enhanced solubility of aluminum in SiC. Deformation was also found to enhance the 3C → 4H transformation in the sample containing entirely β-phase, which is due to the accelerated solution-precipitation process assisted by grain boundary sliding. The current study showed that the β- →α-phase transformation had little effect on texture development in SiC. Hot forging generally produced the strongest texture, with the calculated maximum of 2.2 times random in samples started with pure α-SiC phase. The mechanism for texture development was explained based on the microstructural observations.     

Microstructural Development of Silicon Carbide Containing Large Seed Grains

Fine (}0.1μm) β-SiC powders, with 3.3 wt% large (}0.44μm) α-SiC or β-SiC particles (seeds) added, were hot-pressed at 1750°C and then annealed at 1850°C to enhance grain growth. Microstructural development during annealing was investigated using image analysis. The introduction of larger seeds into β-SiC accelerated the grain growth of elongated large grains during annealing, in which no appreciable β→α phase transformation occurred. The growth of matrix grains in materials with β-SiC seeds was slower than that in materials with α-SiC seeds. The material with β-SiC seeds, which was annealed at 1850°C for 4 h, had a bimodal microstructure of small matrix grains and large elongated grains. In contrast, the material with α-SiC seeds, also annealed at 1850°C for 4 h, had a uniform microstructure consisting of elongated grains. The fracture toughnesses of the annealed materials with α-SiC and β-SiC seeds were 5.5 and 5.4 MPa·^1/2, respectively. Such results suggested that further optimization of microstructure should be possible with β-SiC seeds, because of the remnant driving force for grain growth caused by the bimodal microstructure.     

Self-Propagating High-Temperature Synthesis of Ti3SiC2: I, Ultra-High-Speed Neutron Diffraction Study of the Reaction Mechanism

In situ neutron diffraction at 0.9 s time resolution was used to reveal the reaction mechanism during the self-propagating high-temperature synthesis (SHS) of Ti₃SiC₂ from furnace-ignited stoichiometric 3Ti + SiC + C mixtures. The diffraction patterns indicate that the SHS proceeded in five stages: (i) preheating of the reactants, (ii) the α→β phase transformation in Ti, (iii) preignition reactions, (iv) the formation of a single solid intermediate phase in <0.9 s, and (v) the rapid nucleation and growth of the product phase Ti₃SiC₂. No amorphous contribution to the diffraction patterns from a liquid phase was detected and, as such, it is unlikely that a liquid phase plays a major role in this SHS reaction. The intermediate phase is believed to be a solid solution of Si in TiC such that the overall stoichiometry is ∼3Ti:1Si:2C. Lattice parameters and known thermal expansion data were used to estimate the ignition temperature at 923 ± 10°C (supported by the α→β phase transformation in Ti) and the combustion temperature at 2320 ± 50°C.     

Investigation of Phase Stability in the System Sic-AlN

Dense samples of several compositions in the system SiC-AIN were fabricated by hot-pressing. The SiC-AIN powder was prepared by carbothermal reduction of an intimate mixture of alumina, silica, and carbon in a nitrogen atmosphere. X-ray diffraction and electron and optical microscopy were used to determine the chemical and microstructural characteristics of the hot-pressed specimens. Materials with bulk compositions between 15 and 75 wt% AIN were found to be nonhomo-geneous when hot-pressed below 2100°C. These materials were determined to be a mixture of SiC-AIN solid solutions with different compositions. The observed compositional variations were distinctly bimodal. The source of the in-homogeneity was the starting SiC-AIN powder. The powders, as well as the hot-pressed samples, consisted of a mixture of small crystals rich in SiC and large AIN-rich crystals. Compositions outside the 15 to 75 wt% AIN region were found to be single phase and to have the wurtzite structure. Hot-pressing SiC-AIN in the intermediate composition range at 2300°C produced an optically and chemically homogeneous material. The precipitation of an SiC-rich phase from a 75 wt% AIN solid solution and the precipitation of an AIN-rich phase from a 47 wt% AIN alloy when annealed at 1700°C are strong indications that a miscibility gas exists in the system SiC-AIN.     

Microstructural Control for Strengthening of Silicon Carbide Ceramics

Fine-grained (<1 μm) silicon carbide ceramics with high strength were obtained by using ultrafine (∼90 nm) β-SiC starting powders and a seeding technique for microstructural control. The microstructures of the as-hot-pressed and annealed ceramics without α-SiC seeds consisted of fine, uniform, and equiaxed grains. In contrast, the annealed material with seeds had a uniform, anisotropic microstructure consisting of elongated grains, owing to the overgrowth of β-phase on α-seeds. The strength, the Weibull modulus, and the fracture toughness of fine-grained SiC ceramics increased with increasing grain size up to ∼1 μm. Such results suggested that a small amount of grain growth in the fine grained region (<1 μm) was beneficial for mechanical properties. The flexural strength and the fracture toughness of the annealed seeded materials were 835 MPa and 4.3 MPa·m^1/2, respectively.     

Effect of Annealing Conditions on Microstructural Development and Phase Transformation in Silicon Carbide

The effect of annealing with and without applied pressure on the microstructural development and phase transformation was investigated in fine-grained β-SiC ceramics containing α-SiC seeds. Materials annealed without pressure had a microstructure consisting of elongated grains, while materials annealed with pressure showed a duplex microstructure consisting of small matrix grains and some of elongated grains. However, annealing with pressure (25 MPa) was found to greatly retard phase transformation from β→α polytypes and inhibit grain growth. This change in lattice parameter suggests that the retardation of phase transformation and grain growth might be attributed to a reduced mass transport rate, which is the result of Al being introduced into the SiC by the annealing pressure.     

The β→α Transformation in Polycrystalline SiC: IV, A Comparison of Conventionally Sintered, Hot-Pressed, Reaction-Sintered, and Chemically Vapor-Deposited Samples

Microstructural characterization of conventionally sintered, hot-pressed, reaction-sintered, and chemically vapor-deposited polycrystalline SiC shows that the initial stages of the β→α transformation in the first three materials are similar, the process being dominated by the elimination of high-energy β→α interfaces. In the final stage of transformation, all four materials transform by nucleation and growth of α lamellae at {111}β twin boundaries or at β stacking faults.     

Coagulated concentrated anatase slurry leads to improved strength of ceramic TiO2 bone scaffolds

Slurry behaviour has an important influence on the properties of ceramic scaffolds produced by the polymer sponge method. By adding chloride salts to the TiO₂ slurry, the viscosity was increased depending on the chloride concentration at low pH and high particle concentration. Slurries with higher viscosity led to closed and dense scaffold struts combined with high porosity, resulting in a compressive strength over 1.6 MPa. Furthermore, scaffold prepared with 0.1 M CaCl₂ and SrCl₂ showed the formation of Ca- and Sr-rich phases at the grain boundaries. These ions were also shown to reduce the activation energy for grain growth in the TiO₂ scaffold as indicated by the significantly larger grain size. Ca²⁺-doped scaffolds had the highest compressive strength, while the strength of Sr²⁺-doped scaffolds was reduced by the formation of a solid solution phase below the sintering temperature.     

Effect of the Amount of Additives and Post-Heat Treatment on the Microstructure and Mechanical Properties of Yttrium–α-Sialon Ceramics

The yttrium–sialon ceramics with the composition of Y_0.333Si₁₀Al₂ON₁₅ and an excess addition of Y₂O₃ (2 or 5 wt%) were fabricated by hot isostatic press (HIP) sintering at 1800°C for 1 h. The resulting materials were subsequently heat-treated in the temperature range 1300–1900°C to investigate its effect on the α→β-sialon phase transformation, the morphology of α-sialon grains, and mechanical properties. The results show that α-sialons stabilized by yttrium have high thermal stability. An adjustment of the α-sialon phase composition is the dominating reaction in the investigated Y–α-sialon ceramics during low-temperature annealing. Incorporation of excess Y₂O₃ could effectively promote the formation of elongated α-sialon grains during post-heat-treating at relatively higher temperature (1700° and 1900°C) and hence resulted in a high fracture toughness ( K _IC= 6.3 MPa·m^1/2) via grain debonding and pullout effects. Although the addition of 5 wt% Y₂O₃ could promote the growth of elongated α grains with a higher aspect ratio, the higher liquid-phase content increased the interfacial bonding strength and therefore hindered interface debonding and crack deflection. The heat treatment at 1500°C significantly changed the morphology of α-sialon grains from elongated to equiaxed and hence decreased its toughness.     

Microstructural Evolution in Liquid-Phase-Sintered SiC: Part III, Effect of Nitrogen-Gas Sintering Atmosphere

Effects of N₂ sintering atmosphere and the starting SiC powder on the microstructural evolution of liquid-phase-sintered (LPS) SiC were studied. It was found that, for the β-SiC starting powder case, there was complete suppression of the β→α phase transformation, which otherwise goes to completion in Ar atmosphere. It was also found that the microstructures were equiaxed and that the coarsening was severely retarded, which was in contrast with the Ar-atmosphere case. Chemical analyses of the specimens sintered in N₂ atmosphere revealed the presence of significant amounts of nitrogen, which was believed to reside mostly in the intergranular phase. It was argued that the presence of nitrogen in the LPS SiC helped stabilize the β-SiC phase, thereby preventing the β→α phase transformation and the attendant formation of elongated grains. To investigate the coarsening retardation, internal friction measurements were performed on LPS SiC specimens sintered in either Ar or N₂ atmosphere. For specimens sintered in N₂ atmosphere, a remarkable shift of the grain-boundary sliding relaxation peak toward higher temperatures and very high activation energy values were observed, possibly due to the incorporation of nitrogen into the structure of the intergranular liquid phase. The highly refractory and viscous nature of the intergranular phase was deemed responsible for retarding the solution–reprecipitation coarsening in these materials. Parallel experiments with specimens sintered using α-SiC starting powders further reinforce these arguments. Thus, processing of LPS SiC in N₂ atmosphere open the possibility of tailoring their microstructures for room-temperature mechanical properties and for making high-temperature materials that are highly resistant to coarsening and creep.     

Thermal decomposition of TiH<Subscript>2</Subscript>: A TRXRD study

Thermal decomposition of SHS-produced TiH2 powder in vacuum at temperatures below 570°C was explored by time-resolved XRD. The process got started with transformation of starting TiH₂ into solid solution of hydrogen in β-Ti (β-Ti[H]) and then followed by the polymorphic β-Ti[H] → α-Ti[H] transition and subsequent hydrogen elimination to yield α-Ti. Marked changes in the phase composition of starting TiH₂ were found to get started around 450°C.     

Phase Transformations in Dicalcium Silicate: II, TEM Studies of Crystallography, Microstructure, and Mechanisms

The crystallography, microstructures, and phase transformation mechanisms in dicalcium silicate (Ca₂SiO₄) were studied by TEM. Three types of superlattice structures were observed in the α'_L and β phases. Almost all β grains were twinned and strained. Symmetry-related domain structures inherited from previous high-temperature transformations were observed in β grains. Both the α→α'_H and α'_L→β transformations were considered to be ferroelastic, and spontaneous strains were calculated. In terms of the crystal structures, the major driving force for the β→γ transformation is proposed to be strains and cation charge repulsions in the β structure. This mechanism can be displacive, but it needs to overcome a comparatively high energy barrier.     

Fine-Grained Silicon Carbide Ceramics with Oxynitride Glass

By using an oxynitride glass composition from the Y-Mg-Si-Al-O-N system as a sintering additive, the effect of atmosphere on densification was investigated during the liquid-phase sintering of SiC, and the resulting microstructure and mechanical properties of the sintered and subsequently annealed materials were investigated. SiC ceramics that were densified with 10 wt% oxynitride glass showed higher sinterability in a nitrogen atmosphere. Oxynitride glass enlarged the stability region of β-SiC and suppressed β→ alpha phase transformation, which resulted in an equiaxed microstructure. Grain growth of fine-grained SiC in some extent (up to ∼300 nm) was beneficial in improving both room-temperature strength and toughness. The best results were obtained when the ceramics were hot-pressed at 1800°C for 1 h in a nitrogen atmosphere and subsequently annealed at 1900°C for 3 h in an argon atmosphere. The room-temperature flexural strength and fracture toughness of the material were 847 MPa and 3.5 MPa·m^1/2, respectively.     

Microstructural Evolution in Liquid-Phase-Sintered SiC: Part I, Effect of Starting Powder

The effect of starting SiC powder (β-SiC or α-SiC), with simultaneous additions of Al₂O₃ and Y₂O₃, on the microstructural evolution of liquid-phase-sintered (LPS) SiC has been studied. When using α-SiC starting powder, the resulting microstructures contain hexagonal platelike α-SiC grains with an average aspect ratio of 1.4. This anisotropic coarsening is consistent with interface energy anisotropy in α-SiC. When using β-SiC starting powder, the β→α phase transformation induces additional anisotropy in the coarsening of platelike SiC grains. A strong correlation between the extent of β→α phase transformation, as determined using quantitative XRD analysis, and the average grain aspect ratio is observed, with the maximum average aspect ratio reaching 3.8. Based on these observations and additional SEM and TEM characterizations of the microstructures, a model for the growth of these high-aspect-ratio SiC grains is proposed.     

Effects of Microstructure on Superplastic Behavior and Deformation Mechanisms in β-Silicon Nitride Ceramics

The influence of grain shape and size on superplastic behavior and deformation mechanisms was investigated in annealed β-silicon nitride materials and compared with the results for hot-pressed material. The microstructure of the annealed materials consisted of fine equiaxed β-grains together with some elongated ones. Similar to the deformation behavior in the hot-pressed material, strain hardening did not occur in these annealed materials. Moreover, in contrast to the deformation behavior under tension, grain alignment under compression resulting from the development of a mild texture did not give rise to strain hardening. An annealed material with small elongated grains had a flow-stress dependency of n = 1, whereas other annealed materials with large elongated grains exhibited a flow-stress dependency of n = 1.6. In terms of texture development and the effect of grain shape on the creep rate when diffusion was the rate-controlling mechanism, a single curve with a stress exponent of ∼1 and a grain-size exponent of 3 were obtained for all materials. This suggests that the deformation mechanism in these annealed materials was the same as that of fine equiaxed β-silicon nitride.     

Synthesis of nonstoichiometric high entropy Nb-added carbides

A novel class of nonstoichiometric high-entropy carbide (HEC_x) materials, namely, Nb/TiC/TaC, Nb/TiC/TaC/VC and Nb/TiC/TaC/VC/WC, were produced by mechanically milled and spark plasma sintering (SPS) from Nb and carbides. XRD, SEM-EDS and S/TEM-EDS were used to characterize the phase constitution, microstructure and compositional distribution of samples, respectively. HEC_x exhibits a single-phase rock-salt crystal structure with a relatively uniform elemental distribution. Among the three different HEC_x materials, Nb/TiC/TaC/VC/WC with an average grain size of 2.15 μm sintered at 1600 °C shows an enhanced fracture toughness of 5.1 ± 0.1 MPa m^1/2 compared with transition metal carbides. The mechanically mixed and low sintering temperature lead to the formation of finer grains. The higher fracture toughness can be attributed to atomic relaxation resulting from carbon vacancies and solid solution strengthening.