SiOC modified carbon-bonded carbon fiber composite with SiC nanowires enhanced interfibrous junctions

Carbon-bonded carbon fiber (CBCF) composites are promising lightweight and high efficient thermal insulators to be applied in aerospace area, but their practical applications are usually restricted by the low mechanical performance and poor oxidation resistance. To overcome these drawbacks, many efforts have been made in the fabrication of ceramic coated CBCF composites. However, the densities of these modified composites are usually very high, which would result in the reduction in their thermal insulation performance. Herein, we prepared a CBCF composite with SiC nanowires enhanced interfibrous junctions and SiOC ceramic coated carbon fibers (SiCNWs-SiOC-CBCF). Similar to CBCF, the SiCNWs-SiOC-CBCF exhibits a low density of 0.35 g/cm³ and an anisotropic and highly porous architecture. The SiCNWs-SiOC-CBCF possesses a compressive strength of 3.8 MPa and a compression modulus of 195.7 MPa in the X (or Y) direction, ~26.7% and 150% higher than those of CBCF respectively. It can also suffer from an isothermal treatment in air at 900°C for 120 minutes. The combination of these properties makes the SiCNWs-SiOC-CBCF a good candidate for thermal insulator to be applied in extreme conditions.     

Enhanced microwave-absorption properties of polymer-derived SiC/SiOC composite ceramics modified by carbon nanowires

Novel microwave-absorbing SiOC composite ceramics with dual nanowires (carbon nanowires (CNWs) and SiC nanowires) with high performances were fabricated by using the polymer-derivation method and heat treatment in Ar atmosphere. The introduction of CNWs in the amorphous SiOC ceramics promotes the ceramic crystallization into SiC nanoparticles and SiC nanowires at lower annealing temperatures, which leads to multi-phases and multiple nano heterogeneous interfaces. The distinctive architectures largely increase the interfacial and dipole polarizations of the composite ceramics. The CNWs/SiC/SiOC composite ceramics exhibit excellent microwave-absorption properties in the Ku band (12.4–18 GHz). The minimum reflection coefficient (RC) is -24.5 dB at a thickness of 1.8 mm, while the maximum effective absorption bandwidth (EAB, the corresponding frequency band in which RC is smaller than -10 dB) is 4.8 GHz at a thickness of 1.9 mm, which make the CNWs/SiC/SiOC composite ceramics promising electromagnetic-wave-absorbing materials.     

Lightweight and resilient SiOC/SiC foam with efficient electromagnetic wave absorption and high-temperature stability

Integrating multiple functions such as high electromagnetic (EM) wave absorption, thermal insulation, and resilience into one material is critical, especially for applications in harsh environment. SiC ceramic has received considerable attention as high-temperature wave absorber, but its applications are limited by common wave absorption performance and brittleness of ceramics. Here by incorporating SiO₂ with SiC in a unique three-dimensional network structure, SiOC/SiC foam consisting of abundant SiOC thin flakes interconnected by numerous long interweaving SiC nanowires have been prepared. The foam shows high EM wave absorption with minimum reflection loss of −30.23 dB, broad effective absorption bandwidth of 5.4 GHz, and a nearly complete compressive resilience from 10% strain. Besides, the foam displays high-temperature resistance up to 1400°C in air and good thermal insulation performance. Such multifunctional material is promising for applications in advanced aerospace industry under extreme conditions.     

SiC纳米线增强反应烧结碳化硅陶瓷的性能研究

以单晶SiC纳米线作为增强体,碳化硅-碳为陶瓷基体,在1550℃下,采用反应烧结制备碳化硅基陶瓷复合材料(SiCnf/SiC).结合X射线衍射、万能试验机和扫描电镜等检测和分析,研究SiC纳米线对复合材料的微结构和力学性能的影响.研究表明:与未加入SiC纳米线的反应烧结碳化硅陶瓷相比,添加SiC纳米线的复合陶瓷的抗弯强度和断裂韧性都得到显著的提高,抗弯强度提高了52％,达到320 MPa(SiC纳米线含量为12wt％),断裂韧性提高了40.6％,达到4.5 MPa· m1/2(SiC纳米线含量为15wt％);反应后的SiC纳米线仍然可以保持原有的竹节状结构,且随着SiC纳米线的加入,复合陶瓷的断口可以观察到SiC纳米线拔出现象.但由于SiC纳米线“架桥”的现象,添加过量的纳米线会降低复合陶瓷的密度和限制复合陶瓷力学性能的提高.同时还讨论了SiCnf/SiC的增强机理.     

Synthesis and microwave absorption properties of SiC nanowires reinforced SiOC ceramic

Silicon carbide nanowires (SiC NWs) reinforced SiOC ceramics were fabricated through in situ growth of SiC NWs in SiOC ceramics by pyrolysis of polysiloxane. SiC NWs were in situ formed by the addition of ferrocene, the content of SiC NWs increased with the increases of annealing temperature and ferrocene content. Due to the formation of SiC NWs in the inter-particle pores of SiOC ceramics, the SiOC particles were bridged by SiC NWs, which led to the increase of electrical conductivity. With the increase of SiC NWs content, the real permittivity and the imaginary permittivity increased from 3.63 and 0.14 to 10.72 and 12.17, respectively, and the minimum reflection coefficient decreased from −1.22 dB to −20.01 dB, demonstrating the SiOC ceramics with SiC NWs had a superior microwave-absorbing ability.     

3D printing of PDC-SiOC@SiC twins with high permittivity and electromagnetic interference shielding effectiveness

Effective electromagnetic interference (EMI) shielding requires materials with high permittivity. The current study reports 3D printed polymer-derived SiOC ceramics (PDC) modified with SiC nanowires (SiC_nw) exhibiting both high real and imaginary parts of permittivity within X-band. SEM results indicated that a large number of pores and cracks exist in the SiOC, and twinned SiC_nw were uniformly grown among them along with the existence of graphite microcrystals when the sintering temperature was 1500 ℃. The real part of permittivity ranged from 16.6 to 28.9 while the imaginary part from 31.7 to 34.2 in X-band. The EMI total shielding effectiveness (SE_T) of the ceramics could reach 34.7 dB with absorption loss (SE_A) of 29.3 dB and reflection loss (SE_R) of 5.4 dB. Meanwhile, the 3D printed PDC-SiOC ceramics at 900 ℃ sintering temperature possess certain mechanical properties with the magnitude of compressive strength being 12.57 MPa.     

Polymer‐derived ceramic aerogels as sorbent materials for the removal of organic dyes from aqueous solutions

Polymer‐derived SiC and SiOC aerogels have been synthesized and characterized both from the microstructural point of view and as sorbent materials for removing organic dyes (Methylene Blue, MB, and Rhodamine B, RB) from water solutions. Their adsorbent behavior has been compared with a polymer‐derived SiC foam and a commercial mesoporous silica. The aerogels can efficiently remove MB and RB from water solution and their capacity is higher compared to the SiC foams due to the higher surface area. The SiOC aerogel remains monolithic after the water treatment (allowing for an easy removal without the need of a filtration step) and its maximum capacity for removing MB is 42.2 mg/g, which is higher compared to the studied mesoporous silica and many C‐based porous adsorbents reported in the literature. The reason for this high adsorption capacity has been related to the unique structure of the polymer‐derived SiOC, which consists of an amorphous silicon oxycarbide network and a free carbon phase.     

Processing and characterization of particles reinforced SiOC composites via pyrolysis of polysiloxane with SiC or/and Al fillers

Polysiloxane loaded with SiC as inert filler, and Al as active filler, was pyrolyzed in nitrogen to fabricate SiOC composites, and the processing and properties of the filled SiOC composites were investigated. Adding SiC fillers could reduce the linear shrinkage of filler-free cured polysiloxane in order to obtain monolithic SiC/SiOC composites. The flexural strength of SiC/SiOC composites reached 201.3 MPa at a SiC filler content of 27.6 vol.%. However, SiC/SiOC composites exhibited poor oxidation resistance, thermal shock resistance and high temperature resistance. Al fillers could react with hydrocarbon generated during polysiloxane pyrolysis at 600 °C and N₂ at 800 °C to form Al₄C₃ and AlN, respectively. The volume expansions resulting from these two reactions were in favor of the reduction in linear shrinkage and the improvement in flexural strength of SiC/SiOC composites. The flexural strength of Al-containing SiC/SiOC composites was 1.36 times that of SiC/SiOC composites without Al at an Al filler content of 20 vol.%. The addition of Al fillers remarkably improved the high temperature resistance and oxidation resistance of SiC/SiOC composites, but not thermal shock resistance.     

Microstructural and compositional characterisation of the pyrocarbon interlayer in SiC coated low density carbon/carbon composites

SiC coated carbon bonded carbon fibre (CBCF) composites, a special class of carbon/carbon composites for thermal insulation, were investigated. Successful deposition of SiC requires the CBCF material to be first given a pyrocarbon coating. SiC coating on pyrocarbon coated CBCF was assessed using several analytical techniques. X-ray diffraction identified the coating as β SiC. The fibre orientation in two perpendicular planes was determined using X-ray microtomography, and it was found to be random in one plane whereas there was a preferred orientation in the other plane. A comparison was made between the uncoated and pyrocarbon coated substrates in terms of surface roughness, purity and crystallinity, using white light interferometry, neutron activation analysis/secondary ion mass spectrometry and transmission electron microscopy, respectively. The higher roughness, greater purity and increased levels of crystallinity of pyrocarbon coated CBCF are considered to be responsible for the successful deposition of a SiC coating on this material.     

In-situ pyrolyzed polymethylsilsesquioxane multi-walled carbon nanotubes derived ceramic nanocomposites for electromagnetic wave absorption

Iron acetylacetonate (Fe(acac)₃) modified polymethylsilsesquioxane (PMS), simplified as PMS(Fe), was firstly obtained from PMS and Fe(acac)₃ via the condensation reaction. Multi-walled carbon nanotubes (MWCNTs) were then introduced to fabricate the corresponding MWCNTs/SiC nanocrystals/amorphous SiOC ceramic composites via pyrolyzed process. Owing to the catalytic effect of iron and heterogeneous nucleation promoted by MWCNTs, SiC nanocrystals were separated from SiOC amorphous ceramic matrix under 1400?°C. When the mass fraction of MWCNTs was 9?wt%, the obtained MWCNTs/SiC nanocrystals/amorphous SiOC ceramic composite (C9) demonstrated high microwave-absorbing properties. The minimum reflection loss (RL_min) and effective absorption bandwidth (EBA) of the obtained C9 at X-band (8.2–12.4) reached ?61.8?dB and 2.6?GHz (a thickness of 2.19?mm), respectively. Compared with other polymer-derived ceramics (PDCs), the RL_min was higher and the required thickness was thinner. This excellent microwave-absorbing property was due to the interfacial polarization relaxation generated between nanocrystals (MWCNTs & SiC) and amorphous SiOC, and the formed complete conductive networks inside the ceramic composites.     

Stereolithography-based additive manufacturing of polymer-derived SiOC/SiC ceramic composites

In order to overcome challenges typically encountered during additive manufacturing of ceramics via the polymer precursor route, a novel polymer-derived SiOC/SiC composite system suitable for advanced geometric designs achievable by lithography-based ceramic manufacturing was established. The photoreactive resin system filled with 20 wt% SiC exhibits suitable viscosity characteristics, adequate stability against sedimentation, and a fast photocuring behavior. After printing and pyrolytic conversion, SiC particulates were well-dispersed within the polymer-derived SiOC matrix. A direct comparison with the unfilled polysiloxane-based resin system showed that the addition of particulate SiC increases handleability, reduces shrinkage, and significantly increases critical wall thicknesses up to 5 mm. The biaxial Ball-on-Three-Balls testing methodology yielded a characteristic strength of 325 MPa for SiOC/SiC composites. The results highlight the high potential of particle-filled preceramic polymer systems toward the fabrication of high-performance SiC-based materials by lithography-based additive manufacturing.     

Synthesis of 6H-SiC nanowires on bamboo leaves by carbothermal method

6H silicon carbide (SiC) nanowires were fabricated on bamboo leaves infiltrated with tetraethyl orthosilicate (TEOS) by carbothermal method at 1300–1400 °C. The bamboo leaves were the carbon source and template for the growth of SiC. The TEOS was the silicon source. The crystalline structure, morphology, and the distribution of the prepared SiC were characterized by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. The SiC had a hexagonal 6H- structure with diameter of 60 to 160 nm and length up to tens of microns. The yield of SiC grown on the top surface of the bamboo leaf was higher and had a branched structure. The SiC on the bottom surface showed a bamboo-like structure. The nanowires were mainly 6H phase, however cubic 3C-SiC phase was found on the divisions in the branch structure and the nodes in the bamboo-like structure. The difference in density of SiC nanowires between the two surfaces is proposed to be related to the structural and compositional differences of the two surfaces. TEOS was preferred to attach the hydrophilic top surface, which led to larger amount of SiC. Meanwhile, the Al content inside the bottom surface prohibited the growth of the SiC nanowires. The growth mechanism of the SiC nanowires is also discussed.     

In-situ formation of titanium carbide in carbon-rich silicon oxycarbide ceramic for enhanced thermal stability

Silicon oxycarbide (SiOC) ceramic has attracted great attention as fascinating candidate of high-temperature material, however, its thermal stability is significantly limited by the phase separation at high temperature. Here, a TiC/SiOC ceramic was prepared by pyrolysis of a tetrabutyl titanate modified carbon-rich polysiloxane (TBT/PSO) precursor. The TiC phase is in-situ formed by the carbothermal reaction of TBT-derived amorphous TiO₂ phase with excess free-carbon phase during pyrolysis, and its size and amount increase with the pyrolysis temperature. The SiC phase appears at a higher temperature than the TiC phase and is hindered by the increased Ti content in the TBT/PSO precursor. Thus, the TiC/SiOC ceramic exhibits better thermal stability and crystallization resistance than the TiC-free SiOC ceramic under the thermal treatment (1500 °C) in argon atmosphere. The in-situ formation of metal carbide into the carbon-rich SiOC ceramic would further expand its application at high temperature environments.     

Effect of in situ grown SiC nanowires on microstructure and mechanical properties of C/SiC composites

Hexagonal-shaped SiC nanowires were in situ formed in C/SiC composites with ferrocene as catalyst in the densification process of polymer impregnation and pyrolysis. The effect of SiC nanowires on microstructure and properties of the composites were studied. The results show that the in situ formed SiC nanowires were hexagonal, mostly with diamer of about 250 nm, and grew by the vapor–liquid–solid (VLS) mechanism. The C/SiC composite with nanowires shows higher bulk density and flexural strength than the one with no SiC nanowires, and the high temperature flexural strength behavior of C/SiC composites with SiC nanowires was evaluated.     

Enhanced electromagnetic wave absorption properties of a novel SiC nanowires reinforced SiO2/3Al2O3·2SiO2 porous ceramic

To realize the broad-bandwidth and high-efficiency absorption characteristics, a novel SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ porous ceramic was successfully fabricated by method of precursor infiltration pyrolysis (PIP). Polycarbosilane (PCS) and ferrocene (Fe(C₅H₅)₂) were used as the precursor and catalyst to incorporate SiC nanowires into the SiO₂/3Al₂O₃·2SiO₂ porous ceramic. The curvy SiC nanowires formed three-dimensional (3D) networks with a proper nanometer heterostructure, thereby consuming the microwave energies. The influence of SiC nanowires contents on the microwave absorption properties was investigated. The results indicate that the SiC nanowires contents can be tuned by controlling the PIP cycles, thereby modifying the dielectric properties of as-prepared composite ceramics. The dielectric and electromagnetic wave absorption performances are gradually enhanced with an increasing of SiC nanowires contents. The SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ composite ceramic exhibits excellent electromagnetic wave absorption abilities when the SiC nanowires content is 23.9% (PIP5). The minimum reflection coefficient (RC_min) of the composite ceramic is −30 dB at 10.0 GHz, corresponding to more than 99.9% of the electromagnetic wave consumption. The effective absorption bandwidth (EAB) can cover the frequency ranges of 8.2–12.4 GHz (the entire X-band) at the thickness of 5.0 mm. In general, the novel SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ composite ceramic can be considered as a promising electromagnetic wave absorbing material.     

Effects of pyrocarbon on morphology stability of SiC nanowires at high temperatures

To understand the effect of pyrocarbon (PyC) on the morphology stability of SiC nanowires at high temperatures (1800‐2100°C), a PyC layer was prepared to wrap the 3C‐SiC nanowire by chemical vapor deposition. The results showed that the existence and thickness of PyC layer played a crucial role in stabilizing the structures and morphology of SiC nanowires. The SiC nanowires without PyC layer transformed to platelet‐shaped structures above 1800°C. The SiC nanowires with a ~1.5 μm PyC layer could keep their structures and morphology at 2100°C, while the SiC nanowires with a ~1 μm PyC layer could not maintain their microstructures at this temperature. The stability of SiC nanowires at high temperature might be related to the vapor phase nucleation, thermodynamics phase transformation and the stacking faults (SFs) expansion, which could be limited by the PyC layer. Therefore, preparing a protective PyC layer with an appropriate thickness might be a potential method to extend the practical applications of SiC nanowires at high temperatures.     

Synthesize and crystallization behavior of SiOC/SiC nanocomposites derived from organosilane slurry residue

A route preparing SiOC/SiC nanocomposites directly by pyrolysis of organosilane slurry residue was investigated. Organosilane slurry residue's unique composition, containing both silicon and carbon, offers an intriguing platform for developing advanced ceramic materials. The pyrolysis process is examined comprehensively, revealing the chemical reactions and structural changes leading to SiC crystals formation. The phase evolution at various annealing temperatures was revealed. Crystallization behavior in the process were studied. The results reveal that SiOC matrix was generated at annealed temperature 800°C and SiC nanoparticles were formed at 1300°C. In comparison to phase separation of SiOC, carbothermal reduction of SiO₂ was domain in SiC formation. This research advances the understanding of SiOC/SiC nanocomposites, highlighting the value of repurposing industrial byproducts for sustainable and innovative materials development.     

In-situ TEM study of Kr ion irradiation tolerance of SiFeOC nanocomposite

In this work, ion irradiation of polymer derived SiFeOC nanocomposite was carried out using 1.2 MeV Kr ions at room temperature and 600°C. The starting composite was composed of Fe₃Si, SiC, SiOC, SiO₂, and graphitic C. In-situ TEM investigations show uniform distribution of nano-crystalline Fe₃Si and SiC phases in the amorphous SiOC matrix. During ion irradiation, the SiOC bulk microstructure and interfaces between Fe₃Si or SiC crystallites and the SiOC matrix remain defect-free and demonstrate outstanding ion irradiation resistance. At room temperature, the crystalline domains are stable up to 2 dpa. At 600°C, Fe₃Si crystallites are more stable than SiC; SiC crystallites are stable up to 4 dpa while the Fe₃Si crystallites are stable up to 10 dpa. These crystallites also coalescence and amorphize simultaneously during ion irradiation. The exceptional tolerance to defect formation and irradiation of the SiFeOC nanocomposite provides important guidance to developing irradiation resistant fuels for advanced gas cooled reactors.     

Large-scale synthesis of SiC/PyC core-shell structure nanowires via chemical liquid-vapor deposition

In carbon/carbon (C/C) composites, SiC/PyC core-shell structure nanowires were successfully fabricated via chemical liquid-vapor deposition (CLVD). The influences of heat-treatment temperature on the microstructure and composition of SiC nanowires were studied, and meanwhile the growth mechanism of SiC nanowires was discussed. Additionally, the microstructure and morphology of SiC/PyC core-shell structure nanowires were also investigated. The results displayed that the low heat-treatment temperature could not meet the requirements of SiC nanowires growth, but the too high temperature made the nanowires appear agglomerate easily. Only when the heat-treatment temperature was 1800 °C, SiC nanowires possessed a uniform distribution. The diameter of SiC nanowire was about 300 nm, and there was a SiO₂ layer with the thickness of about 1 nm existing on the surface of SiC nanowire. The growth behavior of SiC nanowire was governed by vapor-solid (V–S) mechanism. After the PyC deposition, SiC/PyC core-shell structure nanowires were constructed, and the nanowires were about 450 nm in diameter. These nanowires displayed a core-shell structure with three layers, which were SiC nanowire core, SiO₂ interlayer and PyC shell, respectively. Meanwhile, SiC/PyC core-shell structure nanowires connected the matrices with each other, and the core-shell structure nanowires generated a stable network.     

Process and Mechanical Properties of in Situ Silicon Carbide-Nanowire-Reinforced Chemical Vapor Infiltrated Silicon Carbide/Silicon Carbide Composite

A SiC nanowire/Tyranno-SA fiber-reinforced SiC/SiC composite was fabricated via simple in situ growth of SiC nanowires directly in the fibrous preform before CVI matrix densification; the purpose of the SiC nanowires was to markedly improve strength and toughness. The nanowires consisted of single-crystal β-phase SiC with a uniform ∼5 nm carbon shell; the nanowires had diameters of several tens to one hundred nanometers. The volume fraction of the nanowires in the fabricated composite was ∼5%. However, the composite did not show significant increase in strength and toughness, likely because of strong bonding between the nanowires and the matrix caused by the very thin carbon coating on the nanowires. Little debonding and pullout of SiC nanowires from the matrix were observed at the fracture surfaces of the composite.