Low-temperature preparation of porous SiC ceramics using phosphoric acid as a pore-forming agent and a binder

Porous SiC ceramics combine the properties of both SiC ceramics and porous materials. Herein, we design a facile method via pressureless sintering at relatively low temperatures for the synthesis of porous SiC ceramics. In the synthesis process, phosphoric acid was used as the sintering additive that reacted with SiO₂ on the surface of SiC to form phosphates. The formed phosphates acted as a binder to connect the SiC particles. At a fixed temperature, the phosphates were partially decomposed and released a large amount of gas. This changed the pore structure of the ceramics and greatly improved their porosity. Finally, we obtained the porous SiC ceramics with high porosity and high strength. We investigate the effects of H₃PO₄ content on the phase composition, microstructure, porosity, mechanical properties and thermal expansion coefficient of the prepared porous SiC ceramics. It was shown that at the sintering temperature of 1200 °C, the highest porosity of the samples can reach 70.42% when the H₃PO₄ content is 25 wt%, and their bending strength reaches 36.11 MPa at room temperature when the H₃PO₄ content is 15 wt%. In addition, the porous SiC ceramics show good high-temperature stability with a bending strength of 42.05 MPa at 1000 °C and the thermal expansion coefficient of 3.966 × 10⁻⁶/°C.     

Direct ink writing of porous SiC ceramics with geopolymer as binder

We herein report a novel strategy for direct ink writing of porous SiC parts by using geopolymers (GP) as binders and sintering SiC/GP composites at high temperatures via carbothermal reduction. The effects of treatment temperatures on the microstructure, pore size distribution and compressive strength of SiC/GP composites were systematically investigated. The total porosity of porous SiC carriers was as high as 76.4 vol% after being sintered at 1800 °C and exhibited a much broader pore size distribution (pore volumes) between 39 nm and 13.951 µm (~1.68 mL/g) accompanied by an interconnected hierarchical porous structure. After loading lamellar graphene oxide into the porous SiC carrier to form GO/SiC adsorbents, they exhibited fast and near-unity removal of methylene blue, and the adsorption efficiency still exceeded 82.0% after multiple times usage. These results prove that it is possible to remove hazardous materials from wastewater using reusable porous SiC ceramics as reusable adsorbent carriers.     

Processing and properties of silica-bonded porous nano-SiC ceramics with extremely low thermal conductivity

Silica-bonded porous nano-SiC ceramics with extremely low thermal conductivity were prepared by sintering nano-SiC powder-carbon black template compacts at 600–1200 °C for 2 h in air. The microstructure of the silica-bonded porous nano-SiC ceramics consisted of SiC core/silica shell particles, a silica bonding phase, and hierarchical (meso/macro) pores. The porosity and thermal conductivity of the silica-bonded porous nano-SiC ceramics can be controlled in the ranges of 8.5–70.2 % and 0.057–2.575 Wm⁻¹ K⁻¹, respectively, by adjusting both, the sintering temperature and template content. Silica-bonded porous nano-SiC ceramics with extremely low thermal conductivity (0.057 Wm⁻¹ K⁻¹) were developed at a very low processing temperature (600 °C). The typical porosity, average pore size, compressive strength, and specific compressive strength of the porous nano-SiC ceramics were ∼70 %, 50 nm, 2.5 MPa, and 2.7 MPa·cm³/g, respectively. The silica-bonded porous nano-SiC ceramics were thermally stable up to 1000 °C in both air and argon atmospheres.     

Fabrication of porous silicon carbide ceramics with high porosity and high strength

Unique porous SiC ceramics with a honeycomb structure were fabricated by a sintering-decarburization process. In this new process, first a SiC ceramic bonded carbon (SiC/CBC) is sintered in vacuum by spark plasma sintering, and then carbon particles in SiC/CBC are volatized by heating in air at 1000 °C without shrinkage. The honeycomb structure has at least two different sizes of pores; ∼20 μm in size resulting from carbon removal; and smaller open pores of 2.1 μm remaining in the sintered SiC shell. The total porosity is around 70% and the bulk density is 0.93 mg/m³. The bending and compressive strengths are 26 MPa, and 105 MPa, respectively.     

Recycling of waste red mud for fabrication of SiC/mullite composite porous ceramics

SiC/mullite composite porous ceramics were fabricated from recycled solid red mud (RM) waste. The porous ceramics were formed using a graphite pore forming agent, RM, Al(OH)₃ and SiC in the presence of catalysts. The influence of firing temperature and the pore-forming agent content on the mechanical performance, porosity and the microstructure of the porous SiC ceramics were investigated. Optimal preparation condition were determined by some testing. The results indicated that the flexural strength of specimens increased as a function of firing temperature and a reduction in graphite content, which concomitantly decreased porosity. The ceramic prepared under optimal conditions having 15?wt% graphite and sintered at 1350?°C, demonstrated excellent performance. Under optimal preparation conditions the flexural strength and porosity of the ceramic were 49.4?MPa and 31.4%, respectively. Scanning electron microscopy observation result showed that rod-shape mullite grains endowed the samples with high flexural strength and porosity. X-ray diffraction analysis indicated that the main crystallization phases of the porous ceramics were 6H-SiC, mullite, cristobalite and alumina. This work demonstrates that RM can be sucessfully reused as a new raw material for SiC/mullite composite porous ceramics.     

Joining of SiC ceramics via a novel liquid preceramic polymer (V-PMS)

A novel liquid preceramic polymer (V-PMS) was synthsized by modifying polymethylsilane (PMS) with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane ([CH₃(CH₂CH)SiO]₄, D4Vi), for joining SiC ceramics under ambient pressure. The obtained V-PMS with a viscosity of 125 Pas at room temperature exhibits excellent thermal properties and bonding strength. The ceramic yield of V-PMS treated at 1200 °C under Ar atmosphere is 84.5%, which is 38.3% higher than the original PMS. The shear strengths of the SiC joints joined by V-PMS at 800 °C, 1000 °C and 1200 °C under N₂ atmosphere are 11.9 MPa, 34.5 MPa and 29.9 MPa, respectively. The excellent performances make the obtained V-PMS promising candidates for joining SiC ceramics in high-temperature applications.     

Design and characterization of porous mullite based semi-vitrified ceramics

Three porous ceramic composites were prepared from readily available raw materials (kaolin, bauxite, feldspar and kyanite). The porous ceramic formulations were sintered at different temperatures ranging from 1200 to 1400°C. The fired specimens were characterized by determining their porosity, bulk density, flexural strength, thermochemical stability, microstructure, water and mercury permeability. Apparent porosity and bulk density in the range 15.57 ± 1.56–42.73 ± 2.28?vol% and 2.23 ± 0.31–2.68 ± 0.41?g?cm^?3 respectively were obtained after firing. The flexural strength was in the range of 32.31 ± 2.1–74.88 ± 2.57?MPa and the thermal expansion coefficient of 5–9 × 10^?6 C^?1. The values of water permeability were 745.4, 641.45 and 525.91?L/m² h?kPa respectively for PK3, PK4 and PK5. It was found that at high temperature (1400?°C), kyanite particles enhanced the porosity and thermal stability by reducing glass formation and improving crystallization. The presence of the interconnected pores with size between 0.03 and 4.50?µm, the high total volume of pores together with the high flexural strength and thermal stability make the synthesized porous ceramics suitable for high-pressure filtering applications.     

Development of ethylene glycol-based gelcasting for the preparation of highly porous SiC ceramics

Aqueous gelcasting is inappropriate for the preparation of highly porous ceramics, due to the large drying shrinkage of green bodies caused by the high surface tension of water. To solve this problem, non-aqueous gelcasting using organic solvents with much lower surface tension was developed. However, for most organic solvents, the precipitation polymerization of gels led to the low strength of green bodies, which was inconvenient for the fabrication of large size workpieces. In this work, a novel ethylene glycol-based gelcasting was developed to prepare highly porous SiC ceramics. Ethylene glycol induced the solution polymerization of gels and increased the strength of green bodies effectively. In addition, the high flexibility of the ethylene glycol-based gels could release the inner stress in the drying process. Highly porous SiC ceramics with large size were successfully prepared by the optimized gelcasting method.     

Synthesis of hierarchical porous silicon oxycarbide ceramics from preceramic polymer and wood biomass composites

Hierarchical porous SiOC ceramics were successfully prepared using a polysiloxane preceramic polymer mixed with wood biomass by annealing at different temperatures under Ar atmosphere. These SiOC ceramics display a trimodal pore size distribution in the micro-, meso- (micropores + mesopores, 1.7–14 nm) and macro-size scale (1–15 μm). The mesopores and micropores mainly originate from the formation of large amounts of SiC crystals and nanowires, graphite-like microcrystallites, and nm-scale pores of ray parenchyma cells and pits of the wood biomass. The SiOC sample prepared at a higher temperature processes the specific surface area up to 180.5 m²/g. The specific surface area, pore volume and average pore width of the samples can be controlled by adjusting the pyrolysis temperature.     

Effects of porosity on electrical and thermal conductivities of porous SiC ceramics

The effects of porosity on the electrical and thermal conductivities of porous SiC ceramics, containing Y₂O₃–AlN additives, were investigated. The porosity of the porous SiC ceramic could be controlled in the range of 28–64 % by adjusting the sacrificial template (polymer microbead) content (0–30 wt%) and sintering temperature (1800–2000 °C). Both electrical and thermal conductivities of the porous SiC ceramics decreased, from 7.7 to 1.7 Ω⁻¹ cm⁻¹ and from 37.9 to 5.8 W/(m·K), respectively, with the increase in porosity from 30 to 63 %. The porous SiC ceramic with a coarser microstructure exhibited higher electrical and thermal conductivities than those of the ceramic with a finer microstructure at the equivalent porosity because of the smaller number of grain boundaries per unit volume. The decoupling of the electrical conductivity from the thermal conductivity was possible to some extent by adjusting the sintering temperature, i.e., microstructure, of the porous SiC ceramic.     

Joining SiC ceramics with silicon resin YR3184

Joints between reaction-bonded silicon carbide (RBSiC) and joints between pressureless sintered silicon carbide (SSiC) were produced respectively using a polysiloxane silicon resin (YR3184, GE Toshiba Silicones) as joining material. Samples were heat treated in a nitrogen flux at temperatures around 1200 °C. The maximum three point bending strength of the joints between reaction-bonded silicon carbide is 197 MPa. The maximum three point bending strength of the joints between sintered silicon carbide is 163 MPa. The join layers are continuous, homogeneous and densified and have thickness of 2–5 μm. The joining mechanism is that the amorphous silicon oxycarbide ceramic pyrolyzed from YR3184 acts as an inorganic adhesive.     

Low-temperature joining of SiC ceramics using NITE phase with Al2O3-Ho2O3 additive

In order to avoid the property degradation resulting from high-temperature joining process, nano-infiltrated transient eutectoid (NITE) phase with the Al₂O₃-Ho₂O₃ as the joining adhesives was adopted to join silicon carbide (SiC) ceramics with the attempts to lower down the joining temperature. The liquid-phase-sintered silicon carbide (LPS-SiC) specimens were joined at 1500-1800°C by spark plasma sintering (SPS) under the pressure of 20 MPa. The results of the shear test and microstructure observation showed that the joining process could be finished at a relatively lower temperature (1700°C) compared to other NITE-phase joining. In contrast to the shear strength of 186.4 MPa derived from the SiC substrate, the joint exhibited the shear strength of 157.8 MPa with the fully densified interlayer.     

Spheroidization of SiC powders and their improvement on the properties of SiC porous ceramics

Spherical SiC powders were prepared at high temperature using commercial SiC powders (4.52 µm) with irregular morphology. The influence of spherical SiC powders on the properties of SiC porous ceramics was investigated. In comparison with the as-received powders, the spheroidized SiC powders exhibited a relatively narrow particle size distribution and better flowability. The spheroidization mechanism of irregular SiC powder is surface diffusion. SiC porous ceramics prepared from spheroidized SiC powders showed more uniform pore size distribution and higher bending strength than that from as-received SiC powders. The improvement in the performance of SiC porous ceramics from spheroidized powder was attributed to tighter stacking of spherical SiC particles. After sintering at 1800 °C, the open porosity, average pore diameter, and bending strength of SiC porous ceramics prepared from spheroidized SiC powder were 39%, 2803.4 nm, and 66.89 MPa, respectively. Hence, SiC porous ceramics prepared from spheroidized SiC powder could be used as membrane for micro-filtration or as support of membrane for ultra/nano-filtration.     

Synthesis and characterization of Si/SiC ceramics prepared using cotton fabric

A Si/SiC ceramic was prepared from cotton fabric by the reactive infiltration of liquid silicon into the carbon template. A large density difference between the samples has been observed. This may be due to the variation in the pore size and its distribution within the sample. Scanning electron microscopy with energy dispersive spectroscopy shows the presence of three distinct phases, i.e., SiC, free Si and free carbon. X-ray diffraction pattern also confirms the presence of SiC and Si phases. However, there is no peak corresponding to carbon. So, it is inferred that the carbon exists in amorphous form. Micro-hardness, fracture toughness and bending strength of the ceramics were also studied. The values are lower than commercially available SiC ceramics. This may be due to the highly porous nature of cotton fabric-based SiC, as compared to commercially available SiC.     

Fabrication and properties of SiC porous ceramics using a polyurethane preparation process

SiC porous ceramics can be prepared by introducing the polyurethane preparation method into the production process of ceramic biscuits, followed by sintering at 1300?°C for 2?h under N₂ flux after the cross-linking of polycarbosilane at 220?°C for 4?h in air. The microstructures, mechanical properties and infiltrations of the SiC porous ceramics are investigated in detail. The best dispersal effect comes from the SiC slurry with xylene as the solvent and a mixture of Silok®7096 (1?wt%) and Anjeka®6041 (4?wt%) as the dispersant. The compressive strength of SiC porous ceramics with high porosity (69.53%) reaches 16.9?MPa. The heat treatment can increase infiltration, the rate of which (4.296?×?10^?7 mm²) after the heat treatment at 750?°C in air is approximately two times faster than that before the heat treatment. The SiC porous ceramics fabricated in this study will have potential application in active thermal protection systems.     

Pressureless fabrication of dense monolithic SiC ceramics from a polycarbosilane

This paper presents the pressureless preparation of dense and crack-free near stoichiometric SiC monoliths via cross-linking and pyrolysis of a polycarbosilane, followed by polymer-infiltration-pyrolysis cycles. The composition and the porosity of the samples strongly depend on the processing temperature. Thus, at 1050–1100 °C, the SiC monoliths are X-ray amorphous and exhibit low amounts of oxygen and excess carbon; their porosity was rather high (>10%). Higher processing temperatures induced the crystallization of β-SiC. The removal of oxygen and excess carbon due to CO release allowed for obtaining near-stoichiometric compositions at 1700 °C. However, the residual porosity of the samples increased. The use of the PIP technique led already after six cycles to dense monoliths (residual porosity ca. 0.5%).The present study emphasizes the potential of the polymer processing technique for the fabrication of near stoichiometric and dense SiC monoliths, which might be used for structural applications in harsh conditions.     

Improved mechanical strength and thermal resistance of porous SiC ceramics with gradient pore sizes

Thermal insulation applications of porous SiC ceramics require low thermal conductivity and high mechanical strength. However, low thermal conductivity and high mechanical strength possess a trade-off relationship, because improving the mechanical strength requires decreasing the porosity, which increases the thermal conductivity. In this study, we established a new strategy for improving both the mechanical strengths and thermal resistances of porous SiC ceramics with micron-sized pores by applying a double-layer coating with successively decreasing pore sizes (submicron- and nano-sized pores). This resulted in a unique gradient pore structure. The double-layer coating increased the flexural strengths and decreased the thermal conductivities of the porous SiC ceramics by 24–70 % and 29–49 % depending on the porosity (48–62 %), improving both their mechanical strengths and thermal resistances. This strategy may be applicable to other porous ceramics for thermal insulation applications.     

Effect of bentonite addition on fabrication of reticulated porous SiC ceramics for liquid metal infiltration

SiC with different particles and a clay mineral bentonite (montmorillonite) were mixed in water to prepare ceramic slurry. The slurry was then infiltrated high porous polyurethane sponge. Excess slurry was squeezed out to adjust ceramic rate in the infiltrated body. The pore walls were coated with ceramic mix after the infiltrated body was dried. The polyurethane containing SiC particles and bentonite was fired in a box furnace to burn out the polyurethane from the body at 500 °C for 30 min. The remaining porous ceramic bodies were sintered at elevated temperatures to give strength. SiC particles with bentonite surface coating took polyurethane pore forms after firing the sponge. Bentonite was both used as binder for ceramic slurry at room temperatures and the sintering additives at elevated temperatures. Therefore, increasing bentonite addition gives higher strength to the resulting ceramic performs.     

Fabrication of wood-like porous silicon carbide ceramics without templates

The porous silicon carbide ceramics with wood-like structure have been fabricated via high temperature recrystallization process by mimicking the formation mechanism of the cellular structure of woods. Silicon carbide decomposes to produce the gas mixture of Si, Si₂C and SiC₂ at high temperature, and silicon gas plays a role of a transport medium for carbon and silicon carbide. The directional flow of gas mixture in the porous green body induces the surface ablation, rearrangement and recrystallization of silicon carbide grains, which leads to the formation of the aligned columnar fibrous silicon carbide crystals and tubular pores in the axial direction. The orientation degree of silicon carbide crystals and pores in the axial direction strongly depends on the temperature and furnace pressure such as it increases with increasing temperature while it decreases with increasing furnace pressure.     

Achieving high permeability of in-situ formed lightweight Cf/SiC(rGO)px/SiC porous ceramics with improved interfacial compatibility for transpiration cooling

Making lightweight porous ceramics with excellent permeability applied for transpiration cooling is still challenging. Herein, an ingenious fabrication method is proposed to successfully prepare C_f/SiC(rGO)_px/SiC porous ceramics possessing low density, high permeability and satisfactory mechanical properties. The introduction of carbon fibers for constructing channels and SiC(rGO)_p with three-dimensional (3D) honeycomb cellular net-like structure, could effectively decrease density and improve porosity. Meanwhile, self-supporting porous skeleton, high open porosity and uniform pores distribution contribute to brilliant permeability of the products. Good interfacial compatibility among SiC(rGO)_p, carbon fibers and β-SiC/SiOxCy/C_free matrix, as well as toughening effects of carbon fibers are beneficial for enhancing fracture toughness and compressive strength. Particularly, C_f/SiC(rGO)_p0.6/SiC porous ceramics exhibit low density (1.12 g·cm^?3), low linear shrinkage (3.22%), especially high permeability (1.36 ×10^?7 mm²), satisfactory fracture toughness (1.77 MPa·m^1/2), excellent hardness (3.88 GPa) and compressive strength (6.41 MPa), focusing on potential applications as coolant medium in transpiration cooling.