Thermal stability and crosslinking of hydropolysilanes for use as silicon carbide precursors

Thermal stability of [(CH₃SiH)₃₀(C₆H₅SiCH₃)₇₀]_n a hydropolysilane copolymer, in vacuum and its crosslinking reactions with vinylic silanes as crosslinking agents was evaluated in order to obtain high yields of oxygen-free silicon carbide ceramics. It was found that the polymer was thermally stable in vacuum up to 140 °C for 20 hrs based on Fourier transform infrared spectroscopy analysis. The crosslinking reactions of the polymer occurred to various extents depending on the type of vinylic silanes used as evidenced by Fourier transform infrared spectroscopy, ultraviolet spectroscopy, gel permeation chromatography, thermogravimetry and solubility data. The additions of vinylic silanes to Si-H in the hydropolysilane were found to obey anti-Farmer's rule, despite Farmer's addition of unsaturated hydrocarbons to Si-H.     

Improved electrical and thermal conductivities of polysiloxane-derived silicon oxycarbide ceramics by barium addition

The electrical and thermal conductivities of bulk barium-added silicon oxycarbide (SiOC-Ba) ceramics are investigated. The SiOC-Ba ceramics exhibited improved electrical and thermal conductivities upon increasing the sintering temperature from 1450 °C to 1650 °C. Precipitation of graphitic carbon clusters observed by Raman spectroscopy and high-resolution transmission electron microscopy is attributed to the phase separation during the fabrication process. The increase in the electrical conductivity can be rationalized in terms of an increase in the density of the sp² CC bonds within the carbon clusters. The increase in the thermal conductivity is mainly attributed to the formation of interconnected graphitic clusters in the SiOC matrix and SiC embedded in the clusters. The electrical and thermal conductivities of the SiOC-Ba ceramics sintered at 1650 °C are 14.0 Ω^?1 cm^?1 and 5.6 W/m K, respectively, at room temperature. The electrical conductivity of SiOC-Ba sintered at 1550 °C is 5.3 Ω^?1 cm^?1 and 7.0 Ω^?1 cm^?1 at 2 and 300 K, respectively.     

Electrical and thermal response of silicon oxycarbide materials obtained by spark plasma sintering

In order to obtain dense silicon oxycarbide (SiOC) materials that maintain the properties of glass, non-conventional spark plasma sintering was used to sinter SiOC powders from 1300 to 1700 °C and with 40 MPa of pressure. The concurrence of electrical current, high pressure and low vacuum while the material is being heating produces a dense SiOC-derived material composed of a SiO₂ glassy matrix reinforced with SiC nanowires grown in situ, graphene-like carbon and turbostratic graphite. SiOC materials with high electrical and thermal response are obtained as a result of this new processing technique. Electrical resistivity undergoes an extraordinary decrease of five orders of magnitude from 1300 (1.0 × 10⁵ Ω m) to 1700 °C (0.78 Ω m), ranging from insulate to semiconductor material; and thermal conductivity increases by 30%, for these sintering temperatures.     

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.     

Thermophysical property and electrical conductivity of titanium isopropoxide – polysiloxane derived ceramics

In this study, high temperature resistant Si-O-C-Ti has been successfully prepared based on the pyrolysis of polysiloxane (PSO) and titanium (IV) isopropoxide (TTIP) at 1200–1400 °C. PSO can homogeneously mix with TTIP to enhance its conversion to TiC. The carbothermal reactions between TiO₂ (product of thermal decomposition of TTIP) and carbon result in the formation of TiC. All the Si-O-C-Ti composites pyrolyzed at 1200–1300 °C are stable up to 1000 °C in an oxidizing air atmosphere. TiC leads to high electrical conductivity at elevated temperatures; the maximum conductivity is 1176.55 S/m at 950 °C, which is the first reported value of >1000 S/m conductivity for Si-O-C-Ti ceramics. However, too high a pyrolysis temperature, such as 1400 °C, can potentially ‘destabilize’ the Si-O-C-Ti system by consuming the free carbon and result in lower conductivities.     

Influence of silicon carbide as a mineralizer on mechanical and thermal properties of silica-based ceramic cores

Ceramic cores have been designed with compounds based on fused silica due to its excellent thermal stability and chemical inertness against molten metals. To endure the high temperatures present during investment casting, mineralizers have been widely used to enhance the flexural strength and shrinkage of ceramic cores. In this study, we demonstrated a silica-based ceramic core with silicon carbide as a mineralizer for improving the mechanical and thermal properties. The SiC in the silica-based ceramic cores can enhance the mechanical properties (i.e., flexural strength and linear shrinkage) by playing a role as a seed for the crystallization of fused silica to cristobalite. The SiC also improves the thermal conductivity due to its higher value compared with fused silica. The results suggest that using the optimal amount of silicon carbide in silica-based ceramic cores can provide excellent mechanical properties of flexural strength and linear shrinkage and improved thermal conductivity.     

High-temperature behavior of silicon oxycarbide glasses in air environment

Silicon oxycarbide glasses (SiOC) have been produced by siloxane resin under flowing argon at 1000 °C and then their evolutions in air from 800 to 1700 °C were investigated. Those glasses annealed at various temperatures were characterized by X-ray diffraction, ²⁹Si MAS NMR, Raman spectroscopy, and chemical element analysis. It can be found that oxidation reactions of the SiOC glasses occurred at above 1000 °C; carbothermal reduction was indiscernible at temperature below 1600 °C but almost finished at 1700 °C; and the decomposition of SiO_xC_4−x network was complete at 1400 °C.     

An optimized process for in situ formation of multi-walled carbon nanotubes in templated pores of polymer-derived silicon oxycarbide

A reliable and optimized process to grow carbon nanotubes (CNTs) in templated pores of polymer derived ceramic (PDC) matrix was developed. It is realized through the pyrolysis of a preceramic polymer, i.e., poly (methyl-phenyl-silsesquioxane) (denoted as PMPS), in argon atmosphere at 1000 °C together with nickel-catalyst-coated poly-methyl-methacrylate (PMMA) microbeads (denoted as PMMA-Ni). PMPS served as both a precursor for the ceramic matrix and a carbon source for the CNT growth. PMMA microbeads were used as sacrificial pore formers and coated with nickel via an electroless plating method, which provides an improved control of particle size of the catalyst and its distribution in the material. The influence of PMMA-Ni loading on the in situ growth of CNTs and the properties of CNTs/SiOC nanocomposites were studied through thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and density/porosity measurements. Under optimized conditions, uniform distribution of in situ grown CNTs was observed within the templated pores of the SiOC matrix. The optimized process leads to reproducible high yield of CNTs in the pores. The development of such novel CNT/cellular ceramic nanocomposite materials is of significant interest for a variety of sensor applications.     

High surface area silicon carbide doped with zirconium for use as catalyst support. Preparation, characterization and catalytic application

Zirconium doped SiC with a surface area from 88 to 200 m² g⁻¹ was synthesized using the shape memory concept method followed by calcination in air at a temperature of ≤480°C. The material obtained was composed of β-SiC and small ZrO₂ particles dispersed throughout the material matrix and a significant amount of an amorphous phase containing Si, Zr and O. Molybdenum oxycarbide, the active isomerization phase, supported on such a material displayed a similar behavior to that obtained on pure SiC for the n-heptane isomerization reaction. A comparison made with the molybdenum oxycarbide catalyst supported on pure ZrO₂ showed that the Zr doped SiC was not simply made of silicon carbide coated with a layer of ZrO₂ on the surface but probably an amorphous phase containing Si, Zr and O which displays a similar behavior as pure SiC.     

Grinding behavior of biomimetic fractal-branched silicon carbide ceramic inspired from leaf-vein structure

Silicon carbide ceramics are widely used in many industrial fields owing to their outstanding physical and chemical characteristics. However, their inherent hardness and brittleness make the grinding process very difficult compared to that involving ductile materials. In the present study, the effects of the biomimetic fractal-branched structure, inspired from the leaf-vein, on the grinding behavior of silicon carbide were investigated. Two biomimetic fractal-branched structures with different densities of micro-channels were designed and compared with the non-structured silicon carbide surface. The surface of the silicon carbide ceramic was textured through pulsed-laser ablation. Thereafter, the grinding experiment was conducted on the biomimetic fractal-branched and non-structured workpieces. The surface topography, subsurface damage, grinding force, grinding force ratio, surface roughness and grinding wheel wear were examined throughout the experiment. The experimental results indicated that the normal and tangential grinding forces for the fractal-branched structure surface are 7.61–18.21% and 8.34–26.13% lower than those for the non-structured surface. The grinding force ratio also increased significantly with an increase in the micro-channel density. In addition, a larger volume of coolant was transported through the grinding zone of the fractal-branched structure. The research results confirmed that the biomimetic fractal-branched structure on the silicon carbide surface enhanced the grinding performance and improved the grinding quality.     

A novel low cost method for the synthesis of ceramic nano silicon oxycarbide powder

Although different methods have been used for manufacturing micro- Silicon Oxycarbide (SiOC) powder, there is no account of nano-SiOC synthesis in the literature. In this study, a novel low cost sol–gel method was used for the synthesis of nano-silicon oxycarbide (SiOC) powder. An organic–inorganic hybrid, i.e., a Tetraethyl Ortosilicate/Polydimethylsiloxane (TEOS/PDMS) mixture, was used as the starting material. The sol–gel technique was employed to cross-link the precursors using a base catalyst. Consequently, the gel was dried at 90 °C for 24 h. The dried gel was pyrolyzed in a two-step process in argon atmosphere. The synthesized powder was investigated using XRD, FTIR, TGA, FESEM and BET techniques. XRD and FTIR analyses identified the product to be SiOC. BET analysis showed a specific surface area of about 150 m²/g for the synthesized powder, thereby suggesting its nano-sized characteristics. FESEM studies further confirmed that the powder was nano-sized with an average particle size of about 50 nm. The proposed procedure could be, therefore, a simple low cost method for the synthesis of nano-SiOC powder.     

Improving specific stiffness of silicon carbide ceramics by adding boron carbide

A strategy for improving the specific stiffness of silicon carbide (SiC) ceramics by adding B₄C was developed. The addition of B₄C is effective because (1) the mass density of B₄C is lower than that of SiC, (2) its Young’s modulus is higher than that of SiC, and (3) B₄C is an effective additive for sintering SiC ceramics. Specifically, the specific stiffness of SiC ceramics increased from ~142 × 10⁶ m²?s^?2 to ~153 × 10⁶ m²?s^?2 when the B₄C content was increased from 0.7 wt% to 25 wt%. The strength of the SiC ceramics was maximal with the incorporation of 10 wt% B₄C (755 MPa), and the thermal conductivity decreased linearly from ~183 to ~81 W?m^?1?K^?1 when the B₄C content was increased from 0.7 to 30 wt%. The flexural strength and thermal conductivity of the developed SiC ceramic containing 25 wt% B₄C were ~690 MPa and ~95 W?m^?1?K^?1, respectively.     

Effect of grain growth on the thermal conductivity of liquid-phase sintered silicon carbide ceramics

The effect of grain growth on the thermal conductivity of SiC ceramics sintered with 3 vol% equimolar Gd₂O₃-Y₂O₃ was investigated. During prolonged sintering at 2000 °C in an argon or nitrogen atmosphere, the β → α phase transformation, grain growth, and reduction in lattice oxygen content occurs in the ceramics. The effects of these parameters on the thermal conductivity of liquid-phase sintered SiC ceramics were investigated. The results suggest that (1) grain growth achieved by prolonged sintering at 2000 °C accompanies the decrease of lattice oxygen content and the occurrence of the β → α phase transformation; (2) the reduction of lattice oxygen content plays the most important role in enhancing the thermal conductivity; and (3) the thermal conductivity of the SiC ceramic was insensitive to the occurrence of the β → α phase transformation. The highest thermal conductivity obtained was 225 W(m K)⁻¹ after 12 h sintering at 2000 °C under an applied pressure of 40 MPa in argon.     

Synthesis,structure, and properties of silicon oxycarbide aerogels derived from tetraethylortosilicate /polydimethylsiloxane

Porous silicon oxycarbide (SiCO) aerogel monoliths were prepared by the sol-gel method using Tetraethylortosilicate/Polydimethylsiloxane as organic-inorganic precursors. The precursor gels were dried by supercritical ethanol fluid and pyrolyzed at 1200 °C in nitrogen atmosphere to form SiCO aerogels. The as-prepared SiCO aerogels are amorphous and present a network microstructure, surface area of 198.04 m²/g, average pore diameter of 56 nm, and pore volume of 0.648 cm³/g. The thermal conductivity of aerogel monoliths is only 0.027 W/m·K at 25 °C (Hot disk method). The atom ratios of Si, C, O elements in the SiCO aerogels are 30.77%, 14.67%, 54.56% respectively. The network microstructure of the SiCO aerogels are retained until 1100 °C, and the chemical groups and crystal phase structures are kept up until 1200 °C. There is only 1.65% of weight-loss until the same heated at 1200 °C in air, which is one of the highest thermally stable temperatures for SiCO aerogels ever reported.     

Influence of silicon carbide addition on the microstructural development of hot pressed zirconium and titanium diborides

The influences of adding SiC on the microstructure and densification behavior of ZrB₂ and TiB₂ ceramics, hot pressed at 1850 °C for 60 min under 20 MPa, were investigated. The sintered samples were characterized by SEM, EDS and XRD methods. A fully dense TiB₂-based ceramic was obtained by adding 30 vol% SiC. The grain size of ZrB₂ or TiB₂ matrices in the final microstructures decreased with increasing SiC content. The XRD analyses, microstructural characterization as well as thermodynamical calculations proved the in-situ formation of TiC in the SiC reinforced TiB₂-based composites. The interfaces between ZrB₂ and SiC grains in the SiC reinforced ZrB₂-based composites were free of any impurities or tertiary interfacial phases such as ZrC. This result was consistent with the X-ray diffraction pattern and thermodynamics.     

The influence of carbon atom distribution in precursors with 1:1 carbon to silicon atoms ratio on structure and thermal evolution of obtained silicon oxycarbide based materials

In this work, a number of precursors with 1:1 silicon to carbon atoms ratio and various carbon atom distributions were synthesized and pyrolyzed in order to obtain silicon oxycarbide based materials. The different carbon atom distributions were obtained using both simple monomers with only one silicon atom, as well as large monomers containing either four or sixteen silicon atoms with predefined carbon atom positions. The silicon oxycarbide based materials were investigated using IR, XRD, ²⁹Si MAS NMR and elemental analysis after annealing at various temperatures, as well as TG. The research shows that carbon atom distribution has great impact on the structure of final material and can be used to tailor the material for its projected uses.     

Synthesis and properties of a new, branched polyhydridocarbosilane as a precursor for silicon carbide

Polymerization of Cl₂Si(CH₃)CH₂Cl with Mg in THF, followed by reduction with LiAlH₄, gave a polycarbosilane with Si-H groups and branches at the Si atoms. The polymer could be cross-linked thermally at 150°C. Pyrolysis of the cross-linked material gave SiC with a yield of 70%.Presented at the XXVIth Silicon-Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Processing and microstructure-permeation properties of silica bonded silicon carbide ceramic membrane

Porous SiC is a valuable membrane material for the microfiltration and ultrafiltration of various wastewaters because of its high hydrophilicity and low fouling tendency, but its preparation has been limited by the high sintering temperature. Here, a silica bonded silicon carbide membrane was prepared by the oxidation of SiC at low temperature. When the SiC substrates were sintered in the temperature range from 1200 to 1400℃, their porosity decreased from 45 % to 37 % while the flexural strength increased from 45 to 59 MPa. For the selective layers made from SiC particles with 0.5 μm in diameter, the average pore sizes that sintered at 1050 and 1150 ℃ were 0.34 and 0.26 μm, respectively, corresponding to the water fluxes of 1080 and 1240 L/(m² h, respectively. Thus, this technique provided a cost-effective path to prepare ceramic membrane at low sintering temperature.     

Recent progress in the pore size control of silicon carbide ceramic membranes

The demand for separation and purification applications under harsh conditions has grown strongly in recent years. Silicon carbide (SiC) ceramic membranes have broad prospects in this aspect due to their unique characteristics, but its pore size control is a crucial problem. Therefore, it is of great significance to develop simple and feasible methods for precise control of the pore size of SiC membranes to improve membrane selectivity and expand their application range. This review describes the pore formation process in the preparation of SiC membranes, focusing on the selection of SiC particles, sintering temperature, sacrificial template, sintering aids, oxidation process and other factors affecting the pore size and analysis. Finally, the control of SiC membrane pore size is summarized and the outlook is proposed.     

Excellent ablation resistance and reusability of silicon carbide fiber reinforced silicon carbide composite in dissociated air plasmas

This work explores the potentials of SiC fiber reinforced SiC matrix composites (SiC_f/SiC) with SiC coating to resist aerodynamic ablations for thermal protection purpose. A plasma wind tunnel is employed to evaluate their anti-ablation property in dissociated air plasmas. The results suggest a critical ablation temperature of SiC coated SiC_f/SiC, ≈ 1910 °C, which is the highest ever reported in literatures. Benefited by ‘all-SiC’ microstructures and relative flat ablated surfaces, the SiC_f/SiC is still ablation-resistant up to ≈ 1820 °C after the occurrence of ablation. This implies an excellent ablation resistance and reusability property of SiC_f/SiC, which surpasses that of traditional carbon fiber reinforced composites. Finally, an ablation mechanism dominated by surface characteristic is proposed. For the SiC coated SiC_f/SiC, ablation is prone to take place at surface cracks formed by thermal mismatch; while for the ablated SiC_f/SiC, ablation is triggered at the exposed fiber bundles which is over-heated in the plasmas.