Nanofibers reinforced silica aerogel composites having flexibility and ultra-low thermal conductivity

For the sake of enhancing the performance of flexible silica aerogel in practical applications, flexible SiO₂/SnO₂ nanofibers (SSNF) reinforced flexible silica aerogel composites (abbreviated as SiO₂-SSNF) were successfully prepared. Firstly, the SiO₂/SnO₂ nanofibers with fine diameter (~320 nm) and excellent flexibility were prepared by electrospinning technology. Then the aerogel composites were synthesized by adding the flexible SSNF to the silica solution and through the sol-gel method and ethanol supercritical drying technology. The effects of different content of the nanofibers on thermal conductivity and Yong's modulus of SiO₂-SSNF aerogel composites were investigated. The SiO₂/SnO₂ nanofibers were randomly dispersed in the flexible silica aerogel and the great integrity of the material result in smaller linear shrinkage, better thermal protection, and mechanical properties compared with those pure SiO₂ aerogels. The final SiO₂-SSNF aerogel composites possess excellent thermal conductivity (0.025-0.029 W/(m∙K)) and higher Yong's modulus (70 kPa), which was twice than that of the pure silica aerogel. This prepared SiO₂-SSNF aerogel composites can be better used in thermal insulation due to its excellent flexible and thermal insulation property.     

The properties of silica aerogels hybridized with SiO2 nanoparticles by ambient pressure drying

In this study, we report the chemical characteristics of silica aerogels that were produced by adding SiO₂ nanoparticles into silica aerogel by ambient pressure drying. We synthesized silica aerogel composites with different weight percentages of SiO₂ nanoparticles ranging from 0 wt% to 0.025 wt% of the total amount of solution. As the wt% of SiO₂ nanoparticles increased, the number of chemical bonds that formed during condensation of the silica aerogel increased because of the presence of surface hydroxyl groups, thus the particle size of the silica aerogels increased. Silica nanoparticle-doping of silica aerogels can be used to control the synthesis of nanocomplex structures.     

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.     

Novel self-reinforcing ZrO2–SiO2 aerogels with high mechanical strength and ultralow thermal conductivity

Novel self-reinforcing ZrO₂–SiO₂ aerogels with high mechanical strength and ultralow thermal conductivity are fabricated by impregnating hydrolyzed ZrO₂–SiO₂ sol into wet gel matrix and drying. The ZrO₂–SiO₂ sol fills the macropores and defects of ZrO₂–SiO₂ aerogel matrix generating during the gelation process, which contributes to the improvement of the mechanical properties of the ZrO₂–SiO₂ aerogel matrix. The mechanical and thermal properties of the as-prepared ZrO₂–SiO₂ aerogel are investigated and discussed. The results show that the mechanical strength of the self-reinforcing aerogels obviously increases from 0.51 to 3.11?MPa with the increase of impregnation times, while the thermal conductivity of the aerogels slightly increases from 0.0235 to 0.0306?W?m^?1 K^?1. The novel self-reinforcing ZrO₂–SiO₂ aerogel could have interesting applications in aerospace and energy because of its outstanding mechanical and thermal properties.     

Opacified graphene-doped silica aerogels with controllable thermal conductivity

In this work, we developed a new type of thermal insulation materials by combining the silica aerogel (SiO₂) and graphene (G) followed by aging and supercritical drying. The effects of different G/SiO₂ mass ratios on the microstructures and properties of opacified G/SiO₂-x composite aerogels were investigated. The results showed that the graphene was well-distributed in the SiO₂ matrix. Meanwhile, the opacified composite aerogels showed high-specific surface area (~?1000 m²/g). Due to the unique bandgap feature and conjugated large π bond of graphene, the thermal insulation property of G/SiO₂-x composite aerogels was enhanced in contrast with the pure SiO₂ aerogel. Moreover, a possible mechanism of heat transfer was discussed to interpret the result.     

Synthesis of monolithic SiC aerogels with high mechanical strength and low thermal conductivity

The monolithic silicon carbide (SiC) aerogels were converted from catechol-formaldehyde/silicon composite (CF/SiO₂) aerogels through carbothermal reduction and calcination. In the process of preparing the CF/SiO₂ aerogel, a new method was proposed to produce more silicon carbide and enhanced the mechanical properties of the SiC aerogel. This method was realized by adding an alkaline silica sol as supplemental silicon source. The principle process of CF/SiO₂ aerogels converting to SiC aerogels was discussed based on experiment and results analysis, while the microstructure, mechanical properties, and thermal properties of the prepared SiC aerogels were investigated. The results show that the as-synthesized SiC aerogels consist of β-SiC and a small amount of α-SiC nanocrystalline. It possessed a mesoporous structure and a low thermal conductivity 0.049 W/(m∙K), a relatively high compressive strength 1.32 MPa, and a relatively high specific surface area 162 m²/g. Due to their outstanding thermal and mechanical properties, the prepared SiC aerogels present potential applications in thermal insulation field, such as space shuttles and aerospace carrier thermal protection materials.     

Comparative studies on the physical properties of TEOS,TMOS and Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript> based silica aerogels by ambient pressure drying method

In order to compare the various precursors of silica aerogels, three different precursors namely TMOS, TEOS and Na₂SiO₃ were studied in this paper. The property differences of the aerogels caused by the three precursors were discussed in terms of reaction process, gelation time, pore size distributions, thermal conductivity, SEM, hydrophobicity and thermal stability. It has been found that the gelation time of the silica gel is strongly dependent on the type of precursor used. During the surface modification process, organic groups were attached to the wet gel skeletons transforming the hydrophilic to the hydrophobic which were characterized by Fourier Transform Infrared spectroscopy (FTIR). It has been found that the contact angle of the Na₂SiO₃ and TMOS precursor based aerogels with water have the higher contact angle of 149° and whereas Na₂SiO₃ precursor based aerogel has the lower contact angle of 130°. The thermal conductivities of the Na₂SiO₃ and TMOS based aerogels have been found to be lower (0.025 and 0.030 W m^?1 K^?1, respectively) compared to the TEOS based (0.050 W m^?1 K^?1) aerogels. The pore sizes obtained from the N₂ adsorption measurements varied from 40 to 180, 70 to 190, and 90 to 200 nm for the TEOS, TMOS and Na₂SiO₃ precursor based aerogels, respectively. The scanning electron microscopy studies of the aerogels indicated that the Na₂SiO₃ and TMOS based aerogels show narrow and uniform pores while the particles of SiO₂ network are very small. On the other hand, TEOS aerogel show non-uniform pores such that the numbers of smaller size pores are less compared to the pores of larger size while the SiO₂ particles of the network are larger as compared to both Na₂SiO₃ and TMOS aerogels. Hence, the surface are of the aerogels prepared using TEOS precursor has been found to be the lowest (~620 m² g^?1) compared to the Na₂SiO₃ (~868 m² g^?1) and TMOS (~764 m² g^?1) aerogels.     

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.     

Improvement of thermal stability of ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> aerogels by an inorganic–organic synergetic surface modification

The thermal stability of ZrO₂–SiO₂ aerogels was significantly improved by inorganic–organic synergetic surface modifications: inorganic ions [Fe(III)] surface modification and hexamethyldisilazane gas phase modification. The replacement of Hs from surface hydroxyl groups on the aerogel by Fe(III) ions and silyl groups played a critical role in isolating the hydrous particles of ZrO₂–SiO₂ aerogels. So the particle growth caused by the condensation of hydroxyl groups upon firing was inhibited. Meanwhile, the decomposition of the silyl groups upon heat treatment produced SiO₂ particles, which could serve as pining particle to inhibit the crystallization of ZrO₂. Hence, the porous microstructure of the modified aerogels was still well preserved up to 1000 °C, with a high specific surface area of 203.5 m²/g, and a considerable pore volume of 0.721 cc/g. These characteristics of the modified aerogels suggest that it has great potential on ultrahigh-temperature applications in the fields of thermal insulation, catalysis, and catalyst support, etc.     

Fiber Reinforced Polyimide Aerogel Composites with High Mechanical Strength for High Temperature Insulation

Glass fiber/polyimide aerogel composites are prepared by adding glass fiber mat to a polyimide sol derived from diamine, 4,4′‐oxydianiline, p‐phenylene diamine, and dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The fiber felt acts as a skeleton for support and shaping, reduces aerogel shrinkage during the preparation process, and improves the mechanical strength and thermal stability of the composite materials. These composites possess a mesoporous structure with densities as low as 0.143–0.177 g cm^?3, with the glass fiber functioning to improve the overall mechanical properties of the polyimide aerogel, which results in its Young's modulus increasing from 42.7 to 113.5 MPa. These composites are found to retain their structure after heating at 500 °C, in contrast to pure aerogels which decompose into shrunken ball‐like structures. These composites maintain their thermal stability in air and N₂ atmospheres, exhibiting a low thermal conductivity range of 0.023 to 0.029 W m^?1 K^?1 at room temperature and 0.057to 0.082 W m^?1 K^?1 at 500 °C. The high mechanical strengths, excellent thermal stabilities, and low thermal conductivities of these aerogel composites should ensure that they are potentially useful materials for insulation applications at high temperature.     

氧化锆气凝胶研究进展

氧化锆气凝胶以其优异的性能受到人们广泛的关注。本文综述了氧化锆气凝胶的制备工艺、掺杂改性工艺、SiO2-ZrO2复合气凝胶、纤维增强氧化锆气凝胶的研究进展以及氧化锆气凝胶的应用。最后,对氧化锆气凝胶的发展方向进行了探讨。     

Preparation and properties of PAN-based carbon fiber-reinforced SiCO aerogel composites

To overcome the brittleness issue of SiCO aerogels, the polyacrylonitrile-based (PAN) carbon fiber was impregnated with SiCO sol to obtain carbon fiber-reinforced SiCO aerogel composites (C/SiCO). SiCO sol was prepared through an acid-alkaline two-step catalysis by using methyltrimethoxysilane (MTMS) and dimethyldiethoxysilane (DMDES) as precursors. C/SiCO-1, C/SiCO-2 and C/SiCO-3 were obtained after repeated impregnation of the SiCO sol and gelating, aging, supercritical drying and pyrolyzing one to three times. SEM images show that the SiCO aerogel fills the pores between the carbon fibers, and the nanoporous structure of the SiCO aerogel can effectively improve the thermal insulation of the composites. As the times of impregnation of the SiCO sol increased, the mechanical properties and oxidation resistance of C/SiCO have been improved significantly. The bending strength of C/SiCO-3 was 32.52 MPa, and the compressive strength (25%ε) was 51.98 MPa. After heating at 1600 °C, the linear shrinkage in the thickness direction of C/SiCO-1 was 20.72%, while that of C/SiCO-3 was only 1.85%. A dense SiO₂ molten oxide film formed on the surface of C/SiCO at high temperature, and its extremely low oxygen permeability effectively protected the inside of the composites.     

Aerogels—Nanoporous materials part I: Sol-gel process and drying of gels

Aerogels are highly porous nanostructured materials made in a sol-gel process, generally followed by supercritical drying in an autoclave. Today considerable activities are also devoted to subcritical drying under ambient conditions. Aerogels have been made of inorganic substances such as SiO₂, Al₂O₃, TiO₂ etc. or organic components (resorcinol and melamine formaldehyde) in transparent, translucent and opaque form. Even electrically conductive carbon aerogels are available today. An important step with respect to mass application is the production of granular SiO₂-aerogels with water glass as a precursor. Also of practical importance is the hot-pressing of aerogel sheets from granular or powdered fills.In this paper we shall describe the formation of the organic and inorganic gels and the various procedures to extract the pore fluid without or with little shrinkage. A subsequent paper will be devoted to the characterization and the application of aerogels.     

Facile preparation for gelatin/hydroxyethyl cellulose-SiO2 composite aerogel with good mechanical strength,heat insulation,and water resistance

The advanced thermal insulation materials with low cost and high mechanical properties play an important role in transport packaging and thermal protection fields. An inorganic/organic composite aerogel was prepared through hydrogen bonds and chemical crosslinking among silica aerogel particles, gelatin (GA), and hydroxyethyl cellulose (HEC). The as-prepared GA/HEC-SiO₂ composite aerogels were characterized by compression tests, scanning electron microscopy, Fourier transform infrared, thermogravimetric analyzer, and contact angle tests to investigate the chemical composition and physical structure. The GA/HEC-SiO₂ composite aerogels exhibited a strong mechanical strength (0.53–4.01 MPa), a high compression modulus (1.33–11.52 MPa), a lower volume density (0.035–0.081 g/cm³), thermal conductivity as low as 0.035 W/[m K]), a porosity of more than 93%, and hydrophobic angle as high as 150.01° after hydrophobic modification. These results indicate that biopolymer composite aerogels embedded with SiO₂ aerogel particles display a bright future in thermal insulation.     

Surface Modification of Silica Aerogels Dried with 2-Methyl-1-Propanol in the Sub-Critical Pressure

Silica aerogels were made by sol-gel techniques using industrial silicon derivatives (polyethoxydisiloxanes, E-40), followed by drying under sub-critical pressure with iso-butanol. The shrinkage (linear), specific surface area, S_BET, SEM, TEM and the pore size distribution of the silica aerogels were investigated. The results show that the shrinkage (linear) is below 5%, diameter of the silica particles is about 6 nm and the pore size of the silica aerogels is 10 nm. The specific surface area of the silica aerogel is 559.2 m²/g. IR and NMR techniques were used to determine the organic groups on the silica matrix, GC/MS was also introduced to analyse the composition of the recycled iso-butanol. The surface modification and the reactions of iso-butanol to the silica aerogel are also discussed.     

Synthesis and characterization of a xonotlite fibers–silica aerogel composite by ambient pressure drying

Xonotlite fibers (XFs) reinforced silica aerogel composites were prepared by a sol–gel method under ambient pressure drying. XFs were synthesized through a dynamic hydrothermal route and had a noodle-like structure with length of 5–10 μm and average diameter of 150–200 nm. The microstructure analysis showed that XFs were inlaid in silica aerogel matrix by physical combination which contributed to restrict the volume shrinkage of alcogels and maintain the integrality aerogels during drying process. The physical, naonporous and thermal properties of the as prepared aerogel composites were investigated and discussed in detail. The new aerogel composites possessed porous nanostructure, which exhibited typical properties of 0.126 g/cm³ density, 4.132 cm³/g pore volume, and thermal conductivity of 0.0285 W/(m K). The results indicated that the introduced XFs didn’t significantly alter the porosity, hydrophobicity or thermal conductivity of aerogel matrix. It was also found that the aerogel composites had much more outstanding porosity than that of pure aerogel upon calcinations at 800 °C. This study fabricated XFs–silica aerogel composites and explored a new way for silica aerogels to endure and remain monolithic under ambient pressure drying.     

Investigation on textural and structural evolution of the novel crack-free equimolar Al2O3-SiO2-TiO2 ternary aerogel during thermal treatment

Crack-free mesoporous equimolar Al₂O₃-SiO₂-TiO₂ ternary nanocomposite aerogel has been synthesized using an ethanol supercritical drying technique. The effects of heat treatment temperatures on its textural and structural evolution during thermal treatment are investigated in this study. XRD results reveal that only anatase phase is detected in the as-dried ternary aerogel, whereas peaks corresponding to silica and alumina phase are not shown due to its much faster polymerization rate of titania precursor. Structural transition from boehmite to γ-Al₂O₃ begins to occur at 450 °C within the ternary aerogel, and this process is completed at nearly 615 °C. The needle-like reticulated γ-Al₂O₃ grows along the anatase backbone, however, it is not evident in the XRD patterns. The morphologies of the ternary aerogel become more homogeneous after the structural transition, as indicated by the SEM analysis, which is also consistent with the BET results. With the increase of heat temperature up to 1050 °C, the γ-Al₂O₃ phase disappears and no separate SiO₂ is detected. At the same time, the silica-alumina network originates in a structure of Al-O-Si, and the silicon atoms incorporate into the alumina phase in the γ-Al₂O₃ structure, disordering the alumina primary particles. When the heat treatment temperature increases to 1200 °C, mullitization begins to occur along the titania backbone, whereas silica crystallization happens at 1300 °C. The 600 °C calcinated ternary aerogel is typically mesoporous, showing high specific surface area (255.37 m²/g), suitable average pore diameter (22.83 nm) and large pore volume (1.34 cm³/g). Moreover, the ternary aerogels show high surface acid activity at temperatures below 1000 °C, which have future applications for ideal catalysts and catalyst supports at elevated temperatures.     

Novel high-temperature-resistant Y2SiO5 aerogel with ultralow thermal conductivity

A novel Y₂SiO₅ ternary aerogel was prepared from tetraethoxysilane and yttrium chloride hexahydrate via the sol-gel method followed by high-temperature calcination. The effects of different calcination temperatures on the microstructure, mechanical and thermal stability of the Y₂SiO₅ aerogels were investigated. The aerogels exhibited low densities of 0.33-0.62 g/cm³, low thermal conductivities of 0.029-0.05 W/(m·K), and a relatively high strength of 0.16-56.47 MPa. Moreover, compared with the Al₂O₃–SiO₂ aerogel, the Y₂SiO₅ aerogel has higher thermal stability and more excellent high-temperature insulation, which has potential applications as a thermal protection material in hypersonic vehicles.     

Novel silica-modified boehmite aerogels and fiber-reinforced insulation composites with ultra-high thermal stability and low thermal conductivity

Alumina–silica composite aerogels have drawn vast attention due to their enhanced thermal stability compared to pristine alumina aerogels. However, they are generally weakly-crystallized and tend to experience inevitable sintering and significant surface area loss especially above 1200 °C. In this study, we developed a hydrothermal treatment and supercritical drying strategy for synthesizing novel, well-crystallized, silica-modified boehmite aerogels and fiber-reinforced composites. For the prepared aerogel, network coarsening was significantly hindered and the α-Al₂O₃ transition was completely prevented even at 1400 °C. As a result, the aerogel exhibits extremely high surface area maintenance (87 % and 53 % after 1300 °C and 1400 °C calcination, respectively) and low linear shrinkage (14 % after 1300 °C calcination) at elevated temperatures. The composite with good toughness shows excellent heat resistance and thermal insulating performance up to 1500 °C. These findings provide a general, direct new idea to improve the thermal tolerance of alumina-based aerogels and extend their applications to higher temperatures.     

Analysis of fluorescence properties of novel Eu3+-doped ZnAl2O4-based ceramic aerogels for high-power optical device applications

A novel series of ZnAl₂O₄:Eu³⁺ aerogels (ZAE) and mullite ceramic phase reinforced ZnAl₂O₄:Eu³⁺ aerogels (MZAE) with high fluorescence thermal stability have been firstly synthesized for the encapsulation of high-power optical devices. However, due to the intrinsic structural brittleness of the aerogel, the structure of ZAE tends to collapse during the heat treatment and the fluorescence performance falls short of expectations. To this end, we propose a simple and effective strategy to enhance the structural rigidity of fluorescent aerogels by introducing the mullite ceramic phase into the network structure of ZAE. This can effectively suppress the agglomeration of Eu³⁺ caused by the collapse of the structure during the heat treatment, thus enhancing the optical properties of the aerogel. Compared with ZAE, MZAE has higher fluorescence thermal stability. The fluorescence intensity of MZAE at 498 K is still 75 % of that at 298 K, and the chromaticity shift is only 22 × 10⁻³.