A. Alaoui

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.

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.

Mechanical Properties and Brittle Behavior of Silica Aerogels

Sets of silica gels: aerogels, xerogels and sintered aerogels, have been studied in the objective to understand the mechanical behavior of these highly porous solids. The mechanical behaviour of gels is described in terms of elastic and brittle materials, like glasses or ceramics. The magnitude of the elastic and rupture modulus is several orders of magnitude lower compared to dense glass. The mechanical behaviours (elastic and brittle) are related to the same kinds of gel characteristics: pore volume, silanol content and pore size. Elastic modulus depends strongly on the volume fraction of pores and on the condensation reaction between silanols. Concerning the brittleness features: rupture modulus and toughness, it is shown that pores size plays an important role. Pores can be considered as flaws in the terms of fracture mechanics and the flaw size is related to the pore size. Weibull’s theory is used to show the statistical nature of flaw. Moreover, stress corrosion behaviour is studied as a function of environmental conditions (water and alcoholic atmosphere) and temperature.

Slow crack growth in aerogels

Abstract The chemical susceptibility was measured by a dynamic method on aerogels immediately after supercritical drying and after oxidation treatment. Five loading speeds between 10 μm/min and 100 mm/min were used. After oxidation treatment, the Weibull modulus increased, which indicates a narrowing of the strength distribution. Toughness of the aerogels was measured by the single edge notch beam technique. ‘As-prepared’ aerogels did not show slow crack propagation. However, as the oxidized materials exhibit a stress corrosion phenomenon, the crack propagation rate was evaluated using the median value of strengths obtained with the highest crosshead speed. The lifetime prediction is estimated as a function of failure probability and from a proof testing experiment.

Large Scale Porous Structure in Gels and Relationship with Their Plastic Behavior

Silica gels (classical aerogels and composite aerogels) have been prepared by classical gelation and addition of silica soot in the gelifying solution before gelation. Due to the aggregation mechanisms, these structures are characterized by a fractal organization. The fractal network previously described in the literature (1–100 nm) which results from the aggregation mechanism of the organosiloxane is affected by the addition of the silica soots. Ultra Small Angle X-ray Scattering (USAXS) experiments (done at ESRF) shows that besides the fractal network built by the organosiloxane, the silica soots are forming another porous structure at a higher scale.The mechanical properties seem to be dependent on this large pore structure. Under isostatic pressure, aerogels display an irreversible shrinkage caused by plastic deformation. As a consequence of this plastic shrinkage it is possible to densify, by the pore collapse tending towards the silica glass. The densification mechanism is different from the one obtained by a sintering at high temperature. The pore collapse mechanism is favored by the large pores structure of the composite aerogels, in contrast to viscous sintering.

Mechanical behaviour of highly porous glasses

The mechanical behaviour of highly porous glassy materials (pore volume higher than 85%) is investigated using Hg porosimetry. Because of the small pore size of these materials, Hg liquid cannot enter their porous network and consequently induces an isostatic pressure. Due to the high compliance of the solid network of these materials, compression results in the sample shrinkage. The experiments described in this paper show that an isostatic pressure applied to highly porous glasses induces an irreversible volume shrinkage which can be associated with an unexpected plastic behaviour and structure strengthening. The magnitude of the plastic shrinkage and the increase of the associated mechanical properties depend on the starting bulk density. The irreversible compaction can be explained by siloxane bond formation between clusters constituting the porous glasses, retaining the strained structure. This densification process could offer a new way to synthesise glasses at room temperature.

Weibull analysis of the mechanical strength of silica gels

Since gels are typically brittle materials, reliable analyses are essential to determine the strength distribution. The mechanical strength of silica gels has been measured by the three point bending technique. Based on the Weibull function, the statistical analysis allows determination of the Weibull modulus (m), which characterizes the strength distribution and the flaw size effect.Two kinds of gels, alcogels and aerogels, have been investigated with respect to their different mechanical behaviour owing to the transformations occurring during the supercritical drying (SD). The toughness of the two materials has been also measured by the SENB technique. It appears that the strength increases by a factor greater than two during SD, the KIC increases slightly. However, m is not greatly affected which would suggest that SD does not induce significant flaws or defects change in the network.

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.