Facile preparation of ultralight polymer-derived SiOCN ceramic aerogels with hierarchical pore structure

SiOCN ceramic aerogels with lightweight, high surface areas, and macro-meso pores have been synthesized by a facile method combining freeze-drying technique and polymer-derived ceramic route. The wet gels are synthesized via the hydrosilylation reaction between polysilazane and divinylbenzene with cyclohexane as solvent. The solvent is then removed by a freeze-drying process to form pre-ceramic aerogels. The SiOCN ceramic aerogels are finally obtained by pyrolyzing the pre-ceramic aerogels at 1000°C in ultrahigh purity N₂. The thermogravimetric and mass spectrometry system (TG/DSC-MS) is used to investigate the polymer-to-ceramic conversion process during pyrolysis. The phase composition, structure, and morphology of the SiOCN ceramic aerogels are investigated by XRD, FT-IR, XPS, and SEM. The results show that SiOCN ceramic aerogels are composed of amorphous matrix phase and “free carbon” phase. The SiOCN aerogels possess three-dimensional (3D) network porous structure with low density (0.19 g/cm³), high specific surface area (134 m²/g), large pore volume (0.49 cm³/g), and hierarchical pore structures of both macro and meso pores. The formation mechanism and evolution process of SiOCN ceramic aerogels are discussed.     

Synthesis,structure, and properties of polymer-derived,metal-reinforced boron carbide cermet composites

We report on a novel polymer-derived synthesis approach that yields boron carbide monoliths and metal-reinforced B₄C cermets. This single-step approach relies on a preceramic powder blend of boron and an acetylenic resin with a high char yield. At low temperatures below 1500°C and without applied pressures, preceramic precursor reaction bond together and form nanocrystalline refractory B₄C matrices. Resulting near net shape boron, carbide monoliths exhibit small crystal grain sizes, maintain chemical purity, and exhibit morphological homogeneity. We reinforce the refractory carbide with five different metals and demonstrate the influence of each on the density, hardness, oxidation stability, and electronic conductivity of resulting cermet composites. We assess the optimal synthesis and reinforcement strategies that tailor these nanostructured materials for inexpensive and high-performing engineering applications.     

Synthesis and thermal shock evaluation of porous SiC ceramic foams for solar thermal applications

Reticulated porous ceramics with structural features spanning across multiple length scales are emerging as the primary media in a variety of demanding mass and heat transfer applications, most notably solar-assisted synthetic fuel processing. In this study, we focus on engineering of the open pore silicon carbide (SiC)-based foams in such catalytic applications. We evaluate the mechanical integrity and thermal stability of these porous structures. X-ray tomography analyses of the 3D structures reveal the presence of dual pore size distribution different by up to an order of magnitude in length scale. We further study the effect of thermal shock—induced via water quenching—on the SiC structures and we conclude that the mechanical properties of the ceramic foams are significantly reduced after thermal stress. Comparison of SEM micrographs—before and after thermal shock—reveals that needle-like features appear inside the foam matrix. These elongated defects may be responsible for structural and mechanical weakening.     

Complex impedance spectra of polymer-derived SiC annealed at ultrahigh temperature

This study reports the complex impedance and alternative current conductivity of polymer-derived ceramic SiC (PDC-SiC) annealed at ultrahigh temperatures. The PDC-SiC shows an inductive response when annealed at temperatures of 1700°C-1900°C due to the percolation of turbostratic carbon. The material returns to a capacitive response at an annealing temperature of 2000°C due to the dissolution of carbon into the SiC lattice. The electrical resistance of the carbon phase decreases with the increase in annealing temperature. These results provide new insights into the effects of processing temperature on microstructure evolution and electrical and dielectric property development of the PDC-SiC ceramic system.     

二氧化硅气凝胶复合隔热材料研究进展

二氧化硅气凝胶具有高孔隙率、低热导率等特点,使其成为新型超级隔热材料。然而,二氧化硅气凝胶的柔韧性、整体性差,并且常温干燥制备的气凝胶在高温时热导率迅速上升,这些都大大限制了二氧化硅气凝胶的应用。近些年,通过原位溶胶-凝胶法和模压成型法制备得到的二氧化硅气凝胶复合隔热材料,在一定程度上提高了其韧性、整体性和高温隔热性能,使得二氧化硅气凝胶作为单独块体隔热材料成为可能。本文阐述了二氧化硅气凝胶隔热材料的隔热机理,综述了近年来抗辐射型、纤维增强型和聚合物增强型二氧化硅气凝胶复合隔热材料的研究现状,最后讨论了该领域今后研究趋势。     

Stress rupture of SiC/SiC composite tubes under high-temperature steam

SiC-fiber–reinforced SiC matrix composite cladding for light water reactor fuel elements must withstand high-temperature steam oxidation in a loss-of-coolant accident scenario (LOCA). Current composite designs include an outer monolithic SiC layer, in part, to increase steam oxidation resistance. However, it is not clear how such a structure would behave under high-temperature steam in the case when the monolithic layer cracks and carbon interphases and SiC fibers are exposed to the environment. To fill this knowledge gap, stress-rupture tests of prototypic SiC composite cladding at 1000°C under steam and inert environments were conducted. The applied stress was ∼120 MPa, which was beyond the initial cracking stress. The failure lifetime under steam was 400–1300 s, while 75% of the composite specimens did not fail after 3 h of total exposure under inert gases. Microstructural observations suggest that steam oxidation activated slow crack growth in the fibers, which led to failure of the composite. The results from this study suggest that stress rupture in steam environments could be a limiting factor of the cladding under reactor LOCA conditions.     

Opacifier embedded and fiber reinforced alumina-based aerogel composites for ultra-high temperature thermal insulation

A novel method was developed to uniformly disperse sub-micron TiO₂ opacifier into fiber reinforcements using agar and silica as binders via freeze drying. TiO₂ opacifier/ fiber/ alumina-based aerogel ternary (TFA) composites with high strength and excellent high-temperature thermal insulation were successfully prepared by sol-gel route, impregnation process and supercritical fluid drying. The microstructure, mechanical and thermal insulation properties of TFA composites were investigated comprehensively. The results show that the mechanical property of TFA composites can be significantly enhanced by mullite fiber felt and the incorporation of SiO₂ binder. The effect of TiO₂ opacifier on the high-temperature thermal conductivity was studied by adjusting the content of TiO₂ from 0 to 15 wt%. The obtained TFA composites exhibit high Young's modulus of up to 3.58 MPa and low high-temperature thermal conductivities of 0.129 W/m·K at 800 °C and 0.168 W/m·K at 1000 °C, respectively. The mechanism of heat transfer in TFA composites at high-temperature was also analyzed.     

The effects of adding nano-alumina filler on the properties of polymer-derived SiC coating

In this paper, SiC coating was prepared using the polymer-derived ceramic method; then the effect of nano-alumina as a filler material was studied. First of all, polycarbosilane(PCS) was dissolved in xylene; after that, different amounts of nano-alumina particles were added to the solution. The coating was deposited on the alumina substrate using the dip-coating method; this was followed by sintering at 1200℃. The phase content and microstructure of the samples were studied by X-ray diffraction and scanning electron microscope methods, respectively. Nanohardness, Young's modulus, and coating adhesion were investigated by a nanoindentation method. The sheet resistance was evaluated using the four-point probe technique; also, the wear resistance of the coating was studied by applying the pin-on-disk method. It was found that the addition of the nano-alumina filler up to 20 wt% drastically improved the adhesion and wear resistance of the SiC coating.     

Formation of Ti3SiC2 interphase coating on SiCf/SiC composite by electrophoretic deposition

To improve the oxidation resistance of SiC composites at high temperature, the feasibility of using Ti₃SiC₂ coated via electrophoretic deposition (EPD) as a SiC fiber reinforced SiC composite interphase material was studied. Through fiber pullout, Ti₃SiC₂, due to its lamellar structure, has the possibility of improving the fracture toughness of SiC_f/SiC composites. In this study, Ti₃SiC₂ coating was produced by EPD on SiC fiber; using Ti₃SiC₂‐coated SiC fabric, SiC_f/SiC composite was fabricated by hot pressing. Platelet Ti₃SiC₂ powder pulverized into nanoparticles through high‐energy wet ball milling was uniformly coated on the SiC fiber in a direction in which the basal plane of the particles was parallel to the fiber. In a 3‐point bending test of the SiC_f/SiC composite using Ti₃SiC₂‐coated SiC fabric, the SiC_f/SiC composite exhibited brittle fracture behavior, but an abrupt slope change in the strength‐displacement curve was observed during loading due to the Ti₃SiC₂ interphase. On the fracture surface, delamination between each layer of SiC fabric was observed.     

High-performance heterocyclic para-aramid aerogels for selective dye adsorption and thermal insulation applications

The high-performance polymer para-aramid (PPTA) is discovered to gel too soon during the polymerization process, resulting in poor processing performance. In this work, a homogeneous polymer solution containing heterocyclic para-aramid (HPPTA) was successfully synthesized by introducing 2,4-aminophenyl-5-aminobenzimidazole groups into the molecular chains of PPTA, and then HPPTA aerogel was prepared using a supercritical drying technique that took advantage of the HPPTA solution's excellent property of slow gelation. When the HPPTA polymer mass fraction was 1 wt%, the aerogel had the lowest density of 0.086 g cm⁻³ with a BET specific surface area of 376.59 m² g⁻¹. The HPPTA-2 aerogel had better adsorption performance for anionic dye methyl orange, with a maximum adsorption capacity of 319.47 mol g⁻¹; however, its adsorption capacity for cationic dye methylene blue and neutral dye dimethyl yellow was very low, at only 19.68 and 0 mol g⁻¹, respectively. The selective adsorption ability of HPPTA aerogel made it a simple and scalable platform for removing anionic dyes from water solutions. Furthermore, the HPPTA aerogel has outstanding thermal properties for thermal insulation applications in severe environments due to the synergistic effect of the 3D porous structure inside the aerogel and the exceptional thermal stability of the HPPTA.     

Dielectric and microwave absorption properties of polymer-derived TiC/SiC/SiOC multiphase ceramics in X band

Polymer-derived TiC/SiC/SiOC ceramics were prepared using tetrabutyl titanate (TBT)-modified polysiloxane (PSO) as precursor. The effects of heat treatment temperature and TBT content in precursor on the microstructure, phase composition, and microwave absorbing properties of TiC/SiC/SiOC ceramics were investigated. The crystallinity of the ceramics increases with the increase of heat treatment temperature. With the increase of TBT content, the TiC content of the ceramics increases and the SiC content decreases. When the TBT content ranges from 1 to 5 wt.%, the increase of TBT content has little effect on the real part of the dielectric constant of TiC/SiC/SiOC ceramics. When the TBT content is 7 wt.%, the imaginary part of the dielectric constant of the ceramics changes. For TiC/SiC/SiOC ceramic obtained from the pyrolysis of PSO-TBT precursor with 7 wt.% TBT, the dielectric constant is within the target electromagnetic parameters. Therefore, it has an effective absorption bandwidth of 4.2 GHz, covering the entire X band, showing an excellent microwave absorbing performance.     

二元炭质-二氧化硅干凝胶和气凝胶制备碳化硅晶须

以炭质水性中间相和正硅酸乙酯(TEOS)为原料,由溶胶-凝胶法分别制得二元干凝胶和气凝胶前驱体.在氩气气氛中,通过碳热还原分别合成了直径在纳米级的SiC晶须.利用红外光谱,X-射线衍射和透射电子显微镜对合成的β-SiC晶须进行了表征,结果表明,SiC晶须的生长过程为"VS"机理,合成温度和前驱体制备工艺对SiC晶须的性质有较大的影响.     

Effect of BN nanoparticle content in SiC matrix on microstructure and mechanical properties of SiC/SiC composites

BN-nanoparticle-containing SiC-matrix-based composites comprising SiC fibers and lacking a fiber/matrix interface (SiC/BN + SiC composites) were fabricated by spark plasma sintering (SPS) at 1800°C for 10 min under 50 MPa in Ar. The content of added BN nanoparticles was varied from 0 to 50 vol.%. The mechanical properties of the SiC/BN + SiC composites were investigated thoroughly. The SiC/BN + SiC composites with a BN nanoparticle content of 50 vol.%, which had a bulk density of 2.73 g/cm³ and an open porosity of 5.8%, exhibited quasiductile fracture behavior, as indicated by a short nonlinear region and significantly shorter fiber pullouts owing to the relatively high modulus. The composites also exhibited high strength as well as bending, proportional limit stress, and ultimate tensile strength values of 496 ± 13, 251 ± 30, and 301 MPa ± 56 MPa, respectively, under ambient conditions. The SiC fibers with contents of BN nanoparticles above 30 vol.% were not severely damaged during SPS and adhered to the matrix to form a relatively weak fiber/matrix interface.     

Analysis of SiC/SiC composites for energy applications at ambient conditions

Plain weave planar and biaxially braided tubular SiC/SiC CMCs are evaluated in tension and four-point bending, respectively, at ambient conditions. Custom-designed fixtures for CMC testing are developed for each loading mode and are coupled with three-dimensional digital image correlation. Stereoscopic image correlation analysis reveals crack initiation and failure sites to provide insight into stress redistribution mechanisms. Scanning electron microscopy is performed postmortem to determine the influence of microstructural features on crack initiation and failure. Crack spacing is measured in situ by stereoscopic image correlation and confirmed by SEM measurements to relate to underlying tow-tow crossing points. Triangulated surface heights of plain weave tow architecture are used to determine that subtle differences in neighboring transverse tow angle, which vary within a range of ±4° from horizontal, have no significant effect on final fracture location. The results presented reaffirm the state of current SiC/SiC CMCs developed for energy applications and will help to further improve SiC/SiC and other CMCs.     

Effect of Interfacial Reaction on the Thermal Conductivity of Al–SiC Composites with SiC Dispersions

The effect of interfacial reactions between Al and SiC on the thermal conductivity of SiC-particle-dispersed Al-matrix composites was investigated by X-ray diffraction and transmission electron microscopy (TEM), and the thermal barrier conductance ( h _c) of the interface in the Al–SiC composites was quantified using a rule of mixture regarding thermal conductivity. Al–SiC composites with a composition of Al (pure Al or Al–11 vol% Si alloy)–66.3 vol% SiC and a variety of SiC particle sizes were used as specimens. The addition of Si to an Al matrix increased the thermal barrier conductance although it decreased overall thermal conductivity. X-ray diffraction showed the formation of Al₄C₃ and Si as byproducts in addition to Al and SiC in some specimens. TEM observation indicated that whiskerlike products, possibly Al₄C₃, were formed at the interface between the SiC particles and the Al matrix. The thermal barrier conductance and the thermal conductivity of the Al–SiC composites decreased with increasing Al₄C₃ content. The role of Si addition to an Al matrix was concluded to be restraining an excessive progress of the interfacial reaction between Al and SiC.     

Cf/SiC复合材料的制备及性能的研究

采用料浆渗积-有机前躯体裂解工艺制备碳纤维增强碳化硅陶瓷基复合材料.制备材料的抗弯强度达283 MPa,断裂韧性达12.1 MPa·m1/2.     

Thermal conductivity mapping of oxidized SiC/SiC composites by time-domain thermoreflectance with heterodyne detection

Silicon carbide/silicon carbide (SiC/SiC) composites are often used in oxidizing environments at high temperatures. Measurements of the thermal conductance of the oxide layer provide a way to better understand the oxidation process with high spatial resolution. We use time-domain thermoreflectance (TDTR) to map the thermal conductance of the oxide layer and the thermal conductivity of the SiC/SiC composite with a spatial resolution of 3 μm. Heterodyne detection using a 50-kHz-modulated probe beam and a 10-MHz-modulated pump suppresses the coherent pick-up and enables faster data acquisition than what has previously been possible using sequential demodulation. By analyzing the noise of the measured signals, we find that in the limit of small integration time constants or low laser powers, the dominant source of noise is the input noise of the preamplifier. The thermal conductance of the oxide that forms on the fiber region is lower than the oxide on the matrix due to small differences in thickness and thermal conductivity.     

陶瓷绝缘材料高温电阻的测量

由于电除尘器用陶瓷绝缘子在高温环境下运行,在生产和验收过程中必须对其高温电阻进行控制和检测。介绍了陶瓷绝缘材料高温电阻的测量方法、电化时间、升温方式和测量操作,探讨了试样选择及处理、电极选择、温度控制,指出应根据不同测量目的采用不同的测量方法,尽量克服测量误差,提高精确度。     

Super-elastic carbon-bonded carbon fibre composites impregnated with carbon aerogel for high-temperature thermal insulation

A novel super-elastic carbon fibre composite was prepared by impregnating carbon aerogel into carbon-bonded carbon fibre (CBCF) through vacuum impregnation. The compressive strength of CBCF-CA was increased to 1.24?MPa in the z-direction, which was 6-fold more than that of neat CBCF. The CBCF-CA spontaneously recovered its size and shape without significant deformation when the pressure was released. The thermal conductivity of CBCF-CA was 0.246?W?(m·K)^?1 at 1400°C in the z-direction, which is lower than that of CBCF (0.341?W?(m·K)^?1). The average electromagnetic interference shielding e?ectiveness of CBCF-CA composites in the range of 12.4–18?GHz was higher than 40?dB, suggesting an absorption-dominant shielding feature. The CBCF-CA composite will be a new multifunctional material due to its low density, low thermal conductivity, high specific strength, excellent processability, super-elastic property and high electromagnetic shielding, which can be used for thermal insulation and protection of aerospace.     

Measuring the effects of heat treatment on SiC/SiC ceramic matrix composites using Raman spectroscopy

The evolution of residual stresses found within a silicon carbide/silicon carbide (SiC/SiC) ceramic matrix composite through thermal treatments was investigated using Raman microspectroscopy. Constituent stress states were measured before, during, and after exposures ranging from 900 to 1300°C for varying times between 1 and 60 minutes. Silicon carbide particles in the as-received condition exhibited average hydrostatic tensile stresses of approximately 300 MPa when measured at room temperature before and after heat treatment. The room temperature Raman profile of the silicon matrix was altered in both shape and location with heat treatment cycles due to increasing activation of boron within the silicon lattice as heat treatment temperatures increased. By accounting for boron activation in the silicon–boron system, little to no permanent change of any constituent stresses were observed, and the silicon matrix subsequently exhibited a complimentary average hydrostatic compressive stress of approximately 300 MPa at room temperature, measured before and after heat treatment. This result builds upon previous literature and offers increased insight into boron activation phenomena measured through Raman spectroscopy methods.