SiC junction enhanced carbon nanofiber aerogels with extremely high specific strength and ultra-low thermal conductivity

C/SiC aerogels with both ultra-low thermal conductivity and extremely high strength were fabricated by freeze casting. SiC junctions originated from pyrolysis of polycarbosilane (PCS) were formed between carbon nanofibers (C_f) to enhance the strength of aerogels. The effects of PCS content and total solid content on the phase composition, pore structure, thermal conductivity and compressive property were studied. The fabricated aerogels possess hierarchical pore structure. In the micro-scale, it contains circular pores with size of about 15 µm, while it is mesoporous and macroporous in the nano-scale. Both thermal conductivity and compressive strength increase with the increase in PCS content. Through tailoring PCS content and total solid content, C_f/SiC aerogels with porosity of 99.5%, thermal conductivity of 33 mW·m⁻¹·K⁻¹ and compressive strength of 7.14 MPa can be obtained. The specific strength of the fabricated C_f/SiC aerogels is up to 467.6 MPa/(g/cm³), which is the highest value for ceramic aerogels.     

Synthesis of SiC–TiO2 hybrid aerogel via supercritical drying combined PDCs route

The SiC-TiO₂ hybrid aerogels were obtained from polycarbosilane (PCS) and tetrabutyltitanate (TBT) as precursors using supercritical drying and polymer derived ceramics route. The polymer to ceramic conversion and the crystallization behavior were studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM), suggesting the preceramic aerogels converted to the SiC-TiO₂ ceramic aerogels through pyrolysis process at different temperatures. At 1200 °C, the ceramic aerogels were homogeneous with well-distributed element components, composed of rutile TiO₂ and the β-SiC crystalline phases. The results show that the SiC-TiO₂ ceramic aerogels with netwoks structure have 23.36 nm average pore size, high surface area (58 m²/g) and pore volume (0.22 cm³/g).     

Large size and low density SiOC aerogel monolith prepared from triethoxyvinylsilane/tetraethoxysilane

Crack-free silicon oxycarbide (SiOC) aerogel monolith was fabricated by pyrolysis of precursor aerogel prepared from triethoxyvinylsilane/tetraethoxysilane (VTES/TEOS) using sol-gel process and ambient drying. Effects of different precursors, the amount of base catalyst (NH₄OH) and the heating rate during pyrolysis on the properties such as monolithicity, bulk density, surface area and pore size distribution of aerogels were investigated. The results show that the crack-free SiOC aerogel can be easily obtained from VTES/TEOS as compared to that of methyltriethoxysilanes/tetraethoxysilane (MTES/TEOS) and phenyltriethoxysilanes/tetraethoxysilane (PhTES/TEOS) precursors. The influence of heating rate during pyrolysis process on shrinkage rate, ceramic yield and surface area of the SiOC aerogels could be ignored, while the variation in the amount of NH₄OH exerted a strong impact on the properties of SiOC aerogels. Increasing the amount of NH₄OH resulted in the decrease of bulk density and surface area of SiOC aerogels from 0.335 g/cm³ and 488 m²/g to 0.265 g/cm³ and 365 m²/g. The resultant SiOC aerogels exhibit high compressive strength (1.45–3.17 MPa). ²⁹Si MAS NMR spectra revealed the retention of Si-C bond in the SiOC aerogels after pyrolysis at 1000 °C. The present work demonstrates VTES/TEOS is a promising co-precursors to easily and low cost synthesize large size SiOC aerogel monolith.     

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.     

Manufacture of Si3N4-SiCN composite bulks with hierarchical pore structure

Si₃N₄-SiCN ceramic foams with hierarchical pore architecture were formed by protein-based gelcasting and precursor infiltration and pyrolysis. The primary pore structure (>100 μm) was generated by protein gelation and precursor ceramization, while the secondary pore structure (10–50 μm) originated from the cell windows after pyrolysis. The network of Si₃N₄ nanowires and the voids among ceramic particles formed the tertiary pore structure (<2 μm). The obtained Si₃N₄-SiCN ceramics had a density of 0.45–0.66 g/cm³ and an open porosity of 72.7–82.8 vol.%. The porous bulks possessed a compressive strength of up to 16.9 ± 1.1 MPa (72.7 vol.% open porosity) at room temperature and 8.6 ± 0.2 MPa at 800 °C. A good gas permeability of the ceramics was indicated with a tested value of 3.27 cm³cm/(cm²·s·kPa). The excellent mechanical property, permeability together with the hierarchical pore structure enabled the Si₃N₄-SiCN composite bulks promising for industrial filtration applications.     

Effect of pyrolysis temperature on the pore structure evolution of polysiloxane-derived ceramics

Homogeneous silicon oxycarbide (SiOC) ceramic powders were prepared by pyrolysis of cross-linked polysiloxane at different temperatures (1250–1500 °C) under vacuum. The effect of pyrolysis temperature on the pore structure evolution was investigated by means of N₂ adsorption, SEM, XRD, IR and element analysis (EA). Studies showed that predominate mesoporous ceramics with the average pore size in the range of 2–13 nm were obtained after pyrolysis in this temperature range. The pore structure transformation is strongly correlated with the thermolytic decomposition process of the used precursor, such as phase separation and carbothermal reduction. At relatively lower temperature (1250–1350 °C), the ceramics had a relative small specific surface areas (35 m²/g) owing to the low degree of carbothermal reduction. However, as the carbothermal degree had an obvious augment at relative higher temperature (1400–1450 °C), the specific surface areas and total pore volume increased and reached to the maximum of 66 m²/g and 0.214 cm³/g, respectively, and subsequently decreased rapidly after 1500 °C for the reason of partial sintering of the nano-sized SiC derived from polysiloxane.     

Fabrication and microstructure evolution of monolithic bridged polysilsesquioxane-derived SiC ceramic aerogels

SiC aerogels are representative high-temperature ceramic aerogels that have demonstrated extensive potential utility in the thermal insulation field under extreme conditions. Although the efficient fabrication of monolithic and highly crystalline SiC aerogels is crucial, it remains highly challenging. Herein, a one-step pyrolysis strategy of a bridged polysilsesquioxane (BPSi) aerogel precursor is reported. The preceramic BP aerogel was prepared via a sol-gel method followed by vacuum drying, and the subsequent pyrolysis process conveniently converted the BPSi aerogel precursor into a SiC aerogel. This circumvents the need for harsh synthetic conditions, high-cost noble metal catalysts, special drying, and additional calcination processes. Furthermore, a competitive mechanism between the “gas-escape” caused by the volatilization of low molecular compounds and carbothermal reduction reaction, and the “volume-shrinkage” resulting from high-temperature sintering was proposed to explain the evolution of phase composition and pore hierarchy of BPSi-derived ceramic aerogels.     

Synthesis and thermal evolution of polysilazane-derived SiCN(O) aerogels with variable C content stable at 1600 °C

Ceramic aerogels possess intriguing thermophysical properties which make them excellent candidates for high temperature thermal insulators. However, their properties can degrade at high temperature because of crystallization phenomena or because of densification (causing a sensible reduction of their specific surface area and porosity).The polymer derived ceramic (PDC) route is a relatively new way of developing ceramic aerogels. Several aspects influence the properties of the final product when dealing with preceramic polymers, among them their chemical composition and molecular architecture.In this work, we investigated the possibility of producing aerogels belonging to the SiCN system from polysilazanes mixtures, namely perhydropolysilazane (PHPS) and a methyl/vinyl-containing polysilazane, namely Durazane 1800®, thus changing the C/Si ratio of the amorphous pyrolyzed products. It is shown that the chemical composition of the ceramic aerogel affects the main properties of the porous materials, such as thermal stability and specific surface area (SSA). Results show that the presence of carbon in the aerogels inhibits crystallization of Si₃N₄ up to 1600 °C in N₂ and allows to maintain a SSA of ~90 m²/g up to this temperature.     

Structural Design of Polymer‐Derived SiOC Ceramic Aerogels for High‐Rate Li Ion Storage Applications

SiOC ceramic aerogels with different porosity, pore size, and specific surface area have been synthesized through the polymer‐derived ceramic route by modifying the synthesis parameters and the pyrolysis steps. Preceramic aerogels are prepared by cross‐linking a linear polysiloxane with divinylbenzene (DVB) via hydrosilylation reaction in the presence of a Pt catalyst under highly diluted conditions. Acetone and cyclohexane are used as solvent in our study. Wet gels are subsequently supercritically dried with CO₂ to get the final preceramic aerogels. The SiOC ceramic aerogels are obtained after a pyrolysis treatment at 900°C in two different atmospheres: pure Ar and H₂ (3%)/Ar mixtures. The nature of the solvent has a profound influence of the aerogel microstructure in terms of porosity, pore size, and specific surface area. Synthesized SiOC ceramic aerogels have similar chemical compositions irrespective of processing conditions with ~40 wt% of free carbon distributed within remaining mixed SiOC matrix. The BET surface areas range from 215 m²/g for acetone samples to 80 m²/g for samples derived from cyclohexane solvent. The electrochemical characterization reveals a high specific reversible capacity of more than 900 mAh/g at a charging rate of C (360 mA/g) along with a good cycling stability. Samples pyrolyzed in H₂/Ar atmosphere show a high reversible capacity of 200 mAh/g even at a high charging/discharging rate of 20 C. Initial capacities were recovered after whole cycling procedure indicating their structural stabilities resisting any kind of exfoliations.     

Synthesis and Characterization of Mesoporous Hybrid Silica-Polyacrylamide Aerogels and Xerogels

We report the synthesis of highly porous hybrid silica-polyacrylamide aerogels where the inorganic network was obtained through the hydrolysis and poly-condensation of tetramethoxysilane via a two-step sol–gel process while the polyacrylamide polymer was made by photo-copolymerization of two organic monomers, the acrylamide and the bis-acrylamide. These aerogels were obtained after a carbon dioxide supercritical drying while the corresponding xerogels were dried by simple evaporation. These materials, as well as pure silica and polyacrylamide aerogels and xerogels, were characterized by FTIR spectroscopy, solid-state ²⁹Si and ¹³C NMR spectroscopy, Thermogravimetric Analysis, a nitrogen adsorption-desorption technique, and Scanning Electron Microscopy. The FTIR and NMR spectra and the TGA/DTA analyses confirm the coexistence of highly branched silica and polyacrylamide networks reflecting the hybrid nature of the materials obtained. Nitrogen adsorption measurements reveal high specific surface areas and pore size distributions disclosing the mesoporous character of these hybrid materials. Hybrid silica-polyacrylamide aerogels having a specific surface area equal to 572 m²/g and a pore volume 1.92 cm³/g were successfully prepared for the first time in this study. The high porosity of these aerogels is due to a better resistance of the silica network to capillary forces during the supercritical drying when silica coexists with a polyacrylamide network.     

Preparation of Micro‐/Mesoporous SiOC Bulk Ceramics

Micro‐/mesoporous SiOC bulk ceramics with high surface area and bimodal pore size distribution were prepared by pyrolysis of polysiloxane in argon atmosphere at 1100°C–1400°C followed by etching in hydrofluoric acid solution. Their thermal behaviors, phase compositions, and microstructures at different nano‐SiO₂ filler contents and pyrolysis temperatures were investigated by XRD, SEM, DSC, and BET. The SiO₂ fillers and SiO₂‐rich clusters in the SiOC matrix act as pore‐forming sites and can be etched away by HF. At the same time, the SiO₂ filler promotes SiOC phase separation during the pyrolysis. The filler content and pyrolysis temperature have important effects on phase compositions and microstructures of porous SiOC ceramics. The resulting porous SiOC bulk ceramic has a maximum specific surface area of 822.7 m²/g and an average pore size of 2.61 nm, and consists of free carbon, silicon carbide, and silicon oxycarbide phases.     

The influence of preparation method on the physicochemical properties of titania–silica aerogels: Part two

Titania–silica aerogels with different titania content were prepared. Four preparation methods differing mainly in approach to precursors hydrolysis were applied, while only three of them allowed total hydrolysis of silica precursor before titania precursor was added. The preparation of mixed products of titania and silica hydrolysis precursors containing gels was followed by high temperature supercritical drying (HTSCD) and thermal treatment at 500 °C. Obtained mixed oxides in form of aerogels were characterized by BET surface areas up to 1000 m²/g, mesopore volumes up to 1.6 cm³/g and bulk densities as low as 0.04 g/cm³. Even 18 h lasting aging did not allow to produce narrow diameter range mesoporous materials, their broad pore diameter distributions resulted in average pore sizes varying from 10 to nearly 30 nm. XRD measurements proved the presence of anatase crystalline form of titania, while silica was present in amorphous form. SEM studies indicated presence of isolated titania particles on titania–silica surface while joint hydrolysis method was applied. Titania–silica aerogels obtained by the simultaneous hydrolysis of precursors and the impregnation method showed high photocatalytic activity in degradation of salicylic acid in water. Activities of these mesoporous photocatalysts were higher than commercial P25 Degussa TiO₂. Comparison of activity of pure TiO₂ (P25 Degussa) and aerogels indicates higher utilization of titania present in mesoporous mixed oxides.     

Preparation of controlled porosity carbon aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO₂ atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O₂ cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O₂ cell using the carbon with the largest pore volume (2.195 cm³/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290 mA h g⁻¹.     

Formation and Pore Structure of Boron Nitride Aerogels

Gels containing a poly(borazinyl amine) and tetrahydrofuran were processed by CO₂ supercritical drying techniques followed by pyrolysis. The resulting BN ceramic aerogels are highly porous, and the microstructure, porosity, and surface area characteristics have been examined. The aerogels show excellent thermal stability exhibiting surface areas in excess of 350 m²/g and porosities greater than 0.8 even when heated in argon at 1500°C for 8 h. By removing solvent via evaporation before supercritical drying, the mean pore radius can be varied between 3.6 and 10 nm.     

Physico-chemical properties of silica aerogels prepared from TMOS/MTMS mixtures

In the present work, results on the physico-chemical properties of the silica aerogels prepared by sol–gel process using mixtures of TMOS and MTMS as precursor are reported. The wide range of precursor mixture was studied with ratio of MTMS/TMOS in precursor mixtures as 0:100, 25:75, 50:50, 75:25, and 100:0 by volume. The gels with these precursor mixtures were successfully prepared using two step acid–base catalysis for gelation. Acetic acid (0.001 M) and NH₄OH (1.5 M) were used for catalysis and resulting alcogels were subsequently dried by supercritical solvent extraction method. FTIR spectroscopy revealed that the aerogels show more intense peak at 1,260 and 790 cm⁻¹ attributed to Si–CH₃ resulting in more hydrophobic nature and these results were concurrent with adsorbed water content measurements made using Karl Fischer’s titration technique. The resulted aerogels were characterized using differential thermal analysis, thermo gravimetric analysis and surface area measurements. The surface area measurements showed an interesting trend that the surface area increased from 395 to 1,037 m²/g with increase in MTMS content in the precursor mixture from 0 to 50% and then again decreased to 512 m²/g for further increase in MTMS content from 50 to 100% in the precursor mixture. It was observed from our studies that silica aerogels prepared using a starting mixture of 50% TMOS and 50% MTMS resulted in high moisture resistance (adsorbed water content of 0.721% w/w), low density of 90 kg/m³ and the highest surface area of 1,037 m²/g, which has great potential for catalysis support applications.     

Planar,Polysilazane‐Derived Porous Ceramic Supports for Membrane and Catalysis Applications

Porous, silicon carbonitride‐based ceramic support structures for potential membrane and catalysis applications were generated from a preceramic polysilazane precursor in combination with spherical, ultrahigh‐molecular weight polyethylene microparticles through a sacrificial filler approach. A screening evaluation was used for the determination of the impact of both porogen content and porogen size on pore structure, strength, and permeability characteristics of planar specimens. By optimizing both the composition as well as cross‐linking parameters, maximum characteristic biaxial flexural strengths of 65 MPa and porosities of 42% were achieved. The evolution of an interconnected, open‐pore network during thermal porogen removal and conversion of the preceramic polymer led to air permeabilities in the order of 10^?14 m². The materials were further exposed to long‐term heat treatments to demonstrate the stability of properties after 100 h at 800°C in oxidizing, inert, and reducing environments. The determined performance, in combination with the versatile preparation method, illustrates the feasibility of this processing approach for the generation of porous ceramic support structures for applications at elevated temperatures in a variety of fields, including membrane and catalysis science.     

High surface area methyltriethoxysilane-derived aerogels by ambient pressure drying

In this paper we report the synthesis of methyltriethoxysilane (MTES) based aerogels by non-supercritical/ambient pressure drying. The alcogels have been aged in different concentrations of silane precursor solutions before drying and aerogels with low density and high porosity were obtained. The 60% vol silane aged aerogel shows a surface area of 416 m²/g with a pore volume of 0.99 cm³/g and a maximum surface area of 727 m²/g was obtained for 80% vol silane aged aerogel. The non-silane aged sample possess a surface area of 471 m²/g with a total pore volume of 0.83 cm³/g. The aerogels show broad pore-size distribution. The FT-IR studies reveal the retention of Si–C bond in the network and the formation of a hydrophobic gel. The ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS-NMR) studies were also employed to characterize the local environment around the silicon atoms and to obtain information on the condensation degree of the gel network. By varying the hydrolysis pH, highly flexible aerogels have also been successfully prepared. The porosity studies on the flexible aerogels are also presented here.     

Enhanced thermal shrinkage behavior of phenolic-derived carbon aerogel-reinforced by HNTs with superior compressive strength performance

A novel carbon/m-HNTs composite aerogel was synthesized by introducing the modified halloysite nanotubes (m-HNTs) into phenolic (PR) aerogels through chemical grafting, followed with carbonization treatment. In order to explore the best proportion of HNTs to phenolic, the micromorphology of PR/m-HNTs were investigated by SEM before carbonization, confirming 10 wt% of m-HNTs is most beneficial to the porous network of aerogels. The interaction between PR and HNTs was studied by FTIR spectra, and microstructure evolution of the target product-carbon/m-HNTs composite aerogel were illustrated by SEM and TEM techniques. SEM patterns indicated that the carbon/m-HNTs aerogels maintain a stable porous structure at 1000 °C (carbonization temperature), while a ~20 nm carbon layer was formed around m-HNTs generating an integral unit through TEM analysis. Specific surface area and pore size distribution of composite aerogels were analyzed based on mercury intrusion porosimetry and N₂ adsorption–desorption method, the obtained results stayed around 500 m²g^?1 and 1.00 cm³g^?1 (pore volume) without significant discrepancy, compared with pure aerogel, showing the uniformity of pore size. The weight loss rate (26.76%) decreased greatly compared with pure aerogel, at the same time, the best volumetric shrinkage rate was only 30.83%, contributed by the existence of HNTs supporting the neighbor structure to avoid over-shrinking. The highest compressive strength reached to 4.43 MPa, while the data of pure aerogel was only 1.52 MPa, demonstrating the excellent mechanical property of carbon/m-HNTs aerogels.     

Thermal conductivity of glass fiber-reinforced silica aerogels using molecular dynamics simulations

Silica aerogels are low-density, low-thermal conductivity, and highly porous solids used in a wide range of applications. In the present work, the glass fibers-reinforced silica aerogels nanocomposite models were investigated for thermal conductivity using molecular dynamics (MD) simulations. Here, the glass fibers weight percentage (% wt) was varied from 2.14 to 21.20%, i. e., the density of the silica aerogel nanocomposite ranged from 252 to 307 kg m^?3. The thermal conductivity increases with the % wt of glass fibers for the considered range. However, the increase was insignificant, i. e., from 0.0357 to 0.048 W m^?1 K^?1. Moreover, the thermal conductivity varies with the density of nanocomposite according to a power-law with an exponent of 1.90 ± 0.18. Furthermore, the obtained thermal conductivity values of silica aerogels and their nanocomposites are in good agreement with experimental and computational studies. The outcome shows that the glass fibers-reinforced silica aerogels nanocomposites can be used for low-thermal conductivity applications.     

Preparation and high-temperature service performance of hierarchically pore-structured BN fiber aerogels

Multifunctional aerogels with high porosity and good thermal insulation have attracted much attention in the field of energy and aerospace engineering. In this work, a three-dimensional BN fiber aerogel with hierarchically porous structure was prepared through a freeze-drying combined with in-situ carbothermal reduction nitridation route. The synthesized BN fiber aerogel exhibits a specific surface area of 154.3 m²/g, a high porosity of 96.8% and hydrophobicity. Moreover, the BN fiber aerogel shows a low thermal conductivity of 0.051 W/(m·K) and excellent thermal insulation properties owing to its hierarchical porous structure. Particularly, the BN fiber aerogel still maintains its low thermal conductivity and a rather high mechanical strength after re-heated at 1473 K for 3 h in Ar atmosphere, suggesting excellent high-temperature service performance. The successfully developed multifunctional BN fiber aerogel holds promising potential in high-temperature thermal insulation fields.