Preparation and Performance Study of Sialon‐Si3N4‐SiC Composite Ceramics for Concentrated Solar Power

For lowering the sintering temperature of silicon carbide ceramics used for solar thermal energy storage technology, O'‐Sialon and silicon nitride were employed as composite phases to construct Sialon‐Si₃N₄‐SiC composite ceramics. The composite ceramics were synthesized using SiC, Si₃N₄, quartz, and different alumina sources as starting materials with noncontact graphite‐buried sintering method. Influences of alumina sources on the physical properties and thermal shock resistance of the composites were studied. The results revealed that the employment of O'‐Sialon and silicon nitride could decrease the sintering temperature greatly to 1540°C. The optimum formula G2 prepared from mullite as alumina source achieved the best performances: 66.7 MPa of bending strength, 10.0 W/(m·K) of thermal conductivity. The composition parameter x = 0.4 of O'‐Sialon decreased to 0.04 after 30 cycles thermal shock, and the bending strength increased with a rate of 11.0% due to the increase of O'‐Sialon grain size, and the optimization of microstructure caused by the transformation of O'‐Sialon grains and densification within the samples. The good thermal shock resistance makes the composites suitable for the use as thermal storage materials of concentrated solar power generation.     

Electromagnetic wave absorption properties of hot-pressed Si3N4-SiC ceramic nanocomposites

High-density Si₃N₄-SiC ceramic nanocomposites have exceptional mechanical properties, but little is known about their electromagnetic wave absorption (EMA) capabilities. In this paper, the effects of sintering temperature and starting material compositions on the dielectric and EMA properties of hot-pressed Si₃N₄-SiC ceramic nanocomposites were investigated. The real and imaginary permittivities of Si₃N₄-SiC ceramic nanocomposites increase with increasing sintering temperature or SiC content, particularly at the sintering temperature of 1850°C and SiC content of 50 wt.%. This is primarily due to the improvement of interfacial and defect polarizations, which is caused by the doping of nitrogen into the SiC nanocrystals during the solution-precipitation process. The real and imaginary permittivities of Si₃N₄-SiC ceramic nanocomposites show decreasing trends as sintering aid content increases. Si₃N₄-SiC ceramic composites have both good EMA and mechanical properties when they are sintered at 1850°C with 30 wt.% SiC and 5–8 wt.% sintering aids. The minimum reflection loss and maximum flexural strength reach -58 dB and 586 MPa, respectively. Materials with multilayered structural designs have both strong and broad EMA properties.     

Low-temperature Pr3Si2C2-assisted liquid-phase sintering of SiC with improved thermal conductivity

A novel Pr₃Si₂C₂ additive was uniformly coated on SiC particles using a molten-salt method to fabricate a high-density SiC ceramics via liquid-phase spark plasma sintering at a relatively low temperature (1400°C). According to the calculated Pr–Si–C-phase diagram, the liquid phase was formed at ∼1217°C, which effectively improved the sintering rate of SiC by the solution–reprecipitation process. When the sintering temperature increased from 1400 to 1600°C, the thermal conductivity of SiC increased from 84 to 126 W/(m K), as a consequence of the grain growth. However, an increasing amount of the sintering additive increased the interfacial thermal resistance, resulting in a decrease of thermal conductivity of the materials. The highest thermal conductivity of 141 W/(m K) was obtained for the material having the largest SiC grains and an optimized amount of the additive at the grain boundaries and triple junctions. The proposed Pr₃Si₂C₂-assisted liquid-phase sintering of SiC can be potentially used for the fabrication of SiC-based ceramic composites, where a low sintering temperature would inhibit the grain growth of SiC fibers.     

Preparation of silicon carbide–silicon nitride composite foams from pre-ceramic polymers

A new method of forming silicon carbide–silicon nitride composite foams is presented. These are prepared by immersing a polyurethane foam in a polysilane precursor solution mixed with Si₃N₄ powder to form a pre-foam followed by heating it in nitrogen at >900°C. X-ray diffraction patterns indicate that a SiC–Si₃N₄ composite was formed after sintering the ceramic foam at >1500°C. Micrographs show that most of these foams have well-defined open-cell structures and macro-defect free struts. The shrinkage is reduced considerably due to the addition of Si₃N₄ particles.     

Thermal conductivity of porous SiC composite ceramics derived from paper precursor

Biomorphic porous SiC composite ceramics were produced by chemical vapor infiltration and reaction (CVI-R) technique using paper precursor as template. The thermal conductivity of four samples with different composition and microstructure was investigated: (a) C-template, (b) C-SiC, (c) C-SiC–Si₃N₄ and (d) SiC coated with a thin layer of TiO₂. The SiC–Si₃N₄ composite ceramic showed enhanced oxidation resistance compared to single phase SiC. However, a key property for the application of these materials at high temperatures is their thermal conductivity. The later was determined experimentally at defined temperatures in the range 293–373 K with a laser flash apparatus. It was found that the thermal conductivity of the porous ceramic composites increases in the following order: C-template < C-SiC < C-SiC–Si₃N₄ < SiC–TiO₂. The results were interpreted in regard to the porosity and the microstructure of the ceramics.     

Effects of discrete and simultaneous addition of SiC and Si3N4 on microstructural development of TiB2 ceramics

The impact of Si₃N₄ and SiC additives incorporation in the microstructure and sintering behavior of TiB₂-based composites were studied. Three ceramic composites including TiB₂–Si₃N₄, TiB₂–SiC, and TiB₂–SiC–Si₃N₄ were manufactured by spark plasma sintering (SPS) at 1950 °C for 8 min under 35 MPa. The acquired ceramics were analyzed by X-ray diffractometry and scanning electron microscopy. In addition, the sintering thermodynamic was investigated using the HSC Chemistry package. X-ray diffraction patterns of the prepared ceramics revealed the in-situ formation of graphite and boron nitride in the final composites initiated from SiC and Si₃N₄, respectively. The thermodynamic assessments proved the role of liquid phase sintering on the sinterability enhancement of all composite samples. Field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy verified the in-situ formation of both BN and graphite components in the sample containing SiC and Si₃N₄ additives. Finally, the fractographical investigations clarified the transgranular breakage as the main fracture mode in the TiB₂-based ceramics.     

Fabrication of Si3N4 ceramics with high thermal conductivity and flexural strength via novel two-step gas-pressure sintering

Si₃N₄ ceramic substrates serving as heat dissipater and supporting component are required to have excellent thermal and mechanical properties. To prepare Si₃N₄ with desirable properties, a novel two-step gas-pressure sintering route including a pre-sintering step followed by a high-temperature sintering step was devised. The effects of pre-sintering temperature (1500 – 1600 °C) on the phase transformation, microstructure, thermal and mechanical properties of the samples were studied. The pre-sintering temperature played an important role in adjusting the Si₃N₄ particles’ rearrangement and α→β transformation rate. Furthermore, the densification process for the Si₃N₄ ceramics prepared via the two-step gas-pressure sintering was revealed. After sintered at 1525 °C for 3 h followed by a high-temperature sintering at 1850 °C for another 3 h, the prepared Si₃N₄ compact with a bimodal microstructure presented the highest thermal conductivity and flexural strength of 79.42 W·m^?1·K^?1 and 801 MPa, respectively, which holds great application prospects as ceramic substrates.     

Fabrication of high thermal conductivity silicon nitride ceramics by pressureless sintering with MgO and Y2O3 as sintering additives

The fabrication of silicon nitride (Si₃N₄) ceramics with a high thermal conductivity was investigated by pressureless sintering at 1800 °C for 4 h in a nitrogen atmosphere with MgO and Y₂O₃ as sintering additives. The phase compositions, relative densities, microstructures, and thermal conductivities of the obtained Si₃N₄ ceramics were investigated systemically. It was found that at the optimal MgO/Y₂O₃ ratio of 3/6, the relative density and thermal conductivity of the obtained Si₃N₄ ceramic doped with 9 wt% sintering aids reached 98.2% and 71.51 W/(m·K), respectively. EDS element mapping showed the distributions of yttrium, magnesium and oxygen elements. The Si₃N₄ ceramics containing rod-like grains and grain boundaries were fabricated by focused ion beam technique. TEM observations revealed that magnesium existed as an amorphous phase and that yttrium produced a new secondary phase.     

Effects of Si3N4 and WC on the oxidation resistance of ZrB2/SiC ceramic tool materials

ZrB₂/SiC, ZrB₂/SiC/Si₃N₄ and ZrB₂/SiC/WC ceramic tool materials were prepared by spark plasma sintering technology, and their oxidation resistance was tested at different oxidation temperatures. When the oxidation temperature is 1300 °C, the oxide layer thickness, oxidation weight gain and flexural strength of ZrB₂/SiC/Si₃N₄ ceramic tool material after oxidation are 8.476 μm, 1.436 mg cm^?2 and 891.0 MPa, respectively. Compared with ZrB₂/SiC ceramic tool materials, the oxide layer thickness and oxidation weight gain are reduced by 8.2% and 11.8%, respectively, and the flexural strength after oxidation is increased by 116.1%. However, the addition of WC significantly reduces the oxidation resistance of the ceramic tool material. A dense oxide film is formed on the surface of ZrB₂/SiC/Si₃N₄ ceramic tool material during oxidation, which effectively prevents oxygen from entering the inside of the material, thereby improving the oxidation resistance of the ceramic tool material.     

Electrical and thermophysical properties of ZrB2 and HfB2 based composites

Electrical resistivities, thermal conductivities and thermal expansion coefficients of hot-pressed ZrB₂–SiC, ZrB₂–SiC–Si₃N₄, ZrB₂–ZrC–SiC–Si₃N₄ and HfB₂–SiC composites have been evaluated. Effects of Si₃N₄ and ZrC additions on electrical and thermophysical properties of ZrB₂–SiC composite have been investigated. Further, properties of ZrB₂–SiC and HfB₂–SiC composites have been compared. Electrical resistivities (at 25 °C), thermal conductivities (between 25 and 1300 °C) and thermal expansion coefficients (over 25–1000 °C) have been determined by four-probe method, laser flash method and thermo-mechanical analyzer, respectively. Experimental results have shown reasonable agreement with theoretical predictions. Electrical resistivities of ZrB₂-based composites are lower than that of HfB₂–SiC composite. Thermal conductivity of ZrB₂ increases with addition of SiC, while it decreases on ZrC addition, which is explained considering relative contributions of electrons and phonons to thermal transport. As expected, thermal expansion coefficient of each composite is reduced by SiC additions in 25–200 °C range, while it exceeds theoretical values at higher temperatures.     

Improved electromagnetic absorbing properties of Si3N4–SiC/SiO2 composite ceramics with multi-shell microstructure

Porous Si₃N₄–SiC composite ceramic was fabricated by infiltrating SiC coating with nano-scale crystals into porous β-Si₃N₄ ceramic via chemical vapor infiltration (CVI). Silica (SiO₂) film was formed on the surface of rod-like Si₃N₄–SiC grains during oxidation at 1100 °C in air. The as-received Si₃N₄–SiC/SiO₂ composite ceramic attains a multi-shell microstructure, and exhibits reduced impedance mismatch, leading to excellent electromagnetic (EM) absorbing properties. The Si₃N₄–SiC/SiO₂ fabricated by oxidation of Si₃N₄–SiC for 10 h in air can achieve a reflection loss of ?30 dB (>99.9% absorption) at 8.7 GHz when the sample thickness is 3.8 mm. When the sample thickness is 3.5 mm, reflection loss of Si₃N₄–SiC/SiO₂ is lower than ?10 dB (>90% absorption) in the frequency range 8.3–12.4 GHz, the effective absorption bandwidth is 4.1 GHz.     

A novel method of strong and tough Si3N4 ceramic from the particle-stabilized foam

The brittleness of Si₃N₄ ceramics has always limited its wide application. In this paper, Si₃N₄ ceramics were prepared based on foam. Combining the unique honeycomb structure of the ceramic foams and the self-toughening mechanism of Si₃N₄, the strengthening and toughening of Si₃N₄ ceramics can be further achieved by adjusting the microstructure of Si₃N₄ ceramic foams. The powder particles are self-assembled by particle-stabilized foaming to form a foam body with a honeycomb structure. It was pretreated at different temperatures (1450–1750°C). The microstructure evolution of foamed ceramics at different pretreatment temperatures and the conversion rate of α-Si₃N₄ to β-Si₃N₄ at different pretreatment temperatures were explored. Then the foamed ceramics with different microstructures are hot-press sintered to prepare Si₃N₄ dense ceramics. The effects of different microstructures of foamed ceramics on the strength and toughness of Si₃N₄ ceramics were analyzed. The experimental results show that the relative density of Si₃N₄ ceramics prepared at a particle pretreatment temperature of 1500°C is 97.8%, and its flexural strength and fracture toughness are relatively the highest, which are 1089 ± 60 MPa and 12.9 ± 1.3 MPa m^1/2, respectively. Compared with the traditional powder hot-pressing sintering, the improvement is 21% and 33%, respectively. It is shown that this method of preparing Si₃N₄ ceramics based on foam has the potential to strengthen and toughen Si₃N₄ ceramics.     

Sintered silicon nitride/nano-silicon carbide materials based on preceramic polymers and ceramic powder

A flexible method is presented, which enables the fabrication of porous as well as dense Si₃N₄/nano-SiC components by using Si₃N₄ powder and a preceramic polymer (polycarbosilazane) as alternative ceramic forming binder. The SiCN polymer benefits consolidation as well as shaping of the green body and partially fills the interstices between the Si₃N₄ particles. Cross-linking of the precursor at 300 °C increases the mechanical stability of the green bodies and facilitates near net shape machining. At first, pyrolysis leads to porous ceramic bodies. Finally, subsequent gas pressure sintering results in dense Si₃N₄/nano-SiC ceramics. Due to the high ceramic yield of the polycarbosilazane binder, the shrinkage during sintering is significantly reduced from 20 to 15 lin.%. Investigations of the sintered ceramics reveal, that the microstructure of the Si₃N₄ ceramic contains approx. 6 vol.% nano-scaled SiC segregations, which are located both at the grain boundaries and as inclusions in the Si₃N₄ grains.     

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.     

Microstructure and mechanical properties of tantalum carbide ceramics: Effects of Si3N4 as sintering aid

Stoichiometric Tantalum carbide (TaC) ceramics were prepared by reaction spark plasma sintering using 0.333–2.50 mol% Si₃N₄ as sintering aid. Effects of the Si₃N₄ addition on densification, microstructure and mechanical properties of the TaC ceramics were investigated. Si₃N₄ reacted with TaC and tantalum oxides such as Ta₂O₅ to form a small concentration of tantalum silicides, SiC and SiO₂, with significant decrease in oxygen content in the consolidated TaC ceramics. Dense TaC ceramics having relative densities >97% could be obtained at 0.667% Si₃N₄ addition and above. Average grain size in the consolidated TaC ceramics decreased from 11 µm at 0.333 mol% Si₃N₄ to 4 µm at 2.50 mol% Si₃N₄ addition. The Young's modulus, Vickers hardness and flexural strength at room temperature of the TaC ceramic with 2.50 mol% Si₃N₄ addition was 508 GPa, 15.5 GPa and 605 MPa, respectively. A slight decrease in bending strength was observed at 1200 °C due to oxidation of the samples.     

Synthesis mechanism of AlN–SiC solid solution reinforced Al2O3 composite by two-step nitriding of Al–Si3N4–Al2O3 compact at 1500 °C

The in-situ controllable synthesis of AlN–SiC solid solution reinforcement in large-sized Al–Si₃N₄–Al₂O₃ composite refractory by two-steps nitriding sintering was examined. In the first step, a dynamic Al@AlN structure was constructed in the composite by pre-nitriding at 580 °C. During the subsequent sintering process, it cracked above ∼900 °C, and micronized Al cluster (mixture of droplets and vapor) was extracted out gradually. As a result, multiple AlN mesophases were formed through different reaction paths, including i) initial AlN shell formed by solid Al with N₂, ii) reaction of Al cluster with N₂, and iii) reaction of Al cluster with Si₃N₄ from 900 °C to 1500 °C. The Si₃N₄ precursor serves as both a solid nitrogen source and an active Si source, and the controllable reaction between Al and Si₃N₄ leading to uniformly distributed AlN and Si mesophases. AlN–SiC solid solution is significantly formed when liquid Si appears. The shell, granule and whisker SiC–AlN solid solution were observed mainly depending on the dynamic AlN mesophase. The SiC–AlN solid solution reinforced Al₂O₃ materials is a novel promising refractory for large-scale blast furnace lining.     

Physical,thermal and ablative performance of CVI densified urethane-mimetic SiC preforms containing in situ grown Si3N4 whiskers

A two-step process has been developed for silicon carbide (SiC) coated polyurethane mimetic SiC preform containing silicon nitride (Si₃N₄) whiskers. SiC/Si₃N₄ preforms were prepared by pyrolysis/siliconization treatment at 1600 °C, of powder compacts containing rigid polyurethane, novolac and Si, forming a porous body with in situ grown Si₃N₄ whiskers. The properties were controlled by varying Si/C mole ratios such as 1–2.5. After densification using a chemical vapour infiltration, the resulting SiC/Si₃N₄/SiC composites showed excellent oxidation resistance, thermal conductivity of 4.32–6.62 Wm⁻¹ K⁻¹, ablation rate of 2.38 × 10⁻³ − 3.24 × 10⁻³ g cm⁻² s and a flexural strength 43.12–55.33 MPa for a final density of 1.39–1.62 gcm⁻³. The presence of a Si₃N₄ phase reduced the thermal expansion mismatch resulting in relatively small cracks and well-bonded layers even after ablation testing. This innovative two-step processing can provide opportunities for expanded design for using SiC/Si₃N₄/SiC composites being lightweight, inexpensive, homogeneous and isotropic for various high temperature applications.     

Joining of Cf/SiC composites and Si3N4 ceramic with Y2O3–Al2O3–SiO2 glass filler for high-temperature applications

C_f/SiC composites and Si₃N₄ ceramics are candidate materials for applications in thermal protection system. This paper investigated the joining of C_f/SiC and Si₃N₄ using Y₂O₃–Al₂O₃–SiO₂ glass. The reliability of joints was evaluated by thermal shock tests. In this present work, the typical joint structure was C_f/SiC-glass-Si₃N₄. The results demonstrate that Direct bonding has been identified as the interfacial bonding mechanism at the SiC/glass and glass/Si₃N₄ interfaces. The maximum shear strength of the C_f/SiC–Si₃N₄ joint was ~34 MPa, which delivered an effective method to achieve strong, reliable bonding between the dissimilar materials. In addition, after thermal shock for 10 cycles, the residual strength remained ~13 MPa. Bubbles instead of microcracks formed in the glass filler, which was the main factor causing the degradation of the joint performance. It is suggested that improving the high temperature resistance of joining materials is the key to realize the application of this joint structure.     

Mechanism of improving the mechanical properties of Si3N4/TiC ceramic tool materials prepared by spark plasma sintering

Spark plasma sintering (SPS) is a new sintering method having shorter sintering time and higher densification speed than the traditional sintering methods. In this paper, the Si₃N₄/TiC ceramic tool material is sintered by SPS. The microstructure and mechanical properties of the material under different sintering parameters are compared. The sintering process of the material is then analyzed, and the best sintering parameters are obtained. Heat the material to 1600°C and keep the temperature for 15 min, then continue to heat to 1700°C and keep the temperature for 10 min, Si₃N₄/TiC ceramic tool material has high mechanical properties, its bending strength, fracture toughness, and Vickers hardness are 959 MPa, 8.61 MPa·m^1/2, and 15.21 GPa, respectively. The scanning electron microscope (SEM) analysis shows that under this condition, the sintering additives and Si₃N₄/TiC material form the liquid phase, which makes the Si₃N₄ particles rearrange, dissolve, precipitate, and transform into rod shape β-Si₃N₄. In addition, under the action of pulse current and external pressure, electric sparks are generated between TiC particles, which allows the material transfer and particle refinement. Therefore, the β-Si₃N₄ has uniform grain size, and it is vertically and horizontally arranged in the structure, which makes the material have excellent mechanical properties.     

Porous SiC–Si3N4 composite ceramics with excellent EMW absorption property prepared by gelcasting using DMAA

The porous SiC–Si₃N₄ composite ceramics with good EMW absorption properties were prepared by combination of gelcasting and carbothermal reduction. The pre-oxidation of Si₃N₄ powders significantly improved the rheological properties of slurries (0.06 Pa s at 103.92 s⁻¹) and also suppressed the generation of NH₃ and N₂ from Si₃N₄ hydrolysis and reaction between Si₃N₄ and initiator APS, thereby reducing the pore defects in green bodies and enhancing mechanical properties with a maximum value of 42.88 MPa. With the extension of oxidation time from 0 h to 10 h, the porosity and pore size of porous SiC–Si₃N₄ composite ceramics increased from approximately 41.86% and 1.0–1.5 μm to 46.33% and ~200 μm due to the production of CO, N₂ and gaseous SiO, while the sintering shrinkage decreased from 16.24% to 10.50%. With oxidation time of 2 h, the Si₂N₂O fibers formed in situ by the reaction of Si₃N₄ and amorphous SiO₂ effectively enhanced the mechanical properties, achieving the highest flexural strength of 129.37 MPa and fracture toughness of 4.25 MPa m^1/2. Compared with monolithic Si₃N₄ ceramics, the electrical conductivity, relative permittivity and dielectric loss were significantly improved by the in-situ introduced PyC from the pyrolysis of three-dimensional network DMAA-MBAM gel in green bodies and the SiC from the carbothermal reduction reaction between PyC and SiO₂ and Si₃N₄. The porous SiC–Si₃N₄ composite ceramics prepared by the unoxidized Si₃N₄ powders demonstrated the optimal EMW absorption properties with reflection loss of −22.35 dB at 8.37 GHz and 2 mm thickness, corresponding to the effective bandwidth of 8.20–9.29 GHz, displaying great application potential in EMW absorption fields.