Improved Sliding-Wear Resistance in In Situ-Toughened Silicon Carbide

The effect of microstructure on the sliding-wear properties has been studied in two types of pressureless liquid-phase-sintered (LPS) SiC ceramics, one with coarse, in situ -grown elongated grains and the other with fine, equiaxed grains. Elongated-grain LPS SiC has been found to have dramatically improved sliding-wear properties over equiaxed-grain LPS SiC, which has been attributed to the interlocking network of elongated SiC grains. The introduction of an interlocking network of elongated grains represents a new guideline for the microstructural design of polycrystalline ceramics that are both sliding-wear resistant and toughened.     

Microstructural design of sliding-wear-resistant liquid-phase-sintered SiC: An overview

We have reviewed the effect of microstructure – content of intergranular phase, grain size, and grain shape – on the lubricated, sliding-wear of pressureless liquid-phase-sintered (LPS) SiC ceramics. The sliding-wear resistance in LPS SiC decreases with an increase in the content of the intergranular phase or an increase in the equiaxed-grain coarsening. However, the sliding-wear resistance is dramatically improved with anisotropic-grain coarsening. Based on these results we suggest two strategies for the microstructural design of low-cost, sliding-wear resistant SiC-based ceramics: (1) grain refinement, and (2) grain elongation. The latter strategy allows the materials to be simultaneously in situ toughened, and we describe its optimization by judicious selection of the SiC starting powder.     

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.     

In Situ-Toughened Silicon Carbide

A new processing strategy based on atmospheric pressure sintering is presented for obtaining dense SiC-based materials with microstructures consisting of (i) uniformly distributed elongate-shaped α-SiC grains and (ii) relatively high amounts (20 vol%) of second-phase yttrium aluminum garnet (YAG). This strategy entails the sintering of β-SiC powder doped with α-SiC, Al₂O₃, and Y₂O₃. The Al₂O₃ and Y₂O₃ aid in the liquid-phase sintering of SiC and form in situ YAG, which has a significant thermal expansion mismatch with SiC. During a subsequent grain-growth heat treatment, it is postulated that the α-SiC "seeds" assist in controlling in situ growth of the elongated α-SiC grains. The fracture pattern in the in situ -toughened SiC is intergranular with evidence of copious crack-wake bridging, akin to toughened Si₃N₄ ceramics. The elongate nature of the α-SiC grains, together with the high thermal-residual stresses in the microstructure, enhance the observed crack-wake bridging. This bridging accounts for a measured twofold increase in the indentation toughness of this new class of in situ -toughened SiC relative to a commercial SiC.     

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.     

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.     

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.     

Effect of Initial α-Phase Content on Microstructure and Mechanical Properties of Sintered Silicon Carbide

By using α- and β-SiC starting powders with similar particle sizes, the effects of initial α-phase content on the microstructure and the mechanical properties of the liquid-phase-sintered and subsequently annealed materials were investigated. The microstructures developed were analyzed by image analysis. When β-SiC powder was used, the grains became elongated. The average diameter decreased with increasing α-SiC content and the aspect ratio showed a maximum at 10%α-SiC and decreased with increasing α-SiC content in the starting powder. Such results suggest that microstructure can be controlled by changing α-phase content in starting powders. The strength increased with increasing α-SiC content in the starting powder while the fracture toughness decreased with increasing α-SiC content. There may be a trade-off in improving both the strength and toughness in SiC ceramics sintered with oxide additives.     

液相烧结SiC陶瓷

采用Al2O3、Y2O3为助烧剂,热压烧结获得了致密的α-SiC和β-SiC陶瓷,研究了起始粉末的性能对烧结体的物相组成和显微结构的影响。实验结果表明,Al2O3、Y2O3原位形成了YAG,材料以液相烧结机制致密化,并通过溶解和再析出机制,促进晶体生长。物相分析表明,β-SiC陶瓷粉末在烧结过程中发生了β→α的相变。显微结构观察显示,β-SiC陶瓷中生成了长柱状晶粒。     

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.     

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.     

Effect of Microstructure on Sliding-Wear Properties of Liquid-Phase-Sintered α-SiC

We have studied, for the first time, the effect of the content of intergranular phase and grain size on the sliding-wear resistance of pressureless, liquid-phase-sintered (LPS) α-SiC (silicon carbide) ceramics. It was found that the sliding-wear behavior of these ceramics is similar to what is observed in other polycrystalline ceramics: initial mild, plasticity-controlled wear followed by severe, fracture-controlled wear, with well-defined wear transition. We have found that the increase in the content of intergranular phase and the grain coarsening leads to the degradation of the sliding-wear resistance in LPS α-SiC ceramics. A mechanistic model is used to rationalize these wear results, and to provide guidelines for the design and fabrication of low cost, highly wear-resistant SiC-based ceramics. This is likely to have important implications because SiC-based materials are being used increasingly in contact-mechanical and tribological applications.     

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 liquid-phase content on the contact-mechanical properties of liquid-phase-sintered α-SiC

Effect of the content of the intergranular phase (Y₃Al₅O₁₂ or yttrium aluminum garnet or YAG) on the room-temperature contact-mechanical properties of pressureless, liquid-phase-sintered (LPS) α-SiC ceramics has been studied. An increase in YAG vol.% is found to result in the expected degradation of the elastic modulus and the indentation yield strength in LPS SiC. However, with increasing YAG vol.% the degradation in the hardness and the sliding-wear resistance is found to be severe, while the indentation toughness first increases and then decreases. These results are analyzed, and discussed in the context of providing guidelines for the design and fabrication of low-cost LPS SiC ceramics with tailored contact-mechanical properties.     

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.     

Complex impedance spectroscopy study of a liquid-phase-sintered α-SiC ceramic

The electrical response of a liquid-phase-sintered (LPS) α-SiC with 10 wt.% Y₃Al₅O₁₂ (YAG) additives was studied from near-ambient temperature up to 800 °C by complex impedance spectroscopy. The electrical conductivity of this LPS SiC ceramic was found to increase with increasing temperature, which was attributed to the semiconductor nature of the SiC grains. It was concluded that the contribution of the SiC grains to the electrical conductivity of the LPS SiC ceramic at moderate temperatures (<450 °C) is a somewhat greater than that of the YAG phase. In contrast, at higher temperatures the SiC grains control the electrical conductivity of the LPS SiC ceramic. It was also found that there are two activation energies for the electrical conduction process of the α-SiC grains. These are 0.19 eV at temperatures lower than ∼400 °C and 2.96 eV at temperatures higher than ∼500 °C. The existence of two temperature-dependence conduction regimes reflects the core–shell substructure that develops within the SiC grains during the liquid-phase sintering, where the core is pure SiC (intrinsic semiconductor) and the shell is mainly Al-doped SiC (extrinsic semiconductor).     

Effects of the initial α-SiC content on the microstructure, mechanical properties, and permeability of macroporous silicon carbide ceramics

By using α- and/or β-SiC staring powders, the effects of the initial α-phase content on the microstructure, mechanical properties, and permeability of macroporous SiC ceramics were investigated. When β-SiC powder or a mixture of α/β powders containing a small amount (≤10%) of α-SiC powder was used, the microstructure consisted of large platelet grains. In contrast, when using α-SiC powder or α/β powders containing a large amount (>10%) of α powders, the microstructure consisted of small equiaxed grains. The development of large α-SiC platelet grains in the microstructure did not result in any improvement of the flexural strength of the macroporous SiC ceramics because of the accompanying pore growth and grain growth. The growth of the platelet-SiC grains was beneficial in increasing the gas permeability of the macroporous SiC ceramics from 4.12 × 10⁻¹³ m² for macroporous SiC with an equiaxed microstructure to 1.89 × 10⁻¹² m² for macroporous SiC ceramics with large platelet grains.     

In Situ Processing of Silicon Carbide Layer Structures

A novel route to low-cost processing of silicon carbide (SiC) layer structures is desribed. The processing involves pressureless liquid-phase cosintering of compacted power layers of SiC, containing alumina (Al₂O₃) and yttria (Y₂O₃ sintering additives to yield and yttrium aluminum garnet (YAG) second phase. By adjusting the β:α SiC phase ratios in the individual starting powders, alternate layers with distinctively different microstructures are produced: (i) "homogeneous" microstructures, with fine equiaxed SiC grains, designed for high strength; and (ii) "heterogeneous: microstructures with coarse and elongate SiC grains, designed for high toughness. By virtue of the common SiC and YAG phases, the interlayer interfaces are chemically compatible and strongly bonded. Exploratory Hertzian indetation tests across a bilayer interface confirm the capacity of the tough heterogeneous layer to inhibit potentially dangerous cracks propagating through the homogeneous layer. The potential for application of this novel processing approach to other layer architectures and other ceramic systems is considered.     

Fabrication and Mechanical Properties of Silicon Carbide-Silicon Nitride Composites with Oxynitride Glass

A microstructure that consisted of uniformly distributed, elongated β-Si₃N₄ grains, equiaxed β-SiC grains, and an amorphous grain-boundary phase was developed by using β-SiC and alpha-Si₃N₄ powders. By hot pressing, elongated β-Si₃N₄ grains were grown via alpha right arrow β phase transformation and equiaxed β-SiC grains were formed because of inhibited grain growth. The strength and fracture toughness of SiC have been improved by adding Si₃N₄ particles, because of the reduced defect size and the enhanced bridging and crack deflection by the elongated β-Si₃N₄ grains. Typical flexural-strength and fracture-toughness values of SiC-35-wt%-Si₃N₄ composites were 1020 MPa and 5.1 MPam^1/2, respectively.     

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.