Pressureless sintered silicon carbide matrix with a new quaternary additive for fully ceramic microencapsulated fuels

This study suggests a new additive composition based on AlN–Y₂O₃–Sc₂O₃–MgO to achieve successful densification of SiC without applied pressure at a temperature as low as 1850 °C. The typical sintered density, flexural strength, fracture toughness, and hardness of the SiC ceramics sintered at 1850 °C without applied pressure were determined as 98.3%, 510 MPa, 6.9 MPa·m^1/2, and 24.7 GPa, respectively.Fully ceramic microencapsulated (FCM) fuels containing 37 vol% tristructural isotropic (TRISO) particles could be successfully sintered at 1850 °C using the above matrix without applied pressure. The residual porosity of the SiC matrix in the FCM fuels was only 1.6%. TRISO particles were not damaged during processing, which included cold isostatic pressing under 204 MPa and sintering at 1850 °C for 2 h in an argon atmosphere. The thermal conductivity of the pressureless sintered FCM pellet with 37 vol% TRISO particles was 44.4 Wm^?1 K^?1 at room temperature.     

Effect of β to α phase transformation on microstructure and thermal conductivity of SiC ceramic densified with Y2O3-MgO additives in argon

SiC ceramic was fabricated by spark plasma sintering of β-SiC powder and Y₂O₃-MgO additives in argon. The effects of β→α phase transformation of SiC on microstructure and thermal conductivity of densified bulks were systematically investigated, in comparison to the counterparts using α-SiC as starting powder. The β→α phase transformation led to a “unimodal to bimodal” transition in grain size distribution. After sintering at 1850 ^oC, the incomplete β→α phase transformation induced the appearance of β/α heterophase boundary with strong effect of phonon-scattering. After sintering at 2050 ^oC, the completion of β→α phase transformation resulted in enlarged grains and disappearance of β/α heterophase boundary in SiC ceramic. The lattice oxygen content was decreased primarily by enhanced grain growth and oxygen picking-up of sintering additives, and possibly some contribution from β→α phase transformation. The optimized microstructure enabled SiC ceramic to obtain a remarkable increase in thermal conductivity from 126 to 204 W/mK after the replacement of α-SiC by β-SiC as starting powder and the accomplishment of β→α phase transformation.     

Stress measurements in ZrB2–SiC composites using Raman spectroscopy and neutron diffraction

Raman spectroscopy and neutron diffraction were used to study the stresses generated in zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics. Dense, hot pressed samples were prepared from ZrB₂ containing 30 vol% α-SiC particles. Raman patterns were acquired from the dispersed SiC particulate phase within the composite and stress values were calculated to be 810 MPa. Neutron diffraction patterns were acquired for the ZrB₂–SiC composite, as well as pure ZrB₂ and SiC powders during cooling from ～1800 °C to room temperature. A residual stress of 775 MPa was calculated as a function of temperature by comparing the lattice parameter values for ZrB₂ and SiC within the composite to those of the individual powders. The temperature at which stresses began to accumulate on cooling was found to be ～1400 °C based on observing the deviation in lattice parameters between pure powder samples and those of the composite.     

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.     

New quaternary additive for processing fully ceramic microencapsulated fuels without applied pressure

To apply SiC ceramics as a matrix for fully ceramic microencapsulated (FCM) fuels, the equivalent boron content (EBC) factors of elements in the sintering additives should be considered as an important criterion. A previously developed quaternary additive composition based on AlN–Y₂O₃–Sc₂O₃–MgO contained Sc, which has a relatively high EBC factor (8.56 × 10^?3). This study proposes a novel quaternary additive composition (AlN–Y₂O₃–CeO₂–MgO), in which Sc is replaced by Ce (EBC factor = 6.36 × 10^-5). The new additive composition achieved successful densification of the SiC matrix at 1850 °C without applied pressure. FCM pellets containing 36 vol% tristructural isotropic (TRISO) particles were successfully sintered at 1850 °C using the above matrix without applied pressure. The thermal conductivities of the FCM pellets prepared via pressureless sintering with 36 vol% TRISO particles were 43.9 W·m^-1·K^-1 and 25.8 W·m^-1·K^-1 at 25 °C and 500 °C, respectively.     

Highly resistive SiC ceramics sintered with Al2O3-AlN-Y2O3 additions

A polycrystalline SiC ceramic prepared by pressureless sintering of α-SiC powders with 3 vol% Al₂O₃-AlN-Y₂O₃ additives in an argon atmosphere exhibited a high electrical resistivity of ~10¹³ Ω cm at room temperature. X-ray diffraction revealed that the SiC ceramics consisted mainly of 6H- and 4H-SiC polytypes. Scanning electron microscopy and high resolution transmission electron microscopy investigations showed that the SiC specimen contained micron-sized grains surrounded by an amorphous Al-Y-Si-O-C-N film with a thickness of ~4.85 nm. The thick boundary film between the grains contributed to the high resistivity of the SiC ceramic.     

Effects of initial α-phase content on properties of pressureless solid-state sintered SiC ceramics

α- and β-SiC starting powders of similar particle sizes were used to investigate the effect of initial α-phase content on the electrical, thermal, and mechanical properties of pressureless solid-state sintered (PSS) SiC ceramics with B₄C and C additives. For β-SiC starting powders, a coarse-grained microstructure with elongated platelet grains was formed by the transformation of 3C to 6H and finally to 4H-SiC phase. In contrast, materials prepared from α-SiC powders exhibited a fine-grained microstructure with platelet grains. This study revealed the beneficial effect of α-SiC starting powders in achieving low electrical resistivity and high thermal conductivity in PSS SiC ceramics, which was attributable to their higher sinterability, lower impurity content, and lower 6H to 4H-SiC phase transformation rate compared with β-SiC powders. The electrical resistivity decreased by an order of magnitude and the thermal conductivity increased by 32% with an increase in initial α-phase content from 0 to 100%. The flexural strength increased by approximately 16% with increasing initial α-phase content due to a decreased flaw size with decreasing grain size. However, the fracture toughness and hardness were insensitive to the change in initial α-phase content.     

The thermal,electrical and mechanical properties of porous α-SiC ceramics bonded with Ti3SiC2 and β-SiC via low temperature in-situ reaction sintering

Porous SiC ceramics have recently attracted wide attention for their applications in the electrically heatable filter. Further improvement of the thermal and electrical conductivity without sacrificing permeability is a critical parameter for such applications. In the present work, porous SiC/Ti₃SiC₂ ceramic composites with Ti₃SiC₂ and micro/nano SiC have been prepared from TiC/Si/α-SiC mixtures at a low sintering temperature (1400 °C). Nano-laminated Ti₃SiC₂ enhanced the electrical conductivity, while the good thermal conductivity was achieved through in-situ formed nano β-SiC and raw coarse α-SiC in the porous ceramics. Along with the increase of initial α-SiC particle size from 0.76 to 16.13 μm, the permeability, thermal and electrical conductivity improved due to the decreased porosity and increased pore size in porous SiC/Ti₃SiC₂ ceramics. The results suggested that the decoupling of the electrical conductivity from the thermal conductivity could be tuned by adjusting the initial α-SiC particle size.     

Mechanical properties of silicon carbide—in situ zirconium carbonitride composites

SiC–Zr₂CN composites were fabricated by conventional hot pressing from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃–Sc₂O₃ as a sintering additive. The effects of the ZrN addition on the room-temperature (RT) mechanical properties and high-temperature flexural strength of the SiC–Zr₂CN composites were investigated. The fracture toughness gradually increased from 4.2 ± 0.3 MPa·m^1/2 for monolithic SiC to 6.3 ± 0.2 MPa·m^1/2 for a SiC–20 vol% ZrN composite, whereas the RT flexural strength (546 ± 32 MPa for the monolithic SiC) reached its maximum of 644 ± 87 MPa for the SiC–10 vol% ZrN composite. The monolithic SiC had improved strength at 1200°C, whereas the SiC–Zr₂CN composites could not retain their RT strengths at 1200°C. The typical flexural strength values of the SiC–0, 10, and 20 vol% ZrN composites at 1200°C were 650 ± 53, 448 ± 31, and 386 ± 19 MPa, whereas their RT strength values were 546 ± 32, 644 ± 87, and 528 ± 117 MPa, respectively.     

Electrical and mechanical properties of pressureless sintered SiC-Ti2CN composites

Highly conductive SiC-Ti₂CN composites were fabricated from β-SiC and TiN powders with 10?vol% Y₂O₃-AlN additives via pressureless sintering. The effect of initial TiN content on the microstructure, and electrical and mechanical properties of the SiC-Ti₂CN composites was investigated. It was found that all specimens could be sintered to ≥98% of the theoretical density. The electrical resistivity of the SiC-Ti₂CN composites decreased with increasing initial TiN content. The SiC-Ti₂CN composites prepared from 25?vol% TiN showed the highest electrical conductivity (～1163 (Ω?cm)^?1) for any pressureless sintered SiC ceramics thus far. The high electrical conductivity of the composites was attributed to the in situ-synthesis of an electrically conductive Ti₂CN phase and the growth of N-doped SiC grains during pressureless sintering. The flexural strength, fracture toughness, and Vickers hardness of the composite fabricated with 25?vol% TiN were 430?MPa, 4.9?MPa?m^1/2, and 23.1?GPa, respectively, at room temperature.     

Plastic deformation-induced improved mechanical and thermal properties in hot-forged SiC-TiC composite

A novel SiC-20 vol% TiC composite prepared via a two-step sintering technique using 6.5 vol% Y₂O₃-Sc₂O₃-MgO exhibited high deformation (60 %) on hot forging attributed to the high-temperature plasticity of TiC (ductile to brittle transition temperature ～800 °C) and fine-grained microstructure (～276 nm). The newly developed SiC-TiC composite exhibited a ～2-fold increase in nominal strain as compared to that of monolithic SiC. The plastic deformation caused by grain-boundary sliding in monolithic SiC was supplemented by the plastic deformation of TiC in the SiC-TiC composite. The hot-forged composite exhibited anisotropy in its microstructure and mechanical and thermal properties due to the preferred alignment of α-SiC platelets formed in situ. The relative density, flexural strength, fracture toughness, and thermal conductivity of the composite increased from 98.4 %, 608 MPa, 5.1 MPa?m^1/2, and 34.6 Wm^?1 K^?1 in the as-sintered specimen to 99.9 %, 718–777 MPa, 6.9–7.8 MPa?m^1/2, and 54.8–74.7 Wm^?1 K^?1, respectively, on hot forging.     

Influence of mechanical activation on combustion synthesis of fine silicon carbide (SiC) powder

The influence of mechanical activation of powder mixtures of Si and C, via high energy attrition milling (up to 12 h), on combustion synthesis of SiC was experimentally investigated. β-SiC fine powder was successfully fabricated in 1.0 MPa N₂ atmosphere without other additional treatments, such as preheating, electric action, or chemical activation. Relatively weak peaks of α-SiC, α-Si₃N₄ and Si₂ON₂ were also found in the final products. The experimental results and their theoretical treatment showed that mechanical activation via high energy ball-milling provides to the initial Si/C powder mixture extra energy, which is needed to increase the reactivity of powder mixture and to make possible the ignition and the sustaining of combustion reaction to form SiC.     

Preparation and properties of porous SiC–Al2O3 ceramics using coal ash

In this paper, we first reported that porous SiC–Al₂O₃ ceramics were prepared from solid waste coal ash, activated carbon, and commercial SiC powder by a carbothermal reduction reaction (CRR) method under Ar atmosphere. The effects of addition amounts of SiC (0, 10, 15, and 20 wt%) on the postsintering properties of as-prepared porous SiC–Al₂O₃ ceramics, such as phase composition, microstructure, apparent porosity, bulk density, pore size distribution, compressive strength, thermal shock resistance, and thermal diffusivity have been investigated. It was found that the final products are β-SiC and α-Al₂O₃. Meanwhile, the SEM shows the pores distribute uniformly and the body gradually contacts closely in the porous SiC–Al₂O₃ ceramics. The properties of as-prepared porous SiC–Al₂O₃ ceramics were found to be remarkably improved by adding proper amounts of SiC (10, 15, and 20 wt%). However, further increasing the amount of SiC leads to a decrease in thermal shock resistance and mechanical properties. Porous SiC–Al₂O₃ ceramics doped with 10 wt% SiC and sintered at 1600°C for 5 hours with the median pore diameter of 4.24 μm, room-temperature compressive strength of 21.70 MPa, apparent porosity of 48%, and thermal diffusivity of 0.0194 cm²/s were successfully obtained.     

Highly conductive SiC ceramics containing Ti2CN

Highly conductive SiC ceramics were fabricated by sintering β-SiC and TiN powder mixture in N₂ atmosphere. SiC ceramics exhibited decreased electrical resistivity (ρ) with increasing TiN content. X-ray diffraction data indicated that the specimens consisted of β-SiC grains without a detectible secondary phase for low TiN content (≤2 vol%) but contained a Ti₂CN phase as the TiN content increased. The temperature-dependent resistivity ρ(T) of specimens revealed semiconductor-like behavior for TiN content up to 10 vol% and metal-like behavior above 20 vol%. For the specimen with TiN content of 15 vol%, ρ(T) remained almost constant (2.06 ± 0.01 × 10⁻³ Ω cm) in the 4–300 K range. The resistivity of metal-like specimens were as low as 3.5 × 10⁻⁴ Ω cm for TiN content of 20 vol%. For semiconductor-like specimens, ρ(T) was primarily affected by N donors in the β-SiC grains. Metal-like specimens were primarily affected by metallic Ti₂CN clusters.     

Electrical resistivity of α-SiC ceramics sintered with Al2O3 or AlN additives

Highly resistive SiC ceramics were prepared by hot pressing α-SiC powders with Al₂O₃-Y₂O₃ additives with a 4:1 molar ratio. X-ray diffraction patterns, Raman spectra, electron probe microanalysis (EMPA), and scanning electron microscopy (SEM) images revealed that the bulk SiC ceramics consisted mostly of micron-sized 6H-SiC grains along with Y₂O₃ and Si clusters. As the additive content increased from 1 to 10 vol%, the electrical resistivity of the ceramics increased from 3.0 × 10⁶ to 1.3 × 10⁸ Ω cm at room temperature. Such high resistivity is ascribed to Al₂O₃ in which Al impurities substituting Si site act as deep acceptors for trapping carriers. More resistive α-SiC ceramics were produced by adding AlN instead of Al₂O₃. The highest resistivity (1.3 × 10¹⁰ Ω cm) was achieved by employing 3 vol% AlN-Y₃Al₅O₁₂ (yttrium aluminum garnet, YAG) as an additive.     

Nanometer silicon carbide powder synthesis and its dielectric behavior in the GHz range

In this paper, the dielectric properties of nano-sized SiC powders have been investigated in the GHz frequency range. The polytypes of SiC have been changed from β type (3C) to α type (12H and 21R) by varying the aluminum contents and the reaction atmospheres. The β-SiC powder has much higher relative permittivity (ε′_r=30∼50) and loss tangent (tgδ=∼0.7) than α-SiC powders. Though the doping of Al and N decrease the resistivity of SiC to the order of 10² Ω cm, the pivotal factor on the dielectric behaviors is ion jump and dipole relaxation, namely the reorientation of lattice defect pairs (V_Si–V_C, Si_C–C_si). The conductivity of SiC has little effect on the dielectric behaviors.     

Grain-growth-induced high electrical conductivity in SiC–BN composites

SiC–BN composites were fabricated by conventional hot-pressing from β-SiC and h-BN nanopowders with 2?vol% yttria as a sintering additive. Electrical and thermal properties of the composites were investigated as a function of initial BN content. Owing to the nanosize of the starting powders, the grain-growth-assisted N-doping of the SiC lattice was significantly enhanced during liquid-phase sintering, yielding the highest-reported electrical conductivity of ~124 (Ω?cm)^?1 for a SiC–4-vol% BN composite. The typical values of electrical resistivity and thermal conductivity of the SiC–4-vol% BN composite at room temperature were 8.1?×?10^?3 Ω?cm and 92.4?W?m^?1 K^?1, respectively.     

Thermal and Mechanical Properties of SiC–TiC0.5N0.5 Composites

SiC–TiC_0.5N_0.5 composites were fabricated from β‐SiC and TiN powders with 2 vol% equimolar Y₂O₃–Sc₂O₃ additives by conventional hot pressing. Thermal and mechanical properties of the SiC–TiC_0.5N_0.5 composites were investigated as a function of initial TiN content. Relative densities of ≥98.9% were achieved for all samples. The addition of a small amount of TiN increased thermal conductivity, flexural strength, and fracture toughness of SiC ceramics. However, further addition of TiN in excess of 10 and 20 vol% deteriorated both thermal conductivity and flexural strength of the composites, respectively. In contrast, the fracture toughness of the composites increased continuously from 4.2 to 6.2 MPa?m^1/2 with increasing initial TiN content from 0 to 35 vol%, due to crack deflection by TiC_0.5N_0.5. The maximum values of thermal conductivity and flexural strength were 224 W/m K for a 2 vol% TiC_0.5N_0.5 and 599 MPa for a 10 vol% TiC_0.5N_0.5 composite.     

Pressureless sintering of beta silicon carbide nanoparticles

This study reports the pressureless sintering of cubic phase silicon carbide nanoparticles (β-SiC). Green blended compounds made of SiC nano-sized powder, a fugitive binder and a sintering agent (boron carbide, B₄C), have been prepared. The binder is removed at low temperature (e.g. 800 °C) and the pressureless sintering studied between 1900 and 2100 °C. The nearly theoretical density (98% relative density) was obtained after 30 min at 2100 °C.The structural and microstructural evolutions during the heat treatment were characterised. The high temperatures needed for the sintering result in the β-SiC to α-SiC transformation which is revealed by the change of the composite microstructure. From 1900 °C, dense samples are composed of β-SiC grains surrounding α-SiC platelets in a well-defined orientation.TEM investigations and calculation of the activation energy of the sintering provided insight to the densification mechanism.     

Formation of porous SiC ceramics via recrystallization

In this study, porous SiC ceramics with interconnected huge plate-like grains were fabricated from oxidized β-SiC powder with 1 wt% B₄C. When the β–α SiC phase transformation occurred at 2100 °C, rapid grain growth of α-SiC consumed the unstable β-SiC matrix resulting in an interconnected network structure with huge plate-like grains. The oxidation of β-SiC powder and the addition of B₄C are necessary conditions for rapid grain growth. The observed results are discussed based on thermodynamic considerations. The measured porosity of the specimens sintered at 2100 °C for 30 min was 47% and the mean pore size was 6–7 μm. The strength of the sintered specimen was 45 ± 5 MPa.