Fabrication of non-oxide ceramic powders by carbothermal-reduction from industrial minerals

The most promising method for obtaining a large variety of non-oxide products having important technical uses is carbothermal-reduction reaction (CRR). By using this procedure, SiC and ZrC/SiC powders are obtained from diatomaceous earth and zircon powder. In this way the synthesized powders are obtained at a relatively low temperature due to good homogenization. Starting C/ZrSiO₄ admixtures having different molar ratios (3:1, 4:1, 5:1 and 7:1) and C/SiO₂ having ratios 1:1, 3:1, 4:1, and 7:1 were heated at temperatures between 1300 and 1600 °C in a controlled Ar flow atmosphere. The phase evolution was a function of the raw materials molar ratios and sintering temperature. The optimal parameters for the synthesis of SiC and ZrC/SiC powders were obtained. The results obtained by EDS analysis are in good agreement with those obtained by XRD analysis for the synthesized carbide powders.     

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.     

In situ synthesis of Al2O3–SiC powders via molten-salt-assisted aluminum/carbothermal reduction method

Al₂O₃–SiC composite powder (ASCP) was successfully synthesized using a novel molten-salt-assisted aluminum/carbothermal reduction (MS-ACTR) method with silica fume, aluminum powder, and carbon black as raw materials; NaCl–KCl was used as the molten salt medium. The effects of the synthesis temperature and salt-reactant ratio on the phase composition and microstructure were investigated. The results showed that the Al₂O₃–SiC content increased with an increase in molten salt temperature, and the salt–reactant ratio in the range of 1.5:1–2.5:1 had an impact on the fabrication of ASCP. The optimum condition for synthesizing ASCP from NaCl–KCl molten salt consisted of maintaining the temperature at 1573 K for 4 h. The chemical reaction thermodynamics and growth mechanism indicate that the molten salt plays an important role in the formation of SiC whiskers by following the vapor-solid growth mode in the MS-ACTR treatment. This study demonstrates that the addition of molten salt as a reaction medium is a promising approach for synthesizing high-melting-point composite powders at low temperatures.     

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.     

Synthesis of C/SiC core-shell fibers through siliconization of carbon fibers with SiO gas in semi-closed reactor

Novel C/SiC core-shell fibers have been synthesized through incomplete conversion of carbon fibers by their siliconization with SiO gas. The synthesis was performed in the laboratory-made semi-closed batch-type reactor at 1380 °C for 3 h using a 9:1 M ratio mixture of Si and SiO₂ powders as a solid source of SiO gas. The conversion rate of carbon into SiC was 34.0%. All synthesized fibers had a distinct C/SiC core-shell composite structure. The fiber product was of fairly good uniformity in respect of the shell thickness which varied approximately from 0.6 μm to 0.8 μm depending on the location of fibers inside the reactor. It was revealed that the formation of the shell was the result of inward growth of the SiC product layer. The effectiveness of the proposed semi-closed reactor for the synthesis of C/SiC core-shell fibers has been demonstrated.     

Characterization of sintered TiC–SiC composites

TiC–SiC composites were fabricated using TiC and SiC powders as starting materials at the range of 1650–2000 °C in Ar atmosphere by two-step method. In the first step, the ingots with intragranular SiC or TiC particle were prepared by arc-melting technique, subsequently, crushed and ground into TiC and SiC composite powders. In the second step, TiC–SiC composites were sintered using these as-prepared composite powders by SPS method. It was concluded that these TiC–SiC composites prepared by two-step method showed more excellent properties than that prepared by arc-melting technique. The hardness of the fabricated TiC–SiC composites was 25–27 GPa at the load of 0.98–9.8 N, which was obviously greater than that of arc-melting composites. The thermal conductivity of the TiC–SiC composites was 18–48 W K⁻¹ m⁻¹ at the range of 298–1273 K and slightly decreased with increasing temperature. The electrical conductivity of the composites was (2–5) × 10⁵ S m⁻¹ at the range of 298–1273 K and slightly decreased with increasing temperature.     

Two‐Step Carbothermal Synthesis of AlN–SiC Solid Solution Powder Using Combustion Synthesized Precursor

In the present work, a two‐step carbothermal reduction method is employed to prepare the AlN–SiC solid solution (AlN–SiCss) powders by using a combustion synthesized precursor. The precursor is prepared by low‐temperature combustion synthesis (LCS) method using a mixed solution of aluminum nitrate, silicic acid, polyacrylamide, glucose, and urea. The synthesized LCS precursor exhibits a porous and foamy uniform mixture of Al₂O₃ + SiO₂ + C consisting of flaky particles. The carbothermal reduction in the LCS precursor is carried out in two steps. First, the precursors are calcined at 1600°C in argon for 3 h. Subsequently, the precursors are further calcined at 1600°C–1900°C in nitrogen for 3 h. The results indicate that the precursor calcined at and above 1850°C in nitrogen for 3 h yields the single‐phase AlN–SiCss powders. The synthesized AlN–SiCss powder exhibits near‐spherical particles with diameter of 200–500 nm. The experimental and thermodynamical results reveal that the formation of AlN–SiCss occurs via the diffusion of AlN into SiC by virtue of formation of a highly defective β′ intermediate during the second step reaction.     

Direct Combustion Synthesis of Silicon Carbide Nanopowder from the Elements

Direct synthesis of silicon carbide (SiC) nanopowders (size 50–200 nm, BET ~20 m²/g) in Si–C system is conducted in an inert atmosphere (argon) using a self‐propagating high‐temperature synthesis (SHS) approach. A preliminary short‐term (e.g., minutes) high‐energy ball milling (HEBM) of the initial mixture, which involves pure Si and C powders, is used to enhance system reactivity. Two conditions of HEBM with different force fields (17G and 90G) are applied and the results are compared. The influence of HEBM's conditions on the microstructure of mechanically treated mixtures and combustion products is also investigated and discussed. Obtained results suggest that by changing the intensity of mechanical treatment one may prepare a completely amorphous reactive mixture containing carbon and silicon, or gradually change the ratio of (Si/C)–SiC phases and finally produce pure silicon carbide powder during the milling process. The influence of HEBM on the combustibility of the Si/C mixture possesses a critical character: the self‐sustained reaction becomes feasible only after a critical time of ball milling (i.e., 10 min for 90G; 30 min for 17G). Comparison of the microstructures for as‐milled and as‐synthesized powders reveals that for all investigated conditions the morphologies of the as‐milled reactive Si/C media are essentially the same as that for SiC combustion products. The mechanism for direct synthesis of SiC by combustion reaction is also proposed.     

Neutron adsorption performance of Dy2TiO5 materials obtained from powders synthesized by the molten salt method

Dy₂TiO₅ powders were synthesized by molten salt and solid-state methods. The influences of molten medium on phase compositions and microstructures were analyzed. The addition of molten salt lowered significantly the synthesis temperature and resulted in uniform powders. Green bodies compacted from the prepared powders were pressureless sintered at 1600 °C. Sinterability, mechanical properties and neutron absorption performance of the sintered pellets were studied. Results showed that molten salt synthesis resulted in materials with higher fracture toughness and bending strength, excellent hardness and neutron adsorption performance compared to the solid-state process. The neutron absorption rate reached 86.6% for 8 cm thick pellets.     

Synthesis of nanofibrous carbon with herringbone structure on Ni-supported SiC particles using hot CVD apparatus

A nanofibrous carbon material having a herringbone structure was synthesized using Ni-supported silicon carbide (SiC) particles as the catalyst for the hot chemical vapor deposition (CVD) process using CH₄ as carbon source. The amount of the deposits during the CVD process strongly depended on the CVD treatment temperature. The enhancement of weight and the TG data indicated that the quantity synthesis of the deposits was achieved at 823 K. The specific surface area of the deposits was estimated at ca. 120 m² g^− 1. It was confirmed from the TEM images that the deposits synthesized in this study had a herringbone-like structure. From the data of Raman spectra and XRD patterns, the herringbone-like structure started to deposit after 30 minutes in the case of 823 K. The Ni-supported SiC can be used as the catalyst for the synthesis of nanofibrous carbon materials.     

Thermal plasma synthesis of Si/SiC nanoparticles from silicon and activated carbon powders

In this study, Si/SiC nanocomposites were synthesized by non-transferred arc thermal plasma processing of micron-sized SiC powder. First, micron-sized SiC was synthesized by solid-state method where waste silicon (Si) and activated carbon (C) powder were used as precursor materials. The effect of Si/C mole ratio and solid-state synthesis temperature on structural and phase formation of SiC was investigated. Diffraction pattern confirmed the formation of SiC at 1300 °C. High C content was required for the synthesis of pure SiC as Si remained unreacted when Si/C mole ratio was below 1/1.5. Highly agglomerated micron-size (0.6–10 µm) SiC particles were formed after solid-state synthesis. Thermal plasma processing of solid-state synthesized micron-sized SiC resulted into the formation of uniformly dispersed (20–60 nm) Si/SiC nanoparticles. It was proposed that Si/SiC nanocomposites were formed due to partial decomposition of SiC during high temperature plasma processing. The formation of Si/SiC nanoparticles from micron-sized SiC was resulted from dissociation of grains from their grain boundary during plasma processing.     

Molten salt synthesis of orthorhombic CrB and Cr2AlB2 ceramics

High-purity and fine CrB powders are firstly synthesized from Cr and B powders in (Na, K)Cl molten salt at 850 °C for 2 h. Then the as-achieved CrB powders are used as precursors to synthesize homogeneous and size-controlled Cr₂AlB₂ powders in (Na, K)Cl molten salt at 900 °C for 2 h. Additionally, the formation mechanisms of CrB and Cr₂AlB₂ in (Na, K)Cl molten salt are also investigated. Results show that the Cr atom, formed by disproportionation of Cr²⁺ ions in molten salt, reacts in-situ with B powders to form CrB. For the formation of Cr₂AlB₂, Al and CrB migrate mutually and assemble firstly in the molten salt, and then Al intercalates into CrB to generate Cr₂AlB₂.     

Rapid carbothermic synthesis of silicon carbide nano powders by using microwave heating

This paper reports an improved procedure for synthesis of silicon carbide nanopowders from silica by carbothermic reduction under fast microwave-induced heating. The powders have been prepared by direct solid-state reaction in a 2.45 GHz microwave field in nitrogen atmosphere after 40 h milling. For the first time, the formation of silicon carbide (β-SiC) as a major phase can be achieved at 1200 °C in 5 min of microwave exposure, resulting in nano sized particles ranging from 10 to 40 nm under optimized synthesis condition. The Rietveld quantitative phase-composition analysis confirmed that the major SiC polytype is cubic SiC (β-SiC) with 98.5(4) weight fraction and the remained is minor hexagonal SiC polytypic (α-SiC) phases. Therefore this method is the most efficient one for SiC powder synthesis in terms of energy and time saving as well as preparation of SiC nano powders.     

Green synthesis of blue-green photoluminescent β-SiC nanowires with core-shell structure using coconut shell as carbon source

This work proposes a green method for synthesizing SiC nanowires (NWs) via the chemical vapor deposition (CVD) technique using coconut shell and silicon as raw materials. Using coconut shell as carbon source decreases the synthesis temperature of SiC. A large number of core-shell SiC NWs were obtained after firing at 1200 °C, a thin SiO₂ layer is distributed on the outer shell of SiC NWs. The synthesized SiC NWs grow along the [111] direction, up to dozens of micrometers in length and diameters of 10–75 nm. However, the chain-bead structure of SiC NWs is formed after firing at 1400 °C due to the SiO₂ bead embedded in SiC NWs. The synthesized core-shell SiC NWs fired at 1200 °C emit strong violet-blue light, which has good application prospects in optoelectronic devices.     

Surface modification of superfine SiC powders by ternary modifiers-KH560/sodium humate/SDS and its mechanism

SiC is a promising functional ceramic material with many great properties. High concentrated SiC slurry with excellent rheology and stability is required in some processes of ceramic forming. In this work, the dispersion of SiC powders was obviously improved by ternary modifiers: γ-(2,3-epoxypropoxy) propytrimethoxysilane (KH560), sodium humate and sodium dodecyl sulfate (SDS). Modified SiC slurry showed the lowest viscosity of 0.168 Pa s at a solid content of 50 vol%. The maximum absolute value of zeta potential of SiC increased from 47.3 to 61.6 mV by modification. Sedimentation experiments showed that a highly stable suspension of modified SiC was obtained at pH 10. SiC green body with high density of 2.643 g/cm³ was prepared with modified powders by slip casting. X-ray photoelectron spectra (XPS) and thermogravimetry (TG) measurements indicated the adsorption of modifiers on SiC surface. Therefore, modified SiC powders could stably disperse in aqueous media due to the increase of electrosteric repulsion between particles. The novel strategy used in this study could further improve the dispersion of SiC powders.     

Synthesis of SiC whiskers via catalytic reaction method in self-bonded SiC composites

Catalyzed by in-situ formed Fe nanoparticles (NPs), 3C–SiC whiskers were prepared from expanded graphite and Si powders after firing at 1573 K for 3 h in Argon. The density functional theory calculations revealed that Fe catalysts facilitated the formation of SiC nucleus and the epitaxial growth of SiC whiskers via reducing the bonding strength in CC dimer as well as Si–O and C–O bonds. Moreover, using SiC, expanded graphite and silicon powders as starting materials Fe-catalyzed self-bonded SiC composites were fabricated. Lots of SiC whiskers were synthesized in the as-prepared composites, leading to remarkable enhancements in high temperature mechanical behavior, oxidation resistance and cryolite resistance of the self-bonded SiC composites.     

Electrically induced liquid infiltration for the synthesis of carbon/carbon–silicon carbide composite

The electrically induced liquid infiltration (EILI) method for the synthesis of carbon/carbon–silicon carbide (C/C–SiC) materials was developed. The method involves Joule preheating of a porous carbon/carbon preform surrounded by silicon media, followed by silicon infiltration into the pore structure, and its reaction with carbon to form pore-free C/C–SiC composite. This technique is characterized by high heating rates (10²–10³ K/s) and short processing times (5–20 s), which distinguish it from conventional approaches. The influence of maximum treatment temperature, as well as preheating rate on the depth of infiltration, reaction kinetics, and the material microstructure was investigated. C/C–SiC composite with a compressive strength which was twice that of the initial C/C material was synthesized.     

Microscopic and Spectroscopic Characterization of Stacking‐Sequence Disordered SiC

Nanometric silicon carbide (SiC) powder (~5 nm) with a stacking‐sequence disordered structure (SD‐SiC), synthesized from elemental powders of Si and C, was investigated by microscopic and several spectroscopic methods. The structure of SD‐SiC was characterized by transmission electron microscopy (TEM), ¹³C, and ²⁹Si‐NMR, and by infrared (IR), Raman, and X‐ray photoelectron spectroscopy (XPS) methods. TEM characterizations showed relatively large deviations of the lattice parameters in the as‐synthesized SiC, indicative of the presence of stacking‐sequence disorder. IR analysis showed a weaker Si‐C bond in the SD‐SiC than in the 3C‐SiC. XPS determinations showed that C and Si in SD‐SiC are similar to those in 3C‐SiC. Broader peaks of ²⁹Si and ¹³C MAS‐NMR also indicate that the structure of SD‐SiC is different from that of 3C‐SiC. Raman spectroscopy exhibited activities for the crystalline polytypes and the amorphous of SiC but lack of them for the SD‐SiC. The inactivity of Raman spectroscopy for the SD‐SiC along with large deviation of the lattice constant and the extremely broad X‐ray diffraction peaks would indicate that SD‐SiC is a possible intermediate state between conventional polytype SiC and amorphous SiC, that is, a possible new type of SiC.     

Low‐Temperature Synthesis of Mesoporous SiC Hollow Spheres by Magnesiothermic Reduction

Mesoporous silicon carbide hollow spheres (SiC‐HS) with a large specific surface area (690.2 m² g^?1) are synthesized at a relatively low temperature of 650°C by magnesiothermic reduction using the template of carbon‐coated mesoporous silica hollow spheres and molten salt as the heat absorbent and solvent. The mesoporous SiC‐HS comprising many small primary crystals (2–4 nm) with a well‐maintained microstructure have good thermal stability and adsorption ability, and are promising as adsorbents to remove organic pollution from water. The synthesis technique can be extended to other nanostructured carbide ceramic materials.     

Effect of in situ synthesized and additives on the thermal performance of mullite thermal storage ceramics

High-performance thermal storage ceramics can enable utilization of solar thermal power generation plants. In this work, in situ synthesis was used to prepare mullite thermal storage ceramics. Calcined bauxite, talc, and kaolin were used as raw materials. The effects of additives (e.g., SiC, Si₃N₄, TiC, and ZrB₂) on the density, mechanical durability, phase components, microstructure, and thermal performance of the mullite ceramics were studied. The results showed that the thermal expansion coefficient, thermal conductivity, and heat storage density of the mullite ceramics were affected by their phase components. SiC and Si₃N₄ did not decompose during the in situ syntheses, but TiC and ZrB₂ decomposed. With the addition of 10 wt% SiC, the thermal conductivity improved to 2.72 W (m K)^?1 (298 K). The heat storage density of this material was 688 kJ kg^?1 (273–1073 K). Consequently, the in situ synthesized mullite thermal storage ceramic with added SiC could be a promising candidate material for a compound latent-sensible heat storage system.