Effect of the thermal treatment on microstructure and physical properties of low-density and high transparency silica aerogels via acetonitrile supercritical drying

In this paper, we reported the experimental results about the effect of the thermal treatment on microstructure and physical properties of low-density and high transparent silica aerogels. From our results, with tetramethyl orthosilicate as precursor and via acetonitrile supercritical drying process, silica aerogel monolith was obtained possessing the properties as low-density (0.018 g/cm³), high surface area (923 m²/g), high optical transparency (87.9 %, 800 nm). It should be noted that high transparency of silica aerogel can be maintained up to 600 °C (91.5 %, 800 nm). The mechanical properties of silica aerogel decreased with increasing heat treated temperature to 600 °C, and silica aerogels still maintained crack-free monoliths completely and possessed high homogeneous density even after 600 °C thermal treatment. Furthermore, thermal conductivity of the monoliths at desired temperatures was analyzed by the transient plane heat source method. When the temperature flowed from 25 to 600 °C, thermal conductivity coefficients of silica aerogels changed from 0.021 to 0.065 W (m K)^?1, revealed an excellent heat insulation effect in high-temperature area. Currently, the specific process developed for low-density aerogels affected by thermal treatment has not been reported in previous literature.     

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.     

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.     

Preparation and structural evolution of SiOC preceramic aerogel during high-temperature treatment

Silicon oxycarbide (SiOC) ceramic aerogels in mesopores range have been fabricated by pyrolyzing polycarbosilane aerogels in nitrogen (N₂) atmosphere. The reactants, poly(methylhydrosiloxane) and 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane have been heated in the presence of hydrochloroplatinic acid. As-prepared SiOC preceramic aerogel has specific surface area of 299 m²/g at room temperature, and decomposes during pyrolysis. Structural evolution of the aerogels as a function of heat-treatment temperature has been investigated by Fourier transform infrared spectrophotometer, X-ray diffraction analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Results indicate that tetrahedral Si–O–C network underwent four structural changes during thermal treatment from room temperature to 1600 °C.     

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.     

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.     

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.     

Foreign element doping and thermal stability of alumina aerogels

The addition of foreign elements is considered as an effective method to improve the thermal stability of alumina aerogels at a higher temperature. However, the location and stabilizing mechanism of the foreign elements in the alumina aerogel have not been carefully studied. In this work, Si or La was introduced into the network of alumina aerogels through a sol-gel strategy. The Si-doped alumina aerogel maintained high surface area (92 m²/g) and pore volume (0.572 cm³/g) even at 1300°C. The dopants prevented α-Al₂O₃ transformation at elevated temperatures (1200°C–1300°C). The distribution of foreign ions and their stabilizing mechanism were discussed in detail. The doped alumina aerogels reinforced by mullite fiber felt, with quite low density and thermal conductivity, can be used as high-temperature thermal insulations.     

Zinc deposition and dissolution in sulfuric acid onto a graphite–resin composite electrode as the negative electrode reactions in acidic zinc-based redox flow batteries

Electrodeposition and dissolution of zinc in sulfuric acid were studied as the negative electrode reactions in acidic zinc-based redox flow batteries. The zinc deposition and dissolution is a quasi-reversible reaction with a zinc ion diffusion coefficient of 4.6 × 10^?6 cm² s^?1 obtained. The increase of acid concentration facilitates an improvement in the kinetics of zinc electrodeposition–dissolution process. But too high acid concentration would result in a significant decrease in charge efficiency. The performance of the zinc electrode in a three-electrode system with magnetic stirring was also studied as a function of Zn(II) ion concentration, sulfuric acid concentration, current density, and the addition of additives in 1 M H₂SO₄ medium. The optimum electrolyte composition is suggested at high zinc(II) concentration (1.25 M) and moderate sulfuric acid concentration (1.0–1.5 M) at a current density range of 20–30 mA cm^?2. Whether in acid-free solution or in sulfuric acid solution with or without additives, no dendrite formation is observed after zinc electrodeposition for 1 h at 20 mA cm^?2. The energy efficiency is improved from 77 % in the absence of additives in 1 M H₂SO₄ medium to over 80 % upon the addition of indium oxide or SLS–Sb(III) combined additive as hydrogen suppressants.     

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.     

Chitosan Aerogels Exhibiting High Surface Area for Biomedical Application: Preparation,Characterization, and Antibacterial Study

The objective of the present work is to improve the surface area of aerogel via supercritical carbon dioxide (sc · CO₂) treatment and thus to obtain the chitosan derivative. The resulting mesoporous material exhibits the typical characteristics of aerogels such as high porosity and high surface area. The aerogels were characterized using FTIR, SEM, TEM, and thermal analysis. The specific surface areas and porosities of aerogels were determined using N₂ adsorption. The antibacterial assays were done using E. coli. The prepared chitosan aerogels show important properties such as biocompatibility, non-toxicity, and antibacterial activity, making them suitable for biomedical applications.     

Rapid preparation of Palygorskite/Al2O3 composite aerogels with superhydrophobicity,high-temperature thermal insulation and improved mechanical properties

Al₂O₃ aerogels are widely employed in heat insulation and flame retardancy because of their unique combination of low thermal conductivity and exceptional high-temperature stability. However, the mechanical properties of Al₂O₃ aerogel are poor, and the preparation time is considerably long. In this study, we present a simple and scalable approach to construct monolithic Pal/Al₂O₃ composite aerogels using solvothermal treatment instead of traditional solvent replacement, which remarkably shortened the preparation time. Subsequently, to obtain stable superhydrophobicity (θ > 152°), the Pal/Al₂O₃ aerogel was modified by gas-phase modification method. The obtained Pal/Al₂O₃ composite aerogels demonstrate the integrated properties of low density (0.078–0.106 g/cm³), low thermal conductivity (1000 °C, 0.143 W/(m·K)), good mechanical properties (Young's modulus, 1.6 MPa), and good heat resistance. The monolithic Pal/Al₂O₃ composite aerogels with improved mechanical performance and improved thermal stability can show great potential in the field of thermal insulation.     

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.     

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.     

Development of hydrophobic and optically transparent monolithic silica aerogels for window panel applications

In the present paper, highly transparent, monolithic and hydrophobic silica aerogel monoliths were prepared by using tetraethoxysilane (TEOS) as precursor and methyltriethoxysilane (MTES) as co-precursor with different MTES/TEOS molar ratios (M) by two-step acid–base catalyzed sol–gel process followed by supercritical alcohol drying. The molar ratio of TEOS, ethanol (EtOH), water (0.001 M oxalic acid catalyst) and ammonium hydroxide (1 M NH₄OH) was kept constant at 1:5:3.5:3.5 respectively, while the molar ratio of MTES/TEOS (M) was varied from 0 to 0.75. It has been observed that as the M value increases, the gelation time increases. It has been found that lower (0.25) M values resulted in highly transparent (optical transmission >90 % for a 10 mm thick sample at 700 nm wavelength) and negligible volume shrinkage (<10 %) but less hydrophobic aerogels, whereas higher (0.75) M values resulted in semitransparent (<25 % optical transmission at 700 nm for a 10 mm thick sample) aerogels with >10 % volume shrinkage but excellent hydrophobicity. A good compromise of acceptable optical transmittance (~87 % optical transmission at 700 nm wavelength for a 10 mm thick sample) with negligible volume shrinkage (6 %) were obtained at M = 0.50. The hydrophobicity of the aerogels was tested by measuring the contact angle between a water droplet and silica aerogel surface. The hydrophobicity was confirmed by Fourier transform infra-red spectroscopy and contact angle measurements. the aerogels have been characterized by percentage of volume shrinkage, optical transmittance, scanning electron microscopy, thermal conductivity measurements and thermogravimetric analysis and differential thermal analysis.     

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.     

Thermal Insulation Characteristics of Polybenzoxazine Aerogels

Polybenzoxazine (PBO) aerogels with low densities and low thermal conductivities are prepared from Bisphenol A (BPA) benzoxazine monomers by ring‐opened polymerisation using HCl as a catalyser at 10 °C. The obtained PBO aerogels have cross‐linked and 3D network structures with the densities ranging from 0.084 to 0.526 g cm^?3. The thermal conductivities under different pressures (3–10⁵ Pa, air) and different atmospheres (N₂, Ar, and CO₂, 10⁵ Pa) are investigated. The thermal conductivities are in the range of 0.0335–0.0652 W m K^?1 under ambient pressure and 0.0098–0.0571 W m K^?1 at 3 Pa. The thermal transfer mechanism under different gas pressures is analyzed with increasing pressure. Under different atmospheres, the thermal conductivities decrease as the molecular weight of the gas increases. Compared with the traditional organic foam insulating materials of phenolic foam, polyurethane and polystyrene, which have similar apparent densities, PBO aerogels exhibit lower thermal conductivity of 0.0335 W m K^?1 than that of traditional organic foam at room temperature.     

Filamentous carbon templated SiO2–NiO aerogel: structure and catalytic properties for direct oxidation of hydrogen sulfide into sulfur

Silica aerogels comprising nickel oxide nanoparticles were synthesized with no use of supercritical drying. A high specific surface area (more than 1000 m²/g), mesoporous structure and considerable stability to sintering up to 900 °C are characteristic of these aerogels. The aerogels were synthesized using the sol–gel method. Filamentous carbon was templated by silica, tetraethoxysilane being used for supplying silica. Carbon was burnt later. Analysis of the aerogel structure revealed the presence of silica nanotubes and nanofibers. Aerogel testing for direct oxidation of H₂S into S⁰ demonstrated as high as 60% conversion of hydrogen sulfide at almost 100% selectivity under stoichiometric conditions at the temperature range of 300–350 °C and 73% conversion at 100% selectivity at a considerable excess of oxygen at 160 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of reduction temperature on the preparation of zero-valent iron aerogels for trichloroethylene dechlorination

Zero-valent iron (ZVI) aerogels have been synthesized by sol-gel method and supercritical CO₂ drying, followed by H₂ reduction in the temperature range of 350–500 °C. When applied to trichloroethylene (TCE) dechlorination, the ZVI aerogel reduced at 370 °C showed the highest performance in the conditions employed in this study. Thus, the effect of reduction temperature in preparing ZVI aerogels has been investigated by several characterizations such as BET, XRD, TPR, and TEM analyses. As the reduction temperature decreased from 500 to 350 °C, the BET surface area of the resulting aerogels increased from 6 to 30 m²/g, whereas their Fe⁰ content decreased up to 64%. It was also found that H₂ reduction at low temperatures such as 350 and 370 °C leads to the formation of ZVI aerogel particles consisting of both Fe⁰ and FeO _x in the particle cores with a different amount ratio, where FeO _x is a mixture of maghemite and magnetite. It is, therefore, suggested that reduction at 370 °C for ZVI aerogel preparation yielded particles homogeneously composed of Fe⁰ and FeO _x in the amount ratio of 87/13, resulting in high TCE dechlorination rate. On the other hand, when Pd- and Ni-ZVI aerogels were prepared via cogellation and then applied for TCE dechlorination, we also observed a similar effect of reduction temperature. However, the reduction at 350 or 370 °C produced Pd- or Ni-ZVI aerogel particles in which Fe⁰ and Fe₃O₄ co-exist homogeneously. Since both Fe⁰ and Fe₃O₄ are advantageous in TCE dechlorination, the activities of Pd- and Ni-ZVI aerogels reduced at 350 °C were comparable to those of both aerogels reduced at 370 °C, although the former aerogels have less Fe⁰ content.     

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.