Strong effect of atmosphere on the microstructure and microwave absorption properties of porous SiC ceramics

Excellent microwave absorption properties of porous SiC ceramics were successfully synthesized using SiC/camphene slurries with various polycarbosilane (PCS) contents related to the SiC powder. The compositions of the nanowires (NWs) growth in the pore channels of porous SiC ceramics strongly depended on the pyrolysis atmosphere, with N₂-generating Si₃N₄ NWs and Ar SiC NWs. With the increase of PCS content, the minimum reflection coefficient (RC) of porous SiC ceramics decreased from ?7.6 dB to ?67.4 dB in Ar and from ?10.9 dB to ?24.7 dB in N₂, respectively. The effective absorption bandwidth (EAB) of porous SiC ceramics could be up to 8.1 GHz in Ar and 4.5 GHz in N₂. The enhanced microwave absorption properties of porous SiC ceramics could be attributed to the formation of SiC nano-crystalline, nanosized carbon and the NWs, which would increase the amount of boundaries and defects, leading to the electronic dipole polarization and interfacial scattering.     

Processing,properties and microstructure of SiC foam derived from epoxy-modified polycarbosilane

SiC foams having controlled porosity were fabricated using epoxy modified polycarbosilane (EMPCS). The EMPCS was synthesized by refluxing adequate amount of epoxy and polycarbosilane (PCS) in THF solution at 150 °C. The EMPCS having epoxy content of 0%, 10% and 20% by weight were termed as PCS, 10EMPCS and 20EMPCS respectively. Thermal foaming of the EMPCS was carried out at 1000 °C under inert atmosphere followed by ceramization at 1200, 1400 and 1600 °C under vacuum. The cell size of the ceramized SiC foam was found to be varying between 100 and 700 µm. The ceramized SiC foams were characterized for their density, porosity and compressive strength. Total porosity was found to be 81.8 ± 3.9, 87 ± 4.1 and 90.6 ± 4.6% for the PCS, 10EMPCS and 20EMPCS based SiC foams while their bulk densities were found to be 0.6 ± 0.03, 0.4 ± 0.02 and 0.3 ± 0.01 g/cc respectively. Compressive strength was found to be the highest for the SiC foams ceramized at 1600 °C for all the types of EMPCS. The compressive strength of the 10EMPCS is found to be 2.2 ± 0.2 MPa, 2.5 ± 0.2 MPa and 3.8 ± 0.3 MPa for the foams pyrolyzed at 1200 °C, 1400 °C and 1600 °C respectively while the strength was 1.9 ± 0.1 MPa, 2.1 ± 0.2 MPa and 2.9 ± 0.2 MPa for the 20EMPCS based SiC. The 20EMPCS based SiC foam of thickness 10 mm was exposed to oxy-acetylene flame for 120 s, back face temperature was found to be around 300 °C. Microstructure and phase analysis was carried out to understand the effect of epoxy content and ceramization temperature on physical, mechanical and thermal properties of different types of the SiC foams.     

Structure and mechanical properties of porous silicon oxycarbide ceramics derived from silicone resin with different filler content

Porous silicon oxycarbide ceramics were obtained through pyrolysis of a new silicone resin filled with its pyrolyzed SiOC powders via a simple self-blowing process. The effects of filler content on the porosity, compressive strength and microstructure of the porous ceramics were investigated. The porosity (total and open) increased firstly and then decreased with the filler content increasing. It was possible to control the total and open porosity of porous ceramics within a range of 66.1–88.2% and 42.7–72.5% respectively, by adjusting the filler content from 0 vol% to 30 vol% while keeping the heating rate fixed at 0.5 °C/min. The compressive strength decreased firstly and then increased with the increasing filler content, and the average compressive strength of the porous ceramics was in the range of 1.1–3.4 MPa. Micrographs indicated that the porous ceramics with the filler content less than 20 vol% had a well-defined open-cell and regular pore structure.     

Design of polymer-derived SiC for nuclear applications from the perspective of heterogeneous interfaces

Polymer-derived SiC ceramics have been increasingly used in the field of nuclear energy. Herein, we synthetized polymer-derived SiCs with varying SiC/C heterogeneous interfacial properties by pyrolyzing the ceramics at different temperatures. Subsequently, we studied the effect of these interfacial properties on the irradiation behavior (i.e., volume swelling, amorphization, and mechanical properties) of the SiC ceramics. In the case of crystalline ceramics (pyrolyzed at 1150–1500 °C), the presence of a nano-crystalline graphite (NC-G) phase with sp³/sp² hybridization ratios of 0.40–1.27 further enhanced the swelling resistance of nano-SiC by increasing the defect trapping capability of the interfaces. In contrast, amorphous ceramics (pyrolyzed at 900–1100 °C) showed low penetration depths and superior stabilities upon irradiation. These strong ion cascade blocking characteristics may result from the atomic short-range order of these materials. This approach allows optimum design of polymer-derived SiC with superior swelling resistance and stability under room-temperature irradiation.     

Effects of polycarbosilane infiltration processes on the microstructure and mechanical properties of 3D-Cf/SiC composites

Three-dimensional braided carbon fiber-reinforced silicon carbide (3D-C_f/SiC) composites were prepared through eight cycles of infiltration of polycarbosilane (PCS)/divinylbenzene (DVB) and subsequent pyrolysis under an inert atmosphere. The effects of infiltration processes on the microstructure and mechanical properties of the C_f/SiC composites were investigated. The results showed that increasing temperature could reduce the viscosity of the PCS/DVB solution, which was propitious to the infiltration processes. The density and flexural strength of 3D-C_f/SiC composites fabricated with vacuum infiltration were 1.794 g cm⁻³ and 557 MPa, respectively. Compared to vacuum infiltration, heating and pressure infiltration could improve the infiltration efficiency so that the composites exhibited higher density and flexural strength, i.e., 1.944 g cm⁻³ and 662 MPa. When tested at 1650 °C and 1800 °C in vacuum, the flexural strength reached 647 MPa and 602 MPa, respectively.     

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.     

Effects of inert filler addition on the structure and properties of porous SiOC ceramics derived from silicone resin

Porous SiOC ceramics were obtained from a new self-blowing precursor silicone resin DC217, by pyrolysis at 1200 °C in argon. Silicon carbide powders were incorporated into the silicone resin as inert fillers. The effects of the mean particle size of SiC fillers on the porosity, compressive strength and microstructure of the porous ceramics were investigated. With the mean particle size of SiC powders increasing from 5 μm to 10 μm, the porosity (total and open) of the porous ceramic increased and the compressive strength decreased. However, the porosity, compressive strength and cell morphology of the porous ceramics showed no evident changes when the mean particle size of fillers increased from 10 μm to 15 μm. Micrographs indicated that, when the mean particle size of fillers exceeded 5 μm, the porous ceramics could have a well-defined and regular pore structure. Furthermore, comparing with the porous ceramics which fabricated under the same condition with the SiOC powders as fillers, the cell morphology was similar. But the compressive strength and the oxidation resistance of the porous ceramics with SiC powders as fillers were much better.     

Microstructural characterization using orientation imaging microscopy of cellular Si/SiC ceramics synthesized by replication of Indian dicotyledonous plants

Woods from three dicotyledonous plants of local origin (mango Mangifera indica), jackfruit (Artocarpus integrifolia) and teak (Tectona grandis) were transformed by pyrolysis into carbonaceous preforms and subsequently converted into cellular Si/SiC ceramics by liquid Si-infiltration and reaction. The pyrolyzed mango, jackfruit and teak were characterized in terms of pyrolysis weight loss, shrinkages, bulk density and microstructures. The Si-infiltrated pyrolyzed woods were found to have densities and porosities in the range of 2.46–2.60 gm cm⁻³ and 1.5–3.6 vol.% respectively. SEM imaging confirmed the preservation of microcellular tissue anatomy of the precursor wood structure in the morphologies of final ceramics. The end ceramics were investigated for the phases present and for crystallographic microtexture. A combination of XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffraction) and OIM (orientation imaging microscopy) was used to establish the presence and the relative locations of silicon (Si), silicon carbide (SiC) and graphite (C). Fine SiC grains did typically surround coarse crystals of Si – the latter had significant presence of Σ3 twin boundaries. Graphite was primarily present in the regions containing SiC and was more textured than the SiC. Distinct orientation relationship could be established between the graphite crystals and the Si grains containing them.     

Preparation and characterization of mesoporous silicon oxycarbide ceramics without free carbon from polysiloxane

Mesoporous silicon oxycarbide ceramics without free carbon were prepared by pyrolysis of cross-linked polysiloxane at different temperatures (1300–1450 °C) followed by post treatments. The post treatments comprised two steps (HF etching and oxidation at 650 °C in air). The sample pyrolyzed at 1300 °C after post treatments exhibits the largest specific surface area (SSA) reaching up to 204 m²/g and the biggest total pore volume (0.58 cm³/g) with an average pore size of 11.4 nm. Increasing pyrolysis temperature will lead a quick decline of SSA and total pore volume. The thermal stability of pore structure of the sample pyrolyzed at 1300 °C with post treatments was investigated in air. The SSA and total pore volume almost keeps the same up to 750 °C, and subsequently decreases with a high speed. The most possible reason is the pores are severely closed by viscous flow of SiO₂ produced from SiC nanocrystallites.     

Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide ceramics

The influence of silicon carbide (SiC) particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics was investigated. ZrB₂-based ceramics containing 30 vol.% SiC particles were prepared from four different α-SiC precursor powders with average particle sizes ranging from 0.45 to 10 μm. Examination of the dense ceramics showed that smaller starting SiC particle sizes led to improved densification, finer grain sizes, and higher strength. For example, ceramics prepared from SiC with the particle size of 10 μm had a strength of 389 MPa, but the strength increased to 909 MPa for ceramics prepared from SiC with a starting particle size of 0.45 μm. Analysis indicates that SiC particle size controls the strength of ZrB₂–SiC.     

Development of SiC–SiC joint by reaction bonding method using SiC/C tapes as the interlayer

SiC/C tapes with different compositions and thicknesses were used to join pressureless sintered silicon carbide ceramics by reaction bonding method. The microstructure of the joints and the influences of joint thickness and residual silicon content in joint layer on the 4-point flexural strength of as joined SiC ceramics have been investigated. Specimens with high flexural strength can be achieved through the control of the composition and the thickness of the joint layer. The highest flexural strength of the joined specimens with the joint thickness of 13 μm can reach 346 ± 35 MPa and 439 ± 31 MPa at room temperature and 1250 °C, respectively. The microstructure development and the reaction bonding mechanism were also studied.     

Fabrication of biomorphic SiC composites using wood preforms with different structures

Biomorphic SiC composites were fabricated from wood, including high-density compressed cedar, high-density fiberboard (HDF) and low-density paulownia followed by the fabrication of a preform and liquid silicon infiltration (LSI) process. The degree of molten silicon infiltration was strongly dependent on the cell wall thickness and pore size of the carbon preform. The mechanical properties of the biomorphic SiC composites were characterized by compressive tests at room temperature, 1000 °C and 1200 °C, and the relationship between the mechanical properties and the microstructural characteristics was analyzed. The compressive strength of the biomorphic composites was found to be strongly dependent on their bulk density and decreased as the test temperature increased to 1200 °C. Strength reduction in the biomorphic SiC composites occurred due to the deformation of the remaining Si at elevated temperatures under ambient atmospheric conditions.     

Low-temperature preparation of Si3N4 whiskers bonded/reinforced SiC porous ceramics via foam-gelcasting combined with catalytic nitridation

Porous α-Si₃N₄ whiskers bonded/reinforced SiC (Si₃N_4(w)/SiC) ceramics were successfully prepared at as low as 1473 K for 2 h, via a combined foam-gelcasting and catalytic nitridation route using commercial Si and SiC powders containing some Fe impurity as the main raw materials. Small pores (0.03–5 μm) left by the packing of raw material particles and interlocking of in-situ formed Si₃N₄ whiskers coexisted with large ones (8–400 μm) resultant mainly from the foaming process. The impurity Fe from the raw materials Si and SiC acted as an internal catalyst, accelerating the nitridation of Si by increasing the bond length and weakening the bond strength in the N₂ molecules adsorbed on it. As-prepared Si₃N_4(w)/SiC porous ceramics contained 71.53% porosity and had flexural and compressive strengths of 5.60 ± 0.69 MPa and 12.37 ± 1.05 MPa, respectively.     

Liquid poly(silylacetylene)siloxane resin as a novel precursor of silicon carbide and silicon oxycarbide ceramics

Liquid preceramic poly(silylacetylene)siloxane resin was synthesized via a two-step protocol including organometallic condensation and hydrolysis reactions. The preceramic resin was well soluble in acetone, toluene, and tetrahydrofuran (THF), etc. By thermal cure at 180–250 °C a hard monolithic solid was formed through radical polymerization of secondary ethynyl groups. The poly(silylacetylene)siloxane resin was processed easily to various nonporous shapes to silicon carbide (SiC) and silicon oxycarbide (SiCO). SiCO ceramic was obtained at a yield of >75% by pressureless pyrolysis at 900–1200 °C; while SiC ceramic was obtained at 1500 °C at a yield of ≈67%. The molar ratio of Si/C in the SiC was found at 1:1.1–1:3, based on ICP-MS elemental analysis. X-ray diffraction (XRD) results revealed the typical β-SiC structure in the poly(silylacetylene)siloxane derived SiC ceramics. The SiC ceramics exhibited high thermo-oxidation resistance at elevated temperatures in air atmosphere.     

Process-tolerant pressureless-sintered silicon carbide ceramics with alumina-yttria-calcia-strontia

Process-tolerant SiC ceramics were prepared by pressureless sintering at 1850–1950 °C for 2 h in an argon atmosphere with a new quaternary additive (Al₂O₃-Y₂O₃-CaO-SrO). The SiC ceramics can be sintered to a > 94% theoretical density at 1800–1950 °C by pressureless sintering. Toughened microstructures consisting of relatively large platelet grains and small equiaxed grains were obtained when SiC ceramics were sintered at 1850–1950 °C. The presently fabricated SiC ceramics showed little variability of the microstructure and mechanical properties with sintering within the temperature range of 1850–1950 °C, demonstrating process-tolerant behavior. The thermal conductivity of the SiC ceramics increased with increasing sintering temperature from 1800 °C to 1900 °C due to decreases of the lattice oxygen content of the SiC grains and residual porosity. The flexural strength, fracture toughness, and thermal conductivity of the SiC ceramics sintered at 1850–1950 °C were in the ranges of 444–457 MPa, 4.9–5.0 MPa m^1/2, and 76–82 Wm^?1 K^?1, respectively.     

Improvement of the mechanical properties of SiC reticulated porous ceramics with optimized three-layered struts for porous media combustion

Silicon carbide reticulated porous ceramics (SiC RPCs) with three-layered struts were fabricated by polymer replica method, followed by infiltrating alumina slurries containing silicon (slurry-Si) and andalusite (slurry-An), respectively. The effects of composition of infiltration slurries on the strut structure, mechanical properties and thermal shock resistance of SiC RPCs were investigated. The results showed that the SiC RPCs infiltrated with slurry-Si and slurry-An exhibited better mechanical properties and thermal shock resistance in comparison with those of alumina slurry infiltration, even obtained the considerable strength at 1300 °C. In slurry-Si, silicon was oxidized into SiO₂ in the temperature range from 1300 °C to 1400 °C and it reacted with Al₂O₃ into mullite phase at 1450 °C. Meantime, the addition of silicon in slurry-Si could reduce SiC oxidation of SiC RPCs during firing process in contrast with alumina slurry. With regard to slurry-An, andalusite started to transform into mullite phase at 1300 °C and the secondary mullitization occurred at 1450 °C. The enhanced mechanical properties and thermal shock resistance of SiC RPCs infiltrated alumina slurries containing silicon and andalusite were attributed to the optimized microstructure and the triangular zone (inner layer of strut) with mullite bonded corundum via reaction sintering. In addition, the generation of residual compressive stress together with better interlocked needle-like mullite led to the crack-deflection in SiC skeleton, thus improving the thermal shock resistance of obtained SiC RPCs.     

In-situ synthesis and textural evolution of the novel carbonaceous SiC/mullite aerogel via polymer-derived ceramics route

A novel carbonaceous SiC/mullite composite aerogel is derived from catechol-formaldehyde/silica/alumina hybrid aerogel (CF/SiO₂/AlOOH) via polymer-derived ceramics route (PDCR). The effects of the reactants concentrations on the physicochemical properties of the carbonaceous SiO₂/Al₂O₃ aerogel and SiC/mullite aerogel are investigated. The mechanism of the textural and structural evolution for the novel carbonaceous SiC/mullite is further discussed based on the experimental results. Smaller reactants concentration is favorable to formation of mullite. Reactants concentration of 25% is selected as the optimal condition in considering of the mullite formation and bulk densities of the preceramic aerogels. Spherical large silica particles are also produced during heat treatment, and amorphous silica is remained after this reaction. With further heat treatment at 1400 °C, silicon carbide and mullite coexist in the aerogel matrix. The mullite addition decreases the temperature of SiC formation, when compared with the conventional methods. However, after heat treatment at 1450 °C, the amount of mullite begins to decrease due to the further reaction between carbon and mullite, forming more silicon carbide and alumina. The carbonaceous SiC/mullite can be transferred to SiC/mullite binary aerogel after carbon combustion under air atmosphere. The carbonaceous SiC/mullite has a composition of SiC (31%), mullite (19.1%), SiO₂ (14.4%), and carbon (35%). It also possesses a 6.531 nm average pore diameter, high surface area (69.61 m²/g), and BJH desorption pore volume (0.1744 cm³/g). The oxidation resistance of the carbonaceous SiC/mullite is improved for 85 °C when compared with the carbon based aerogel.     

Preparation of reaction-bonded silicon carbide with well controlled structure by tape casting method

Tape casting is a reliable and cost effective method for producing thin ceramic sheets with uniform and tailored microstructures, especially for multilayered composite materials. In this paper, SiC/C tapes were prepared by tape casting method. After lamination and binder removal, porous preforms with homogeneous microstructure and narrow pore sizes distribution were developed. Then, dense reaction bonded SiC ceramics (RBSCs) were obtained by silicon infiltration into these preforms. The highest bending strength of the RBSCs can reach 410 ± 14 MPa. Moreover, impregnation of phenolic resin into the porous preforms before silicon infiltration could help to develop RBSCs with lower residual silicon content and higher flexural strength which can be as high as 598 ± 112 MPa.     

An advanced method to manufacture hierarchically structured carbide-derived carbon monoliths

The preparation of carbide-derived carbon (CDC) monoliths with a hierarchically structure in the nm and μm range is presented. Basis is the manufacturing of porous cellular SiC ceramics based on a biomorphous approach with μm porosity and subsequent conformal conversion to CDC by reactive extraction with chlorine. The SiC ceramics can be sintered at low temperatures and short times (1500 °C, 2 h) compared to classical preparation methods. The SiC ceramics show a macro pore volume (1–10 μm channel size) of 0.56 ml g⁻¹, which corresponds to 1.5 ml g⁻¹ in the resulting CDC. The final carbon material exhibits an additional nano pore volume of 0.525 ml g⁻¹ with a mean slit pore size of 0.86 nm. Mechanical stabilities of the highly porous CDC are excellent (bending strength 2.1 ± 0.2 MPa, corrected Weibull modulus 8.7, characteristic strength 2.2 MPa and Youngs modulus 10.0 ± 0.5 GPa). The reactive extraction of the carbide monoliths shows very high reaction rates, approx. two dimensions faster (95×) compared to non-porous samples. Thus the manufacturing of the structured carbide and CDC can be performed at lower costs.     

Porous SiC/SiCN composite ceramics fabricated by foaming and reaction sintering

Porous SiC/SiCN composite ceramics with heterogeneous pore structure and rod-like SiCN grains were fabricated by foaming and reaction sintering. The mixture slurry containing SiC and silicon as raw materials, cornstarch as binder, Y₂O₃ as sintering additive and an electrosteric dispersant was stirred with foams derived from pre-foaming using foaming agent. The casted green body was sintered at 1650 °C under nitrogen atmosphere. The results demonstrated that the porous SiC/SiCN ceramics exhibited hierarchical vias ranging from 1 μm to 1 mm and the rod-like crystalline SiCN grains generated in the SiC matrix.