Numerical Study of Pore Sizes Distribution in Gels

We introduce a new numerical technique for the calculation of the pore size distribution in two-dimensional disordered systems. Our method is based on a triangulation technique which allows a closer measurement of pores surface without any morphological hypothesis.In this work, we focus our calculations in simulated gels. Such materials are modeled in two different conditions: by means of the Diffusion-Limited and Reaction-Limited Cluster-cluster Aggregation algorithms, DLCA and RLCA, respectively. In both situations, when the particles concentration decreases, the average pores size increases. The more compact cluster in RLCA, compared with DLCA, is consistent with the pore size distribution we have calculated. The simulated mean pore size is quantitatively in agreement with experimental data from literature.     

Solid state polymorphism of liquid crystals in confined geometries

Solid polymorphism of 4-alkyl-4'-cyanobiphenyl (nCB) was studied so far as a function of thermal history. In this paper we show that metastable solid phases of 4-octyl-4'-cyanobiphenyl (8CB) are also formed when the mesogens are confined in porous silica matrices and we study their structure by neutron diffraction and by Raman spectroscopy. Three metastable solid states are identified: one crystalline phase K', two frozen-in smectic-like phases K(s) and K'(s). We discuss the relation between the structure of the metastable solid phases and that of the mesomorph phases.     

Raman study of structural defects in SiO2 aerogels

The structure of the silica aerogels was studied by Raman spectroscopy. The spectra of the solid network resembles that of bulk silica with additional bands related to organic groups and a large amount of OH groups.The typical bands due to ring breathing also called defect bands D ₁ and D ₂ located at 490 and 610 cm^–1 are present. However, the evolution of the D ₂ band compared to that of OH band (980 cm^–1) seems apparently, in contradiction with the results previously reported in the literature. During heat treatments between 25 and 300°C the D ₂ and the OH bands increase simultaneously. Generally, in silica glass the defect band D ₂ grows at the expense of the OH groups.This result is explained by the oxidation of the organic compounds which, in this temperature range, leads to the formation of the both species (OH) and those related to siloxane rings. ²⁹Si MAS NMR results are in agreement with the Raman study.     

Brittle Fracture of Aerogels: Stress Corrosion in Alcoholic Environment

The mechanical behaviour of silica aerogels in alcoholic environment has been interpreted in terms of stress corrosion in analogy with silica glass. The chemical susceptibility factor has been determined by the dynamical method and we also measured the Weibull’s modulus which characterizes the strength distribution. These data show a stress corrosion effect which is significant in alcoholic atmosphere. The results could explain a possible fracture of gels during the supercritical drying treatment as already observed.     

Mechanical Properties of Gel-Derived Materials

The mechanical behaviour of xerogels and aerogels is generally described in terms of brittle and elastic materials, like glasses or ceramics. The main difference compared to silica glass is the order of magnitude of the elastic and rupture moduli which are 10⁴ times lower. However, if this analogy is pertinent when gels are under a tension stress (bending test) they exhibit a more complicated response when the structure is submitted to a compressive stress. The network is linearly elastic under small strains, then exhibits yield followed by densification and plastic hardening. As a consequence of the plastic shrinkage it is possible to densify and stiffen the gel at room temperature. These opposite behaviours (elastic and plastic) are surprisingly related to the same two kinds of gel features: the silanol content and the pore volume. Both elastic modulus and plastic shrinkage depend strongly on the volume fraction of pores and on the condensation reaction between silanols. On the mechanical point of view (rupture modulus and toughness), it is shown that pores and silanols play also an important role. Pores can be considered as flaws in the terms of fracture mechanics and the flaw size, calculated from rupture strength and toughness is related to the pore size distribution. Different kinds of gels structure (fractal or not fractal) have been synthesized by a control of the different steps of transformation such as sintering and plastic compaction. The relationships between structural and the elastic properties are discussed in terms of the percolation theory and fractal structure.     

Stress in aerogel during depressurization of autoclave: II. Silica gels

Although supercritical drying avoids the capillary stresses that tend to warp and crack xerogels, there are other sources of stress that interfere with the preparation of monolithic aerogels. In this paper, we present experimental results showing that there is a limit to the rate at which the pressure can be released from the autoclave without causing cracking, and that the maximum rate decreases as the gel size increases. Using an analysis developed in a companion paper, the stresses generated during depressurization are compared to the modulus of rupture of our aerogels. The calculations require knowledge of the pressure-dependence of the density of the vapor (ethanol, in our experiments), as well as the permeability and modulus of the gel network. Measurements of those properties were performed on a series of silica gels made under basic and neutral conditions. We find that the calculated stresses are large enough to account for the cracking of our gels at high rates of depressurization; moreover, the predicted dependence of stress on gel diameter is in agreement with experiment.     

The sintering of silica aerogels studied by thermoporometry

The evolution of the texture of silica aerogels during sintering is studied by thermoporometry for both neutral and base catalysed materials.During the densification the macroporous volume drops and the analysis of the mesopore size distribution evolution shows that the collapse of the smallest mesopores is responsible for the macropore volume transformation. However, corrections of the measured volumes are necessary to characterize the most compliant materials.     

Allophane: a natural gel in volcanic soils with interesting environmental properties

Volcanic (allophanic) soils are interesting in terms of the control of the greenhouse effect and the knowledge of the porous features is of importance to understand the mechanism of C and N sequestration. These soils contain a peculiar clay: allophane aggregates quite close to the synthetic mineral gels aggregates. These volcanic materials behave as gels during drying with a large irreversible shrinkage that can modify the soil physical properties. Consequently, as for silica gels, we use the CO₂ supercritical drying procedure (SD) to control the drying step and to preserve the structural and textural properties of the soils. The experimental results show that the N and C content in the soils is clearly dependent on the allophane content. We also show that the textural properties, such as specific surface area, are higher for the supercritically dried samples, compared to the classically dried samples, and SAXS results confirm the preserving effect of the SD. With these data, we propose possible effects of the specific surface area on the C and N content of the allophanic soils.     

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.     

Comparison between flexural and uniaxial compression tests to measure the elastic modulus of silica aerogel

The Young’s moduli of a set of silica aerogels have been measured by two techniques: 3-point bending and uniaxial compression. The data found by the two methods differ strongly. The uniaxial compression test gives generally underestimated values of Young’s modulus, because of geometrical effects. The appropriate gauge lengths were estimated based on the discussion of Euler buckling and nonuniform stress distribution. The measured compressive moduli were analyzed to correct for machine compliance and possible misalignment under compression of the aerogels. Similarly, moduli obtained by 3-point bending depend on the length/thickness ratio of the sample, reaching equilibrium only for ratios above about 10. The corrected compressive moduli were comparable to those measured by 3-point bending on samples of sufficient length.