Globally anisotropic high porosity silica aerogels

We discuss two methods by which high porosity silica aerogels can be engineered to exhibit global anisotropy. First, anisotropy can be introduced with axial strain (i.e. axial compression). In addition, intrinsic anisotropy can result during growth and drying stages and, suitably controlled, it can be correlated with preferential radial shrinkage in cylindrical samples. We have performed small angle X-ray scattering (SAXS) to characterize these two types of anisotropy. We show that global anisotropy originating from either strain or shrinkage leads to optical birefringence and that optical cross-polarization studies are a useful characterization of the uniformity of the imposed global anisotropy.     

Mechanical strength of silica aerogels

Pure silica aerogels are obtained by hypercritical evacuation of the solvent. The strength is measured by the three-point flexural test on monolithic parallelepipedic samples and by a diametral compression test on cylindrical samples. The stress-strain curve shows a perfect elastic behaviour and the “conchoidal” fracture morphology indicates that the material is as brittle as a conventional glass. The mechanical properties are followed as a function of the bulk density. Aerogels with the highest porosity (P > 95%) reveal a maximum flexural strength lower than 10⁻² MPa. A model is proposed to account for the obtained mechanical properties.     

Enhancing mechanical properties of silica aerogels

Low-density monolithic silica and hexylene-bridged polysilsesquioxane aerogels were chemical vapor deposition (CVD) treated with hexamethyldisilazane or hexachlorodisilane silylating agents producing TMS (trimethylsilane) or Si layers on the aerogel. Reinforcing the weak aerogels by controlled deposition process improved their compressive strength and preserved their properties characteristic of low-density aerogels. When the silica and hexylene-bridged polysilsesquioxane aerogels were CVD treated with hexamethyldisilazane, the compressive modulus more than doubled in some cases. However, when treating hexylene-bridged aerogels with hexachlorodisilane the compressive modulus increased six fold. Not only did CVD treatment of the aerogels improve the compressive modulus, but the low densities, high surface areas, high porosities, and the transparency of the aerogels were not significantly affected.     

A SAXS study of silica aerogels

Aerogels produced by hypercritical drying of gels from hydrolysis of TMOS in various pH conditions and subjected to a densification process were studied by SAXS using the LURE synchrotron facility. The evaluation of scattering data combined with BET measurements leads to a model of aerogels consisting of a light density matrix in which meso- and macro-pores are embedded. No fractal features were observed for the gels, the Porod's limit having an exponent n = 4. This could mean that either these aerogels are not fractals or that the SAXS method suffers from an inherent ambiguity for fractal dimension D = 3.     

High resolution patterning of silica aerogels

Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag⁺ ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 × 70 μm, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed by Ag clusters with a size of several μm, separated by thin layers of silica.     

Large deformation of chlorotrimethylsilane treated silica aerogels

Silica aerogels were prepared through an acid-base process and surface modified with chlorotrimethylsilane. This novel application of a common non-crosslinking surface modification to improve mechanical properties allows the treated aerogels to deform plastically to compressive strains greater than 80% without macroscopic damage. This improvement in mechanical properties remains after heating in air at 500 °C for 3 h, as do residual organic groups. Heating at 700 °C for 1 h removes all organics and the aerogel behaves similar to the unmodified control. The treated aerogels also exhibit a greater resistance to sintering. Nitrogen adsorption measurements show a reduction in the number of micropores with surface modification. It is concluded that the organic monolayer increases the ductility of the silica network by filling and strengthening surface micropores that serve as crack initiators, and that these organics remain effective at elevated temperatures.     

Ultralow density silica aerogels prepared with PEDS

This paper deals with the synthesis of ultralow density silica aerogels using polyethoxydisiloxanes (PEDS) as the precursor via sol-gel process followed by supercritical drying using ethanol solvent extraction. Ultralow density silica aerogels with 5 mg/cc of density were made for the molar ratio by this method. A remarkable reduction in the gelation time was observed by the effect of the catalyst NH₄OH at room temperature. The microstructure and morphology of the ultralow density silica aerogels were characterized by the specific surface area, S_BET, SEM, TEM and the pore size distribution techniques. The results show that the diameter of the silica particles is about 13 nm and the pore size of the silica aerogels is about several nm. The specific surface area of the silica aerogel is 339 m²/g and the specific surface area, pore volume and average pore diameter decrease with increasing density of the silica aerogel.     

Superhydrophobic silica aerogels based on methyltrimethoxysilane precursor

The experimental results on the synthesis and physicochemical properties of superhydrophobic silica aerogels, with the highest ever obtained contact angle (173°), using methyltrimethoxysilane (MTMS) precursor, methanol (MeOH) solvent and ammonium hydroxide (NH₄OH) catalyst, are reported. The molar ratios of NH₄OH/MTMS (N), H₂O/MTMS (H) and MeOH/MTMS (M) were varied from 4.25 × 10⁻² to 3.5 × 10⁻¹, 2 to 10 and 1.75 to 17, respectively. It has been found that the gelation time decreases with increase in N and H values and it increases with increase in M values. The bulk density of the aerogels was found to decrease with increase in N, H and M values. It has been observed that the volume shrinkage increases with decrease in N and H values and increases with M values. In the case of catalyst concentration variation, the contact angle (θ) increases slightly from 159° to 167° with increase in N values. On the other hand, in the case of H₂O and MeOH variations, the θ first increases from 162° and 160° up to the values of 173° and 167° and then decreases to 160° and 159° with increase in H and M values, respectively. All the MTMS aerogels are opaque to the visible light. The aerogels retain their hydrophobicity up to a temperature of 480 ° C. The thermal conductivity of the aerogels was found to be around 0.095 W/m K except for the aerogels with higher bulk density (>0.3 g/cm³, at a lower H value of 2) whose thermal conductivity was around 0.109 W/m K. The aerogels have been characterized by Fourier transform infrared spectra (FTIR), thermogravimetric and differential thermal analyses (TGA-DTA) and scanning electron microscopy (SEM) techniques. The results have been discussed by taking into account the hydrolysis and condensation reactions and SEM observations.     

Nanostructural damage associated with isostatic compression of silica aerogels

Isostatic compression of silica aerogels is known to allow densification of these highly porous materials. However, at the onset of compression, hydrophobic and consequently slightly reacting aerogels, exhibit a decrease in bulk modulus. This unusual behavior is associated with damage occurring at low pressures which recovers with further density increase. Damage development and healing are analyzed measuring elastic modulus and, for the first time, internal friction as a function of compression. It is proposed that the origin of damage and healing could be associated with the rupture of tenuous links between clusters of dense silica particles at low density levels, and with the creation of new links between the resulting arms and reacting species that are revealed at cluster interface under higher pressure.     

A new route to aerogels: Monolithic silica cryogels

We have explored several different gel syntheses and drying procedures for producing silica cryogels with similar properties to those of silica aerogels, particularly in terms of monolithicity, density, porosity and surface area. These materials could be a suitable alternative to silica aerogels and ambigels. Some successful preparation methods are presented and properties of the corresponding cryogels are discussed, including comparison of these materials to supercritically dried products and an assessment of the effects of the experimental variables in the preparation process on the properties of the resultant cryogels. Two routes for the preparation of cryogels are highlighted, one of which is especially attractive as it has the advantage (compared to the known syntheses of APD aerogels) of not requiring any solvent exchange step.     

Effect of uni-axial loading on the nanostructure of silica aerogels

Aerogels are unique materials offering a combination of remarkable properties that make them useful in a wide range of applications. However, aerogel materials can be difficult to work with because they are fragile. The intent of the work presented here was to study the relationship between axial loading and pore structure in aerogel material. Silica aerogel samples with a bulk density of 0.1 g/mL were compressed by uni-axial force loads from 1 to 5 kN which resulted in stress levels up to 23 MPa. The resulting change in the pore distribution was observed using nitrogen desorption analysis and scanning electron microscopy. Uncompressed aerogel samples exhibit peak pore volume at diameters of about 20 nm. As the aerogels are subjected to increased loading, the location of the peak volume moves to smaller diameters with a reduced volume of pores occurring above this diameter. The peak diameter, the average pore diameter and pore volume all decrease and scale with increasing maximum stress while the surface area of the aerogel samples remains unaffected at about 520 m²/g. When combined with data from the literature, the relation between maximum pore diameter and applied stress suggests a failure mechanism dominated by bending induced fracture.     

Mechanical properties of polymer-modified silica aerogels dried under ambient pressure

Silica gels prepared by copolymerizing tetraethylorthosilicate with 3-aminopropyltriethoxy-silane were modified using polymer derived from toluene diisocyanate and dried under ambient pressure. The successful preparation of silica aerogels depended on the effective control of shrinkage during drying. The resulting material, polymer-modified silica aerogel, was then characterized by thermogravimetric analysis and uniaxial compression tests. Results indicated that the apparent elastic modulus and compressive strength of the polymer-modified silica aerogels decreased with increasing amounts of incorporated polymer because of decreasing shrinkage and density, while the strains at the surface cracking point and the final failure point increased significantly during compression tests. The strength and modulus of the silica skeleton could be calculated from the apparent strength and modulus of the silica aerogels respectively. It was interestingly shown that the elastic modulus of the silica skeleton of the silica aerogels increased because of the incorporated polymers, while the polymers had no effects on the compressive strength of the silica skeleton. In addition, the relationships between the apparent elastic modulus or the apparent compressive strength of the polymer-modified silica aerogels and their shrinkage were quantitatively expressed.     

Synthesis and characterization of germanium sulfide aerogels

The synthesis of germanium sulfide gels by thiolysis reactions of a non-aqueous solution of Ge(OEt)₄, followed by supercritical fluid extraction to create aerogels, is described. Analysis of the as-prepared GeS_x aerogels by powder X-ray diffraction (PXRD) and surface area analysis reveals an amorphous structure exhibiting very high surface areas, 755 m²/g, that rival those of the best SiO₂ aerogels when compared on a per mole basis. Transmission electron microscopy shows that the aerogel material is composed of a continuous network of GeS_x colloidal particles assembled in a three-dimensional architecture. A detailed comparison of GeS_x aerogels and their xerogel (bench-top dried) counterparts in terms of the influence of the synthetic methodology on morphology and surface area is reported. In the presence of adventitious moisture, the amorphous GeS_x is oxidized to a crystalline phase identified by X-ray photoelectron spectroscopy, Raman spectroscopy and PXRD cell refinement to be hexagonal GeO₂.     

Preparation and characterization of monolithic alumina aerogels

Alumina aerogels were prepared by a sol-gel method combined with the ethanol supercritical drying technique using aluminum tri-sec butoxide and nitric acid as the precursor and catalyzer respectively. This method affords high-surface-area alumina aerogel monoliths without the use of complexing agents. The structure and morphology of the aerogels were investigated by TEM, XRD, FTIR and BET techniques. The results confirmed that the as-prepared alumina aerogel possessed a network microstructure made up of pseudoboehmite fibers and a surface area of 690 m²/g. It was transformed to γ-Al₂O₃ after heat treatment at 800 °C without a significant loss in surface area. DMA analysis and hotdisk thermal analysis were performed to characterize the mechanical and thermal properties of the samples. The results indicated that the alumina aerogel was robust and exhibited excellent thermal insulating properties. The elastic modulus was up to 11.4 MPa after drying, which is the one of the highest modulus of alumina aerogels ever reported. The thermal conductivities at 30 °C and 400 °C were 0.028 W/mK and 0.065 W/mK respectively.     

Porous texture characteristics of a homologous series of base-catalyzed silica aerogels

Eighteen samples of base-catalyzed silica aerogels obtained using various tetraethylorthosilicate (TEOS) and water contents in the reaction system were characterized using N₂ adsorption. From the observed pore size distribution and adsorption isotherms the volumetric and surface fractal dimensions were determined and also the range of power-law behaviour of the porous network. The porous texture of both the bulk aerogel and surface of clusters appeared to be dependent on the concentration of reactants. The water content, however, emerges as a factor controlling surface fractal structure, its principal effect being exerted on the pore volume in the mesopore size range.     

Synthesis of fluorine doped silica gel and its properties at high temperature

Fluorine doped silica gels were synthesized by using the sol-gel processes of (A) SiF₄(g) and H₂O(1) and (B) the mixed solution of Si(OC₂H₅)₄, C₂H₅OH, H₂O and H₂SiF₆. By the former process we obtained a gel of relatively high fluorine content (8–12 at.%F), while we could synthesize the gel of 0–12 at.% F by adjusting the F/Si ratio of the starting solution mixtures by the latter process.

The defluorination behavior and the structural change of these gels at high temperature were studied by heating-mass spectrometry, IR and ESR measurements. The results revealed the following: (1) defluorination by liberation of SiF₄(g) was admitted from temperatures at about 400°C and was controlled by the diffusion of fluorine in the gel bulk. (2) The peak separation analysis for the IR band of 1300-900 cm⁻¹, where the stretching vibrations of Si---O and Si---F appear, showed that the change of the band shape resulted from the increase or the decrease of the Si---F bonds and the change of the bond angle of Si---O---Si as well as the change of the force constant accompanied by fluorination or defluorination. (3) The defects of the Si E′ center were induced by X-ray irradiation depending on the degree of the defluorination, and were reduced by the heat treatment. However, with the heat treatment at temperatures higher than 1000°C, the E′ center increased again. The IR spectra suggest that this behavior might correspond to the gel-glass trasition.     

Cost-effective synthesis of silica aerogels from fly ash via ambient pressure drying

Silica aerogels were synthesized from the industrial fly ash by ambient pressure drying method. The process consists of two stages, preparation of sodium silicate solution from fly ash by hydrothermal reaction with sodium hydroxide, and synthesis of porous silica aerogels from the obtained sodium silicate solution. Silica wet gels were formed by vitriol-catalysis or resin-exchange-alkali-catalysis of the obtained sodium silicate solution. The trimethylchlorosilane(TMCS)/ethanol(EtOH)/hexane mixed solution was used for solvent exchange/surface modification of the wet gel so as to obtain porous silica aerogels via ambient pressure drying. The results indicated that the synthesized silica aerogels were lightweight and hydrophobic. The BET specific surface area, pore volume and average pore diameter were 362.2-907.9 m² g^− 1, 0.738-4.875 cm³ g^− 1, and 7.69-24.09 nm respectively. Particularly, the synthesized silica aerogels by resin-exchange-alkali-catalysis method showed uniform mesoporous structure, and had much higher specific surface area (907.9 m² g^− 1) and pore volume (4.875 cm³ g^− 1) than that of by vitriol-catalysis process.     

Changing poisson’s ratio of mesoporous silica monoliths with high temperature treatment

The elastic moduli of mesoporous (fractal pore structure with a statistical pore size distribution with a maximum in the mesopore region) silica monoliths (silica aerogels) were measured in situ during calcination using the resonant beam technique. Above a temperature of approximately 573 K, a significant increase of the elastic moduli with increasing heat treatment temperature was observed, which was attributed to the rearrangement and completion of the network. Poisson’s ratio is close to zero up to this temperature and then increases to a positive value typical for isotropic bodies.     

Synthesis and characterization of high nickel-containing mesoporous silica via a modified direct synthesis method

A method by modifying tetraethyl orthosilicate (TEOS) with nickel species has been developed for the synthesis of mesoporous silica with high nickel content (up to 14.7 wt% of Ni). Using the method, nickel-containing mesoporous materials were obtained with high BET surface area and pore volume. The materials were characterized by means of X-ray powder diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, N₂ adsorption, Fourier transform infrared. Nickel species were incorporated into the silica frameworks. Formation of nickel phyllosilicates was also confirmed. After activation, mesostructures are still intact. Small nickel clusters embedded in the silica walls were found.