A facile method to fabricate monolithic alumina–silica aerogels with high surface areas and good mechanical properties

In this study, monolithic alumina–silica aerogels with high surface areas and good mechanical properties were synthesized via a facile sol–gel method without solvent exchange. Furthermore, surface areas, microstructures (up to 1300 °C), and mechanical properties of the prepared alumina–silica aerogels were investigated. The sintering and phase transformations of metastable alumina nanoparticles are suppressed owing to the uniformly distributed Si in the alumina–silica aerogels; therefore, the alumina–silica aerogels can maintain much higher specific surface areas after being calcined at 800 °C (575.5 m²/g), 1000 °C (443.2 m²/g), and 1200 °C (120.6 m²/g) compared to pristine alumina aerogels. In addition, the prepared high surface area alumina–silica aerogels show considerably higher strengths than those obtained in previous works. The compressive stress (3 % strain) and elastic modulus of the alumina–silica aerogels reached 1.78 and 65.6 MPa, respectively. The reported alumina–silica aerogels in this study can be good candidates as high-temperature thermal insulators and catalysts.     

Optimization of Alumina and Aluminosilicate Aerogel Structure for High-Temperature Performance

Alumina and aluminosilicate aerogels offer potential for use at temperatures above 700°C, where silica aerogels begin to sinter. Stability of alumina and aluminosilicate pore structures at high temperatures is governed by the starting aerogel structure, which, in turn is controlled by the synthesis route. Structure, morphology, and crystallization behavior are compared for aerogels synthesized from AlCl₃ and propylene oxide with those synthesized from a variety of boehmite precursors. The aerogels possessing a crystalline boehmite structure in the as-synthesized condition retained mesoporous structures to temperatures of 1200°C, while the AlCl₃-derived aerogels, although exhibiting higher as-synthesized surface areas, crystallized and densified at 980–1005°C.     

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.     

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.     

Influences of heat-treatment on the microstructure and properties of silica–titania composite aerogels

Silica–titania composite aerogels were synthesized via ambient pressure drying by using water glass and titanium tetrachloride as raw materials. The influences of heat-treatment at different temperature with different heating rate on the microstructure and properties of the composite aerogels were investigated by differential thermal analyzer, Fourier transform infrared spectrometer, X-ray diffraction, nitrogen adsorption–desorption, scanning electron microscope and transmission electron microscope analysis. The results indicate that the silica–titania composite aerogels heat-treated at 250 °C exhibited highest specific surface area, pore volume and average pore diameter. When the heat-treatment temperature was higher than 450 °C, the –CH₃ groups on the surface of silica–titania composite aerogels would transform into –OH groups gradually, and in the meantime, the composite aerogels network structure would be destroyed gradually and the crystallinity of TiO₂ would be improved with the increase of heat-treatment temperature. Particularly, heat-treatment at temperatures above 750 °C would cause serious damage to the network structure of the composite aerogels. The adsorption/photocatalytic activity experiments showed that the composite aerogels heat-treated at 550 °C exhibit highest darkroom adsorption efficiency, and the 650 °C-heat-treated samples exhibited highest efficiency for removing the Rhodamine B from water.     

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.     

Preparation of highly porous Al2O3 aerogel by one-step solvent-exchange and ambient-pressure drying

This work presents the preparation of alumina aerogel via sol-gel route utilizing ambient-pressure drying. A novel and efficient solvent-exchange process has been utilized as an alternative to conventional solvent-exchange processes by directly boiling the hydro-gel in solvent. High emphasis has been given in the selection of solvent based on polarity, boiling point, and specific gravity compared with water to facilitate efficient solvent-exchange and reuse of the solvent. The ambient-pressure-dried alumina aerogel was thermally treated at temperature from 300°C-1200°C to study the change in density, porosity, specific surface area, and microstructure along with crystalline properties. The ambient-pressure-dried alumina aerogel showed lower tapped density 0.108 g/cm³, specific surface area 519 m²/g, and total weight loss of 36.94% at 900°C. The degree of crystalline structure from amorphous was observed to increase with increase in thermal treatment temperature above 300°C, dominant above 700°C, whereas the transformation of bayerite γ-Al(OH)₃ to boehmite γ-AlO₂H was observed at 150°C-300°C and to γ-Al₂O₃ phase was observed at temperature of 300°C-1200°C.     

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.     

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 aging temperature on the porosity characteristics of subcritically dried silica aerogels

Silica aerogels were synthesised by subcritical drying technique which involves controlled solvent exchange and aging of the wet gel in silane solution followed by drying under controlled conditions. Effect of temperature of aging in silane solution on the porosity characteristics of silica aerogels and the thermal pore stability of the resultant gels were investigated. Aging in silane solution leads to an increased degree of condensation reactions, siloxane crosslinking and the dissolution and reprecipitation of silica monomers to the gel structure and enhances the total strength of the gel. Thermal aging of the wet gel have a pronounced effect on bulk density, linear drying shrinkage, surface area and pore volume. As the temperature of aging increases the bulk density decreases whereas the surface area and pore volume were found to increase. We could achieve a surface area of 1040 m²/g, pore volume 1.2 cc/g and an average pore size of 49 Å corresponding to an aging temperature of 70 °C. Thermal pore stability of the gel was found to be up to 700 °C above which densification of SiO₂ gel starts. The novel findings will help in tailoring the process parameters to prepare mesoporous oxides from sol–gel precursors with specific pore features.     

A comparative study on the thermal stability,textural, and structural properties of mesostructured γ-Al2O3 granules in the presence of La,Sn, and B additives

Mesoporous γ-alumina is widely used as catalyst support in various catalytic reactions of industrial interest. However, due to the instability of γ-alumina at elevated temperatures, many efforts have been reported to inhibit the α-alumina phase transition through doping with suitable metalloids, as well as transition, post-transition, or rare-earth elements. In the present study, undoped and La-, Sn-, and B-doped alumina granules were synthesized via sol-gel/oil drop method with the aim to clarify the role of the additives and their content on the porous structure as well as on the chemical, structural, and microstructural behavior of γ-alumina. XRD and DTA/TG results demonstrated that thermal stability of transition aluminas increases more than 100 °C by 3 wt% lanthanum and tin doping; however, boron doping seems to have only negligible effect on the thermal stability. On the other hand, based on nitrogen adsorption-desorption analysis, tin and boron-doped aluminas showed a higher surface area at 750 °C (between 214.74 m²/g to 245.97 m²/g) but higher loss in the surface area after calcination at 1200 °C (between 25.45 m²/g to 8.57 m²/g). On the contrary, the 3 wt% La-doped alumina sample, with a relatively high surface area at 750 °C (227.17 m²/g), exhibited the highest surface area after calcination at 1200 °C (53.07 m²/g). ²⁷Al MAS NMR and HRTEM studies indicated that the presence of 3 wt% La in alumina structure leads to thermal and mesoporous structure stability up to 1200 °C by inhibiting oxygen lattice restructuring. These results provide a comparative perspective of La, B, and Sn additives' behavior in γ-alumina.     

Improvement of thermal stability of alumina by addition of zirconia

To maintain a large surface area at elevated temperatures, zirconia was added to transition alumina. The addition of a small amount of zirconia resulted in a marked suppression of phase transformation from θ- to α-alumina. After heating at 1200°C, ZrO₂‐containing alumina exhibited a large surface area of 50 m₂/g. UV‐VIS and XRD measurements indicated that zirconia existed in a high dispersion state after calcining at 800°C. XPS measurement also showed that zirconia existed as monolayer. Zirconia monolayers are concluded to cover the alumina surface and the interaction between them may be the cause for the suppression of phase transformation and also for the maintenance of the large surface area at elevated temperatures. The interaction remains up to 1200°C, therefore, θ phase remained at 1200°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Temperature-induced changes in morphology and microstructure of electrospun mullite nanofibers fabricated from a hybrid mullite sol

Mullite nanofibers with small diameter and high surface area are an ideal candidate as the reinforcements in composite materials, and have promising applications in the fields of catalysis, filtration, thermal storage and so forth. In this work, electrospun mullite nanofibers were successfully synthesized using a hybrid mullite sol. The morphology and microstructure of fibers calcined at different temperatures were investigated. The morphology of fibers synthesized at 900 °C is porous with coarse surface, and after crystallization it becomes compact with smooth surface. The densities of fibers increase with the increasing temperatures. At 1200 °C the surface of fibers becomes coarse again, as a result of the grain growth of mullite. The crystallization path of fibers was revealed that the Al-rich mullite (4Al₂O₃·SiO₂) together with amorphous silica formed at 1000 °C, changed into mullite with higher silica contents as temperature further increased, and finally transformed into a stable 3Al₂O₃·2SiO₂ phase at 1200 °C. During this crystallization process, the flow of amorphous silica phase and the formation of mullite crystal structure benefit the densification of fibers, leading to the resultant fibers with fine and compact microstructure. The present findings can provide a guideline for the preparation of the promising high-mechanical mullite nanofibers and the synthesized nanofibers display great potential as reinforcements in structural ceramic composites.     

Research of silica aerogels prepared by acidic silica sol under the condition of atmospheric pressure drying

Acidic silica sol was used as precursor to prepare SiO₂ aerogels using the atmospheric pressure drying technology. The influence of pH, water bath temperature and concentrations of silica sol on the structure parameters and morphology were systematically studied. SiO₂ aerogel prepared with the sol concentration of 20% possessed uniform structure and the best structure parameters. Water bath temperature exhibited an obvious effect on morphology, specific surface area and porosity. Moreover, the optimal SiO₂ aerogel showed a good heat resistance up to 700?°C. A lower thermal conductivity was 0.019 W/m · K at room temperature (25?°C) and 0.044 W/m · K at 600?°C.     

Influence of aging conditions on textural properties of water-glass-based silica aerogels prepared at ambient pressure

The experimental results of aging time and temperature on the textural properties of water-glass (sodium silicate)-based silica aerogels are reported and discussed. Aging of the hydrogel for different times and temperatures led to an ability to increase the stiffness and strength of the networks. These improvements enabled the gel to withstand ambient pressure drying (APD) and, consequently, preserve the highly porous silica network without collapse. The pore size and volume increased with increasing aging temperature and time, while the specific surface area decreased. Monolithic aerogels with extremely low bulk density (～0.069 g/cm³), high specific surface area (820 m²g^?1), large cumulative pore volume (3.8 cm³g^?1), and high porosity (～96%) were obtained by aging at 60 °C for 18 hours. Therefore, easy synthesis of monolithic silica aerogels at ambient pressure is achievable using a relatively inexpensive silica precursor (sodium silicate).     

Solid-state synthesis of mullite from spent catalysts for manufacturing refractory brick coatings

This paper shows the results of the solid-state synthesis of mullite from spent catalysts discarded from fluid catalytic cracking (FCC); the catalysts are mainly composed of silica and alumina but are polluted with SO_X, forming a non-crystalline network. The synthesized mullite was used as a feedstock to thermally spray a coating onto a silica-alumina refractory brick, and its chemical resistance at high temperature was subsequently evaluated by contact with K₂CO₃ at 950 °C. Initially, the spent catalyst was thermally treated for 2 h at 600, 900, and 1200 °C to eliminate the SO_X pollutant. The heat treatment at 1200 °C completely removed the SO_X in the sample. Additionally, four thermal processes were performed by heating the spent FCC catalyst in an electrical furnace to 1500 and 1600 °C and by using an oxyacetylene flame to synthesize mullite. Thermal treatments at 1500 °C were performed with and without alumina added to the spent FCC catalyst, whereas those conducted at 1600 °C and using a flame were performed using only added alumina. In the powders thermally treated at 1500 °C, silica-rich mullite (3Al₂O₃.2SiO₂) accompanied by an excess of alumina or silica was obtained with or without alumina added, respectively. In contrast, the materials treated at 1600 °C formed alumina-rich mullite (2Al₂O₃.SiO₂), which was accompanied by an excess of alumina. Mullite was not synthesized in the flame-heated powder. The silica-rich mullite accompanied by an excess of alumina was used as feedstock powder to modify the surface of a refractory brick, improving its resistance to chemical attack by K₂CO₃ at high temperature.     

Synthesis and characterization of monolithic carbon/silicon carbide composite aerogels

Resorcinol–formaldehyde/silica composite (RF/SiO₂) aerogels were synthesized using sol–gel process followed by supercritical CO₂ drying. Monolithic carbon/silicon carbide composite (C/SiC) aerogels were formed from RF/SiO₂ aerogels after carbothermal reduction. X-ray diffraction and transmission electron microscopy demonstrate that β-SiC was obtained after carbothermal reduction. Scanning electron microscopy and nitrogen adsorption/desorption reveal that the as-prepared C/SiC aerogels are typical mesoporous materials. The pore structural properties were measured by nitrogen adsorption/desorption analysis. The resulting C/SiC aerogels possess a BET surface area of 564 m²/g, a porosity of 95.1 % and a pore volume of 2.59 cm³/g. The mass fraction of SiC in C/SiC aerogels is 31 %.     

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).     

Fabrication and characterization of the monolithic hydrophobic alumina aerogels

The monolithic hydrophobic mesoporous alumina aerogels were successfully synthesized by acid–base sol–gel polymerization of aluminium chloride hexahydrate (AlCl₃·6H₂O) in deionized water/alcohol solution (v/v = 3:7). To minimize shrinkage during drying, alumina hydrogels were aged in tetraethylorthosilicate (TEOS)/acetonitrile solution, and modified using trimethylchlorosilane (TMCS)/acetonitrile solution. Properties of the final product were examined by contact angle measurement, FTIR, FESEM, TEM and BET analyses. Surface modification was confirmed by FTIR spectroscopy. It was found that hydrophobic property of the alumina aerogels was affected by the contents of TMCS. When the molar ratio of TMCS to AlCl₃·6H₂O is 0.35, hydrophobic alumina aerogels shows lower bulk density (0.453 g/cm³) and higher surface area (495 m²/g) than those of unmodified alumina aerogels (0.933 g/cm³, 413 m²/g).     

Alumina nanofibers obtained from poly(vinyl alcohol)/boehmite nanocomposites

Poly(vinyl alcohol) (PVA)/boehmite nanocomposite (precursor) nanofibers were formed by electrospinning using a PVA aqueous solution of dispersed boehmite nanoparticles as the spinning solution. The alumina nanofibers were obtained by calcination of the precursor nanofibers between 500 and 1200°C. The specific surface area of the precursor nanofibers was around 6 m²/g, and that of the γ‐alumina nanofibers calcined at 500°C was around 300 m²/g. The specific surface areas and the fiber diameters were not affected by the alumina contents in the precursors. Also, the diameter of the alumina nanofibers was not affected by the calcination temperature of the precursor nanofibers. The pore characteristics of the alumina nanofibers decreased with increased calcination temperature due to the sintering, and nonporous α‐alumina nanofibers were obtained by calcination of the precursor nanofibers at 1200°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011