Inhibition of grain growth in liquid-phase sintered SiC ceramics by AlN additive and spark plasma sintering

SiC ceramics were prepared from nanosized β-SiC powder with different compositions of AlN and Y₂O₃ sintering additives by spark plasma sintering (SPS) at 1900 °C for 600 s in N₂. The relative density of the sintered SiC specimens increased with increasing amount of AlN, reaching a relative density higher than 99%, while at the same time grain size decreased significantly. The smallest average grain size of 150 nm was observed for SiC sample sintered with 10 vol% of additives consisting of 90 mol% AlN and 10 mol% Y₂O₃. Fully dense nanostructured SiC ceramics with inhibited grain growth were obtained by the AlN additive and SPS technique. The flexural strength of the SiC body containing 70 mol% AlN and 30 mol% Y₂O₃ additives reached the maximum value of 1000 MPa. The SiC bodies prepared with AlN and Y₂O₃ additives had the fracture toughness of around 2.5 MPam^1/2.     

Particle size effect of starting SiC on processing,microstructures and mechanical properties of liquid phase-sintered SiC

Dense SiC (97.3–99.2% relative density) of 1.1–3.5 μm average grain size was prepared by the combination of colloidal processing of bimodal SiC particles with sintering additives (Al₂O₃ plus Y₂O₃, 2–4 vol%) and subsequent hot-pressing at 1900–1950 °C. The fracture toughness of SiC was sensitive to the grain boundary thickness which was controlled by grain size and amount of oxide additives. A maximum fracture toughness (6.2 MPa m^1/2) was measured at 20 nm of grain boundary thickness. The mixing of 30 nm SiC (25 vol%) with 800 nm SiC (75 vol%) was effective to reduce the flaw size of fracture origin, in addition to a high fracture toughness, leading to the increase of flexural strength. However, the processing of a mixture of 30 nm SiC (25 vol%)–330 nm SiC (75 vol%) provided too small grains (1.1 μm average grain size), resultant thin grain boundaries (12 nm), decreased fracture toughness, and relatively large defect of fracture origin, resulting in the decreased strength.     

The effect of rare earth oxides on the pressureless liquid phase sintering of α-SiC

Silicon carbide (SiC) ceramics have been fabricated by pressureless liquid phase sintering with Al₂O₃ and rare-earth oxides (Lu₂O₃, Er₂O₃ and CeO₂) as sintering additives. The effect was investigated of the different types of rare earth oxides on the mechanical property, thermal conductivity and microstructure of pressureless liquid phase sintered SiC ceramics. The room temperature mechanical properties of the ceramics were affected by the type of rare earth oxides. The high temperature performances of the ceramics were influenced by the triple junction grain boundary phases. With well crystallized triple junction grain boundary phase, the SiC ceramic with Al₂O₃–Lu₂O₃ as sintering additive showed good high temperature (1300 °C) performance. With clean SiC grain boundary, the SiC ceramic with Al₂O₃–CeO₂ as sintering additive showed good room temperature thermal conductivity. By using appropriate rare earth oxide, targeted tailoring of the demanding properties of pressureless liquid phase sintered SiC ceramics can be achieved.     

Spark plasma sintering and pressureless sintering of SiC using aluminum borocarbide additives

Aluminum borocarbide powders (Al₃BC₃ and Al₈B₄C₇) were synthesized, and the ternary powders were used as a sintering additive of SiC. The densification of SiC was nearly completed at 1670 °C using spark plasma sintering (SPS) and pressureless sintering was possible at 1950 °C. The sintering behavior of SiC using the new additive systems was nearly identical with that using the conventional Al–B–C system, but grain growth was suppressed when adding the borocarbides. In addition, oxidation of the fine additive powders did not intensively occur in air, which has been a problem in the case of the Al–B–C system for industrial application. The hardness, Young's modulus and fracture toughness of a sintered SiC specimen were 21.6 GPa, 439 GPa and 4.6 MPa m^1/2, respectively. The ternary borocarbide powders are efficient sintering additives of SiC.     

Electrical resistivity of silicon carbide ceramics sintered with 1 wt% aluminum nitride and rare earth oxide

The influence of additive composition on the electrical resistivity of hot-pressed liquid-phase sintered (LPS)-SiC was investigated using AlN–RE₂O₃ (RE = Sc, Nd, Eu, Gd, Ho, Er, Lu) mixtures at a molar ratio of 60:40. It was found that all specimens could be sintered to densities >95% of the theoretical density by adding 5 wt% in situ-synthesized nano-sized SiC and 1 wt% AlN–RE₂O₃ additives. Six out of seven SiC ceramics showed very low electrical resistivity on the order of 10^?4 Ω m. This low electrical resistivity was attributed to the growth of nitrogen-doped SiC grains and the confinement of non-conducting RE-containing phases in the junction areas. The SiC ceramics sintered with AlN–Lu₂O₃ showed a relatively high electrical resistivity (～10^?2 Ω m) due to its lower carrier density (～10¹⁷ cm^?3), which was caused by the growth of faceted grains and the resulting weak interface between SiC grains.     

Densification,microstructure and mechanical properties of ZrB2–SiCw ceramic composites

ZrB₂–SiCw composites were prepared through hot-pressing at a low temperature of 1800 °C, and Al₂O₃ plus Y₂O₃ were added as sintering aids. Analysis revealed that additives may react with impurities (i.e. surface oxygen impurities and residual metallic impurities) to form a transient liquid phase, thus promote the sintering and densification of ZrB₂–SiCw composites. The content of additives was found to have a significant influence on the sinterability, microstructure and mechanical properties of ZrB₂–SiCw composites. ZrB₂–SiCw composite prepared with a small amount of additives (3 vol.%) provided the optimal combination of microstructure (relative density of 98.3%) and excellent properties, including flexural strength of 783 MPa and fracture toughness of 6.7 MPa m^1/2. With further addition of additives, SiC whiskers were inclined to gather together and be enveloped by excessive liquids to form core-rim-like structures, which lead to little decrease in mechanical properties.     

Aqueous gelcasting of ZrB2–SiC ultra high temperature ceramics

ZrB₂–SiC ultra high temperature ceramics containing B₄C and C as sintering additives were successfully prepared by aqueous gelcasting and pressureless sintering. Polyacrylic acid (PAA) was used as the dispersant throughout this research. The various effects of zeta potential, pH value, dispersant concentration, solid loading and ball-milling time on the rheology and fluidity behavior of ZrB₂–SiC suspension were investigated in detail. A well-dispersed suspension with 50 vol.% solid loading was prepared at pH 10 with 0.4 wt.% PAA after ball milling at 240 rpm for 24 h. Then crack-free green ZrB₂–SiC ceramics were obtained by gelcasting process and then pressureless sintered at 2100 °C to about 98% relative density. The microstructure and mechanical properties were examined, and the flexural strength and fracture toughness were 405 ± 27 MPa and 4.3 ± 0.3 MPa m^1/2, respectively.     

Densification,microstructure and mechanical properties of hot pressed ZrB2–SiC ceramic doped with nano-sized carbon black

The effect of nano-sized carbon black on densification behavior, microstructure, and mechanical properties of zirconium diboride (ZrB₂) – silicon carbide (SiC) ceramic was studied. A ZrB₂-based ceramic matrix composite, reinforced with 20 vol% SiC and doped with 10 vol% nano-sized carbon black, was hot pressed at 1850 °C for 1 h under 20 MPa. For comparison, a monolithic ZrB₂ ceramic and a ZrB₂–20 vol% SiC composite were also fabricated by the same processing conditions. By adding 20 vol% SiC, the sintered density slightly improved to ~93%, compared to the relative density of ~90% of the monolithic one. However, adding 10 vol% nano-sized carbon black to ZrB₂–20 vol% SiC composite meaningfully increased the sinterability, as a relatively fully dense sample was obtained (RD=~100%). The average grain size of sintered ZrB₂ was significantly affected and controlled by adding carbon black together with SiC acting as effective grain growth inhibitors. The Vickers hardness, flexural strength and fracture toughness of SiC reinforced and carbon black doped composites were found to be remarkably higher than those of monolithic ZrB₂ ceramic. Moreover, unreacted carbon black additives in the composite sample resulted in the activation of some toughening mechanisms such as crack deflections.     

Sintering and microstructure of rare earth phosphate ceramics REPO4 with RE = La,Ce or Y

Sintering of rare earth phosphates REPO₄ (RE = La, Ce or Y) was studied using dilatometry. The presence of a secondary rare earth metaphosphate phase RE(PO₃)₃ as sintering aid was investigated. It proved to accelerate the densification but it activated fast grain growth, which was very detrimental to the microstructural design of processed ceramics. A temperature of 1400–1450 °C was required to sinter pure LaPO₄ and CePO₄ ceramics with fine grains. Both compounds behave similar while YPO₄ did not densify even at 1500 °C. The influence of specific surface area of starting powders, temperature and holding time on the sintering rate and microstructures of dense REPO₄ materials is also reported.     

Physical characterization and arcjet oxidation of hafnium-based ultra high temperature ceramics fabricated by hot pressing and field-assisted sintering

For this study, HfB₂-based ultra high temperature ceramic (UHTC) samples were prepared by hot pressing and field-assisted sintering (FAS) with 10–20 vol.% SiC (baseline), 5 vol.% TaSi₂, and 5 vol.% iridium. Dense billets were tested for hardness and mechanical strength. When compared, the FAS method consistently yielded materials with a grain size 1.5–2 times finer than samples processed via hot pressing. In general, room temperature flexural strengths of these materials were found to be lower (～400 MPa) than similar fully dense HfB₂–SiC materials, with strengths between 500 and 700 MPa. Oxidation resistance testing of flat-face models was conducted in a simulated re-entry environment, at Q_{Cold Wall} ～250 W/cm² for 5 min. Samples processed by FAS had reduced oxide thickness and SiC depletion zones compared to the baseline HfB₂–20SiC material. In all cases oxide thickness was reduced by ～3× and SiC depletion zone thickness was reduced ～3× over the baseline.     

Densification and mechanical properties of TiC by SPS-effects of holding time,sintering temperature and pressure condition

The influence of sintering temperature, holding time and pressure condition on densification and mechanical properties of bulk titanium carbide (TiC) fabricated by SPS sintering has been systematically investigated. Experimental data demonstrated that relative density and Vickers hardness (H_V) increase with sintering temperature and holding time, but fracture toughness (K_IC) was not significantly influenced by sintering parameters. The H_V and relative density of samples consolidated by SPS technique at 1600 °C for 5 min under 50 MPa pressure (applied entire sintering cycle) reached 30.31 ± 2.23 GPa and 99.90%, respectively. H_V values of ～24–30 GPa and K_IC of ～3.7–5 MPa m^1/2 were obtained in all bulk samples with relative densities of 95.61–99.90% when fabricated under various conditions presented above, without abnormal grain growth. More pronounced effects of pressure condition on grain growth (promoted by grain-boundary diffusion) than on densification were observed. The relationship of fracture toughness and fracture mode is also discussed.     

Microstructure and densification of ZrB2–SiC composites prepared by spark plasma sintering

ZrB₂–SiC composites were prepared by spark plasma sintering (SPS) at temperatures of 1800–2100 °C for 180–300 s under a pressure of 20 MPa and at higher temperatures of above 2100 °C without a holding time under 10 MPa. Densification, microstructure and mechanical properties of ZrB₂–SiC composites were investigated. Fully dense ZrB₂–SiC composites containing 20–60 mass% SiC with a relative density of more than 99% were obtained at 2000 and 2100 °C for 180 s. Below 2120 °C, microstructures consisted of equiaxed ZrB₂ grains with a size of 2–5 μm and α-SiC grains with a size of 2–4 μm. Morphological change from equiaxed to elongated α-SiC grains was observed at higher temperatures. Vickers hardness of ZrB₂–SiC composites increased with increasing sintering temperature and SiC content up to 60 mass%, and ZrB₂–SiC composite containing 60 mass% SiC sintered at 2100 °C for 180 s had the highest value of 26.8 GPa. The highest fracture toughness was observed for ZrB₂–SiC composites containing 50 mass% SiC independent of sintering temperatures.     

Influence of graphite nano-flakes on densification and mechanical properties of hot-pressed ZrB2–SiC composite

Hot pressed monolithic ZrB₂ ceramic (Z), ZrB₂–20 vol% SiC composite (ZS₂₀) and ZrB₂–20 vol% SiC–10 vol% nano-graphite composite (ZS₂₀G_n10) were investigated to determine the influence of graphite nano-flakes on the sintering process, microstructure, and mechanical properties (Vickers hardness and fracture toughness) of ZrB₂–SiC composites. Hot pressing at 1850 °C for 60 min under 20 MPa resulted in a fully dense ZS₂₀G_n10 composite (relative density: 99.6%). The results disclosed that the grain growth of ZrB₂ matrix was efficiently hindered by SiC particles as well as graphite nano-flakes. The fracture toughness of ZS₂₀G_n10 composite (7.1 MPa m^1/2) was essentially improved by incorporating the reinforcements into the ZrB₂ matrix, which was greater than that of Z ceramic (1.8 MPa m^1/2) and ZS₂₀ composite (3.8 MPa m^1/2). The fractographical observations revealed that some graphite nano-flakes were kept in the ZS₂₀G_n10 microstructure, besides SiC grains, which led to toughening of the composite through graphite nano-flakes pull out. Other toughening mechanisms such as crack deflection and branching as well as crack bridging, due to the thermal residual stresses in the interfaces, were also observed in the polished surface.     

Fabrication of continuously porous SiC–Si3N4 composite using SiC powder by extrusion process

Large amounts of waste SiC sludge containing small amounts of Si and organic lubricant were produced during the wire cutting process of single crystal silicon ingots. Waste SiC sludge was purified by washing it with organic solvent and purified SiC powder was used to fabricate the continuously porous SiC–Si₃N₄ composites, using an extrusion process, in which carbon, 6 wt% Y₂O₃ + 2 wt% Al₂O₃ and ethylene vinyl acetate were added as a pore-forming agent, sintering additives and binder, respectively. In the burning-out process, the binder and carbon were fully removed and continuously porous SiC–Si₃N₄ composites were successfully fabricated. The green bodies containing waste SiC, Si powder and sintering additives were nitrided at 1400 °C in a flowing N₂ + 10% H₂ gas mixture. The continuously porous composites contained SiC, α-Si₃N₄, β-Si₃N₄ and few Fe phases. The pore size of the second passed and third passed SiC–Si₃N₄ composites was 260 μm and 35 μm in diameter, respectively. The values of bending strength and hardness in the second passed and third passed samples were 62.97 MPa, 388 Hv and 77.82 MPa, 423 Hv, respectively.     

Toughening of SiC matrix with in-situ created TiB2 particles

SiC–TiB₂ composites with up to 50 vol% TiB₂ were fabricated by in-situ reaction between TiO₂, B₄C and C. The densification of the uniaxially pressed samples was done using pressureless sintering in the presence of sintering aids consisting of Al₂O₃ and Y₂O₃. The influence of the volume fraction of TiB₂ and sintering temperature on density and fracture toughness was examined. It was found that fracture toughness is strongly affected by the volume fraction of TiB₂. The presence of TiB₂ particles suppresses the grain growth of SiC and facilitates different toughening mechanisms to operate which, in turn, increases fracture toughness of the composite. The highest value for fracture toughness of 5.7 MPa m^1/2 was measured in samples with 30 vol% TiB₂ sintered at 1940 °C.     

Two-step sintering assisted consolidation of bulk titania nano-ceramics by spark plasma sintering

This work investigates the feasibility to the fabrication of high density of nano-grained titanium dioxide ceramics by two-step sintering process under spark plasma conditions. First step is carried out by fast-heating-rate sintering in order to obtain an initial high density and a second step is held at a lower temperature by isothermal sintering aiming to increase the density without obvious grain growth. Experiments are conducted to determine the appropriate temperatures for each step. The temperature range between 840 and 850 °C is effective for the first step sintering (T₁) due to its highest densification rate. The isothermal sintering is then carried out at 810–830 °C (T₂) for various hours in order to avoid the abnormal grain growth and improve the density at the same time. TiO₂ bulk ceramics with nano-sized grain were fabricated successfully by combination of spark plasma sintering (SPS) with the two step sintering method (TSS). Titanium dioxide nano-ceramics with >95% theoretical density could be obtained with T₁ and T₂ taken as 850 °C and 830 °C, respectively. The relative grain growth quotient D/D_o for the used starting powder was almost ～1. Further XRD investigations indicated no obvious anatase–rutile transition was found in the prepared nano-crystalline ceramics.     

Two step sintering of a novel calcium magnesium silicate bioceramic: Sintering parameters and mechanical characterization

Two-step sintering (TSS) was applied to control the grain growth during sintering of a novel calcium magnesium silicate (Ca₃MgSi₂O₈ – Merwinite) bioceramic. Sol–gel derived nanopowders with the mean particle size of about 90 nm were sintered under different TSS regimes to investigate the effect of sintering parameters on densification behavior and grain growth suppression. Results showed that sintering of merwinite nanopowder under optimum TSS condition (T₁ = 1300 °C, T₂ = 1250 °C) yielded fully dense bodies with finest microstructure. Merwinite compacts held at T₂ = 1250 °C for 20 h had the average grain size of 633 nm while the relative density of about 98% was achieved. Mechanical testing was performed to investigate the effect of grain growth suppression on the hardness and fracture toughness. Comparison of mechanical data for samples sintered under two sintering regimes, including TSS and normal sintering (NS), showed TSS process resulted in significant enhancement of fracture toughness from 1.77 to 2.68 MPa m^1/2.     

Effects of sintering atmosphere on grain morphology of liquid-phase-sintered SiC with Al2O3 additions

The effects of sintering atmospheres of Ar and N₂ on grain morphology were investigated for pressureless liquid-phase-sintered (LPS) SiC with Al₂O₃ additions. When increasing the sintering temperature, the SiC grain size and its aspect ratio increased in both sintering atmospheres. With a 2 mass% Al₂O₃ addition, no distinct difference was observed between the grain morphology of SiC sintered in the Ar atmosphere and that sintered in the N₂ atmosphere. With a 15 mass% Al₂O₃ addition, sintering in a N₂ atmosphere led to retarded grain growth and this resulted in a fine homogeneous microstructure, whereas sintering in an Ar atmosphere enhanced the grain growth compared with that in 2 mass% Al₂O₃. The effects of atmosphere on the grain morphology depend on the amount of Al₂O₃ addition, and this also affects the grain growth process of solution-reprecipitation. The mechanical properties of the SiC are also considered.     

Synergetic effects of SiC and Csf in ZrB2-based ceramic composites. Part II: Grain growth

The synergetic effects SiC particles and short carbon fibers (C_sf) as well as hot pressing parameters (sintering temperature, dwell time and applied pressure) on the grain growth of ZrB₂-based composites were investigated. Taguchi methodology was employed for the design of experiments to study the microstructure and grain growth of ZrB₂–SiC–C_sf ceramic composites. Three hot pressing parameters and SiC/C_sf ratio were selected as the scrutinized variables. The sintering temperature and SiC/C_sf ratio were identified by ANOVA as the most effective variables on the gain growth of ZrB₂-based samples. Removal of oxide impurities from the surface of starting particles by the reactant C_sf, not only hindered the extraordinary grain growth of ZrB₂ matrix, but also improved the sinterability of the ceramics. A fully dense ceramic with an average grain size of 8.3 µm was obtained by hot pressing at 1850 °C for 30 min under 16 MPa through adding 20 vol% SiC and 10 vol% C_sf to the ZrB₂ matrix. SEM observations and EDS analysis verified the in-situ formation of ZrC which can restrain the growth of ZrB₂ particles, similar to the role of SiC, by the pinning of grain boundaries as another stationary secondary phase.     

Enhancing the sintering ability of TiNx by introduction of nitrogen vacancy defects

Highly nitrogen-deficient non-stoichiometric TiN_x powders within nitrogen vacancy defects (0.3<x<0.5) were prepared by mechanical alloying and consolidated by high pressure sintering. The effects of nitrogen vacancy defects, sintering temperature and pressure on densification and grain growth of TiN_x were investigated for improving sintering ability and mechanical properties. Increasing nitrogen vacancy defects promoted densification and grain growth of TiN_x. Nitrogen vacancies accelerated material transport and diffusion during sintering and altered strong covalent bonding nature was believed to result in enhanced sintering ability. Densification of TiN_x was enhanced by increasing temperature and elevating pressure, grain growth was promoted by increasing temperature, whereas restrained by elevating pressure. TiN_x (x=0.32) ceramic with relative density of 99.4% and average grain size of 21 nm was obtained at 1200 °C, 5 GPa and 10 min. Vickers hardness of 22.6 GPa and fracture toughness of 5.0 MPa m^1/2 were achieved.