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.     

Microstructural Analysis of Liquid-Phase-Sintered β-Silicon Carbide

The microstructures of fine-grained β-SiC materials with α-SiC seeds annealed either with or without uniaxial pressure at 1900°C for 4 h in an argon atmosphere were investigated using analytical electron microscopy and high-resolution electron microscopy (HREM). An applied annealing pressure can greatly retard phase transformation and grain growth. The material annealed with pressure consisted of fine grains with β-SiC as a major phase. In contrast, the microstructure in the material annealed without pressure consisted of elongated grains with half α-SiC. Energy-dispersive X-ray analysis showed no differences in the amount of segregation of aluminum and oxygen atoms at grain boundaries, but did show a significant difference in the segregation of yttrium atoms at grain boundaries along SiC grains for the two materials. The increased segregation of yttrium ions at grain boundaries caused by the applied pressure might be the reason for the retarded phase transformation and grain growth. HREM showed a thin secondary phase of 1 nm at the grain boundary interface for both materials. The development of a composite grain consisting of a mixture of β/α polytypes during annealing was a feature common to both materials. The possible mechanisms for grain growth and phase transformation are discussed.     

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.     

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.     

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.     

In S/Yu-Toughened Silicon Carbide-Titanium Carbide Composites

A process based on liquid-phase sintering and subsequent annealing for grain growth is presented to obtain in situ -toughened SiC-30 wt% TiC composites. Its microstructures consist of uniformly distributed elongated α-SiC grains, matrixlike TiC grains, and yttrium aluminum garnet (YAG) as a grain boundary phase. The composites were fabricated from β-SiC and TiC powders with the liquid forming additives of A1₂O₃ and Y₂O₃ by hot pressing. During the subsequent heat treatment, the β→α phase transformation of SiC led to the in situ growth of elongated α-SiC grains. The fracture toughness of the SiC-30 wt% TiC composites after 6-h annealing was 6.9 MPa-m^1/2, approximately 60% higher than that of as-hot-pressed composites (4.4 MPa-m^1/2). Bridging and crack deflection by the elongated α-SiC grains appear to account for the increased toughness of this new class of composites.     

Mechanism of Grain Growth and α-β'Transformation During Liquid-Phase Sintering of β'-Sialon

The rates of grain coarsening and α-β'transformation during the liquid-phase sintering of Si₃N₄-β'₆₀-YAG sialon have been measured at varying liquid fractions and z values in order to determine the rate-controlling mechanism. The average β'-grain size after sintering for 16 h at 1650°C shows no variation with the liquid-matrix fraction if the z value is fixed and a marked increase with the z value if the liquid fraction is fixed. Similarly, the amount of untransformed α-phase after sintering for 2.5 or 3.5 min at 1600°C shows no variation with the liquid-matrix fraction if the z value is fixed and a marked decrease with the z value if the liquid fraction is fixed. These results show that the grain coarsening and the α-β'transformation are controlled by the interface reaction. This conclusion is consistent with the observations in carbide-Co systems and with the theoretical predictions that the growth of faceted grains is controlled by interface reaction and that of spherical grains by diffusion. A general rule between the shape and the growth mechanism of grains in a liquid matrix is thus proposed.     

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.     

Microstructure and Fracture Toughness of Hot-Pressed Silicon Carbide Reinforced with Silicon Carbide Whisker

The effects of β-SiC whisker addition on the microstructural evolution and fracture toughness ( K _IC) of hot-pressed SiC were investigated. Most of the whiskers added disappeared during the densifcation process by transformation into the α-phase. The remaining whiskers acted as nuclei for grain growth, resulting in the formation of large tabular grains around the whiskers. The tabular grains around the whiskers were believed to be formed because of the extreme anisotropy of the interfacial energy between α- and β-SiC. The K _IC of the material was improved significantly by the whisker addition. The increase in the K _IC was attributed to crack bridging followed by grain pullout as a result of the formation of tabular grains in a fine matrix.     

Nonequiaxial Grain Growth and Polytype Transformation of Sintered α-Silicon Carbide and β-Silicon Carbide

α(6 H )- and β(3 C )-SiC powders were sintered with the addition of AlB₂ and carbon. α-SiC powder could be densified to ∼98% of the theoretical density over a wide range of temperatures from 1900° to 2150°C and with the additives of 0.67–2.7 mass% of AlB₂ and 2.0 mass% of carbon. Sintering of the β-SiC powder required a temperature of >2000°C for densification with these additives. Grains in the α-SiC specimens grew gradually from spherical-shaped to plate-shaped grains at 2000°C; the 6 H polytype transformed mainly to 4 H . On the other hand, grains in the β-SiC largely grew at >2000°C; the 3 C polytype transformed to 4 H , 6 H , and 15 R . The stacking faults introduced in grains were denser in β-SiC than in α-SiC. The rapid grain growth in the β-SiC specimen was attributed to polytype transformation from the unstable 3 C polytype at the sintering temperature.     

Effect of β-to-α Phase Transformation on the Microstructural Development and Mechanical Properties of Fine-Grained Silicon Carbide Ceramics

Ultrafine β-SiC powders mixed with 7 wt% Al₂O_3, 2 wt% Y₂O₃, and 1.785 wt% CaCO₃ were hot-pressed and subsequently annealed in either the absence or the presence of applied pressure. Because the β-SiC to α-SiC phase transformation is dependent on annealing conditions, the novel processing technique of annealing under pressure can control this phase transformation, and, hence, the microstructures and mechanical properties of fine-grained liquid-phase-sintered SiC ceramics. In comparison to annealing without pressure, the application of pressure during annealing greatly suppressed the phase transformation from β-SiC to α-SiC. Materials annealed with pressure exhibited a fine microstructure with equiaxed grains when the phase transformation from β-SiC to α-SiC was <30 vol%, whereas materials annealed without pressure developed microstructures with elongated grains when phase transformation was >30 vol%. These results suggested that the precise control of phase transformation in SiC ceramics and their mechanical properties could be achieved through annealing with or without pressure.     

Microstructural Evolution in Liquid-Phase-Sintered SiC: Part II, Effects of Planar Defects and Seeds in the Starting Powder

The effects of planar-defect density in a β-SiC starting powder and the addition of α-SiC seeds to that powder on microstructural evolution in liquid-phase-sintered (LPS) SiC have been studied separately. Planar-defect density is altered by appropriate heat treatment of an as-received β-SiC starting powder. It was found that a decrease in the planar-defect density in the powder retards the β→α phase transformation rate. It is proposed that, because nucleation of α-SiC occurs on the planar defects present in the β-SiC starting powders, the nucleation rate and the attendant rate of transformation decrease with a reduction in planar-defect density. Consequently, this reduces the frequency of formation of elongated β/α composite grains, resulting in lower average aspect ratios, as the initial untransformed β-SiC grains coarsen in an equiaxed manner. In contrast, addition of external α-SiC seeds has no effect on the β→α phase transformation rate, although a significant reduction in the average aspect ratio occurs. It is proposed that preferential equiaxed coarsening of the α-SiC seeds over elongated coarsening of β/α composite grains occurs, resulting in a reduction of overall coarsening anisotropy.     

Strategies and practices for suppressing abnormal grain growth during liquid phase sintering

Abnormal grain growth (AGG), where a small number of grains grow to sizes much larger than the neighboring matrix grains, is a frequent occurrence in liquid phase sintering of ceramics and cermets. As AGG can be detrimental to the material properties, a considerable amount of research on the nature, causes and suppression of AGG has been carried out. In this review, we outline the mixed control theory of grain growth and the principle of microstructural evolution that have been developed by Kang and coworkers over the last two decades. The theory and the principle, which are based on theories of crystal growth from a liquid, state that grain growth behavior is controlled by the nature of the solid-liquid interfaces, either atomically rough (macroscopically rounded) or smooth (macroscopically faceted). For grains with atomically rough solid-liquid interfaces, growth is controlled by diffusion of solute through the liquid phase and normal grain growth always occurs. For grains with faceted solid-liquid interfaces (or a mixture of rough and faceted interfaces), growth is interface reaction-controlled and diffusion-controlled below and above a critical driving force for growth, respectively. Depending on the relative values of the critical driving force for growth Δg_c and the maximum driving force for the largest grain in the system Δg_max, pseudo-normal, abnormal, and stagnant grain growth can take place. Based on this theory and principle, we present strategies for suppressing AGG by adjusting Δg_c and Δg_max to avoid AGG and examples of the successful use of these strategies.     

Transmission Electron Microscopy Microstructure of 0.95(Na0.5K0.5)NbO3–0.05BaTiO3 Ceramics

Microstructural characterizations using transmission electron microscopy on 0.95(Na_0.5K_0.5)NbO₃–0.05BaTiO₃ ceramics sintered at 1030°–1150°C for 2 h were carried out. The liquid phase was found at the triple junction of the grains in all specimens and abnormal grain growth occurred in the presence of the liquid phase. Abnormally grown grains whose shapes were cuboidal were well developed. Anisotropically faceted amorphous liquid phase pockets were observed inside the grain in a specimen sintered at 1060°C for 2 h. The interface between the grain and the liquid matrix was flat and some were identified to be {100} planes of the grains. A certain amount of liquid at the sintering temperature of 1060°C enhanced the abnormal grain growth and contributed to the improvement of the piezoelectric properties.     

Polytypes, Grain Growth, and Fracture Toughness of Metal Boride Particulate SiC Composites

In order to understand the relation between microstructure and toughening behavior in SiC materials, NbB₂, TaB₂, TiB₂, and ZrB₂ particulate SiC composites were fabricated with pressureless sintering. In the composites, 3(cubic)-SiC powder was used as starting material for the matrix. The p-SiC powder transformed to a(noncubic) phase during sintering. The transformation, the behavior of which was influenced by the existence of metal boride particles, was accompanied by normal or exaggerated grain growth. The metal boride particles suppressed large-scale exaggerated grain growth of SiC, and it had a tendency to simulate grain growth with a high aspect ratio of the SiC grains. Increase in the fracture toughness of the composites was observed when the grain size and the aspect ratio of the SiC grains increased together. The toughening behavior is discussed based on a grain bridging mechanism.     

Sliding-Wear-Resistant Liquid-Phase-Sintered SiC Processed Using α-SiC Starting Powders

Low-cost α-silicon carbide (SiC) starting powder, instead of the more expensive β-SiC starting powder, has been used to process liquid-phase-sintered (LPS) SiC ceramics with different microstructures: (i) elongated SiC grains ( in situ toughened LPS SiC), (ii) fine equiaxed SiC grains, and (iii) coarse equiaxed SiC grains. The effects of microstructure on the sliding-wear properties of these LPS SiC ceramics have been studied. The sliding-wear resistance of the in situ toughened LPS SiC ceramic is found to be significantly better than that of two equiaxed-grain LPS SiC ceramics. This has been attributed to the existence of a hard, interlocking network of elongated SiC grains and the isolated nature of the yttrium aluminum garnet (YAG) second phase in the in situ toughened LPS SiC ceramic. This is in contrast to the equiaxed-grain LPS SiC ceramics, where the equiaxed grains are embedded within a continuous YAG phase matrix. The use of the α-SiC starting powder allows the processing of low-cost LPS SiC ceramics that are both sliding-wear resistant and tough.     

β→α Transformation in Polycrystalline Sic: II, Interfacial Energetics

The β→α transformation in polycrystalline Sic occurs by the rapid growth of composite grains consisting of α-SiC plates "sandwiched" between grains of recrystallizedp-SiC. Growth of these composite grains into the fine-grained β matrix occurs much more rapidly than thickening of the α plates into their β"envelopes." A phenomenological analysis of the energetics of these several growth processes is presented and it is shown that the observations can be explained by the extreme anisotropy of the interfacial energy between β− and α−SiC; {lll}_β(0001)^α interfaces have much lower energies than random, β/α interfaces. In reaction-sintered Sic, this anisotropy is manifested by rapid growth of a seeds along their basal planes into the epitaxial β reaction product; slow growth occurs perpendicular to the basal planes.     

Flaw-Tolerance and R-Curve Behavior of Liquid-Phase-Sintered Silicon Carbides with Different Microstructures

β-SiC powder containing 6 wt% A1₂O₃ and 4 wt% Y₂O₃ as sintering additives was pressureless sintered at 2000°C for 1 h (AYE-SiC) and 3 h (AYP-SiC). AYE-SiC consisted of an equiaxed grain structure and AYP-SiC exhibited a micro-structure with platelike grains as a result of grain growth related to β→α phase transformation during sintering, R -curve behavior and flaw tolerance for these silicon carbides were evaluated by the indentation-strength technique. For comparison, the R -curve behavior of conventional sintered, boron- and carbon-doped SiC (SS-SiC) was evaluated. AYE-SiC and AYP-SiC exhibited rising R -curve behavior with toughening exponents of m = 0.042 and m = 0.135, respectively. AYP-SiC exhibited better flaw tolerance and more sharply rising R -curve behavior than AYE-SiC. The more sharply rising R -curve behavior and the better flaw tolerance of AYP-SiC were attributed mainly to grain bridging of crack faces by platelike grains. Because of the high degree of transgranular fracture, SS-SiC exhibited a flat R -curve despite a microstructural feature with platelike grains.     

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 Ba6Ti17O40/BaTiO3 Interface Structure on {111} Twin Formation and Abnormal Grain Growth in BaTiO3

A structural transition of Ba₆Ti₁₇O₄₀/BaTiO₃ interfaces from faceted to rough was induced by reducing oxygen partial pressure in the atmosphere. As the oxygen partial pressure decreased, the number densities of {111} twins and abnormal grain decreased. TEM observation showed that the twin formation was governed only by the faceting of the interface. Experimental evidence of {111} twin-assisted abnormal growth of faceted BaTiO₃ grains was also obtained.