Aerogel
Aerogels are a class of synthetic porous ultralight material derived from a gel, in which the liquid component for the gel has been replaced with a gas, without significant collapse of the gel structure. The result is a solid with extremely low density and extremely low thermal conductivity. Aerogels can be made from a variety of chemical compounds. Silica aerogels feel like fragile styrofoam to the touch, while some polymer-based aerogels feel like rigid foams.
Aerogels are produced by extracting the liquid component of a gel through supercritical drying or freeze-drying. This allows the liquid to be slowly dried off without causing the solid matrix in the gel to collapse from capillary action, as would happen with conventional evaporation. The first aerogels were produced from silica gels. Kistler's later work involved aerogels based on alumina, chromia, and tin dioxide. Carbon aerogels were first developed in the late 1980s.
History
The first documented example of an aerogel was created by Samuel Stephens Kistler in 1931, as a result of a bet with Charles Learned over who could replace the liquid in "jellies" with gas without causing shrinkage.Properties
Despite the name, aerogels are solid, rigid, and dry materials that do not resemble a gel in their physical properties: the name is because they are made from gels. Pressing softly on an aerogel typically does not leave even a minor mark; pressing more firmly will leave a permanent depression. Pressing extremely firmly will cause a breakdown in the sparse structure causing it to shatter like glass, although more modern variations do not suffer from this. Even though it is prone to shattering, it is very strong structurally. Its impressive load-bearing abilities are due to the dendritic microstructure in which spherical particles of average size 2–5 nm are fused together into clusters. These clusters form a three-dimensional highly porous structure of almost fractal chains, with pores just under 100 nm. The average size and density of the pores can be controlled during the manufacturing process.An aerogel material can range from 50% to 99.98% air by volume, but in practice most aerogels exhibit somewhere between 90 and 99.8% porosity. Aerogels have a porous solid network that contains air pockets, with the air pockets taking up the majority of space within the material.
Aerogels are good thermal insulators because they almost nullify two of the three methods of heat transfer – conduction and convection. They are good conductive insulators because they are composed almost entirely of gases, which are very poor heat conductors. They are good convective inhibitors because air cannot circulate through the lattice. Aerogels are poor radiative insulators because infrared radiation passes through them.
Owing to its hygroscopic nature, aerogel feels dry and acts as a strong desiccant. People handling aerogel for extended periods should wear gloves to prevent the appearance of dry brittle spots on their skin.
The slight color it does have is due to Rayleigh scattering of the shorter wavelengths of visible light by the nano-sized dendritic structure. This causes it to appear smoky blue against dark backgrounds and yellowish against bright backgrounds.
Aerogels by themselves are hydrophilic, and if they absorb moisture they usually suffer a structural change, such as contraction, and deteriorate, but degradation can be prevented by making them hydrophobic, via a chemical treatment. Aerogels with hydrophobic interiors are less susceptible to degradation than aerogels with only an outer hydrophobic layer, especially if a crack penetrates the surface.
Structure
Aerogel structure results from a sol-gel polymerization, which is when monomers react with other monomers to form a sol or a substance that consists of bonded, cross-linked macromolecules with deposits of liquid solution among them. When the material is critically heated, the liquid evaporates and the bonded, cross-linked macromolecule frame is left behind. The result of the polymerization and critical heating is the creation of a material that has a porous strong structure classified as aerogel. Variations in synthesis can alter the surface area and pore size of the aerogel. The smaller the pore size the more susceptible the aerogel is to fracture.Porosity of aerogel
There are several ways to determine the porosity of aerogel: the three main methods are gas adsorption, mercury porosimetry, and scattering method. In gas adsorption, nitrogen at its boiling point is adsorbed into the aerogel sample. The gas being adsorbed is dependent on the size of the pores within the sample and on the partial pressure of the gas relative to its saturation pressure. The volume of the gas adsorbed is measured by using the Brunauer, Emmit and Teller formula, which gives the specific surface area of the sample. At high partial pressure in the adsorption/desorption the Kelvin equation gives the pore size distribution of the sample. In mercury porosimetry, the mercury is forced into the aerogel porous system to determine the pores' size, but this method is highly inefficient since the solid frame of aerogel will collapse from the high compressive force. The scattering method involves the angle-dependent deflection of radiation within the aerogel sample. The sample can be solid particles or pores. The radiation goes into the material and determines the fractal geometry of the aerogel pore network. The best radiation wavelengths to use are X-rays and neutrons. Aerogel is also an open porous network: the difference between an open porous network and a closed porous network is that in the open network, gases can enter and leave the substance without any limitation, while a closed porous network traps the gases within the material forcing them to stay within the pores. The high porosity and surface area of silica aerogels allow them to be used in a variety of environmental filtration applications.Knudsen effect
Aerogels may have a thermal conductivity smaller than that of the gas they contain. This is caused by the Knudsen effect, a reduction of thermal conductivity in gases when the size of the cavity encompassing the gas becomes comparable to the mean free path. Effectively, the cavity restricts the movement of the gas particles, decreasing the thermal conductivity in addition to eliminating convection. For example, thermal conductivity of air is about 25 mW·m−1·K−1 at standard temperature and pressure and in a large container, but decreases to about 5 mW·m−1·K−1 in a pore 30 nanometers in diameter.Waterproofing
Aerogel contains particles that are 2–5 nm in diameter. After the process of creating aerogel, it will contain a large amount of hydroxyl groups on the surface. The hydroxyl groups can cause a strong reaction when the aerogel is placed in water, causing it to dissolve in the water. One way to waterproof the hydrophilic aerogel is by soaking the aerogel with some chemical base that will replace the surface hydroxyl groups with non-polar groups, a process which is most effective when R is an aliphatic group.Production
The preparation of silica aerogels typically involves three distinct steps: the sol-gel transition, the network perfection, and the gel-aerogel transition.Gelation
Silica aerogels are typically synthesized by using a sol-gel process. The first step of the sol-gel process is the creation of a colloidal suspension of solid particles known as a "sol". The precursors are a liquid alcohol such as ethanol which is mixed with a silicon alkoxide, such as tetramethoxysilane, tetraethoxysilane, and polyethoxydisiloxane . The solution of silica is mixed with a catalyst and allowed to gel during a hydrolysis reaction which forms particles of silicon dioxide. The oxide suspension begins to undergo condensation reactions which result in the creation of metal oxide bridges linking the dispersed colloidal particles. These reactions generally have moderately slow reaction rates, and as a result either acidic or basic catalysts are used to improve the processing speed. Basic catalysts tend to produce more transparent aerogels and minimize the shrinkage during the drying process and also strengthen it to prevent pore collapse during drying.For some materials, the transition from a colloidal dispersion into a gel happens without the addition of crosslinking materials. For others, crosslinking materials are added to the dispersion to promote the strong interaction of the solid particles in order to form the gel. The gelation time depends heavily on a variety of factors such as the chemical composition of the precursor solution, the concentration of the precursor materials and additives, the processing temperature, and the pH. Many materials may require additional curing after gelation in order to strengthen the aerogel network.
Drying
Once the gelation is completed, the liquid surrounding the silica network is carefully removed and replaced with air, while keeping the aerogel intact. It is crucial that the gel is dried in such a way as to minimize the surface tension within the pores of the solid network. This is typically accomplished through supercritical fluid extraction using supercritical carbon dioxide or freeze-drying.This section briefly describes and compares the processing strategies of supercritical drying and freeze-drying.Gels where the liquid is allowed to evaporate at a natural rate are known as xerogels. As the liquid evaporates in such manner, forces caused by surface tensions of the liquid-solid interfaces are enough to destroy the fragile gel network. As a result, xerogels cannot achieve the high porosities and instead peak at lower porosities and exhibit large amounts of shrinkage after drying. To avoid the collapse of fibers during slow solvent evaporation and reduce surface tensions of the liquid-solid interfaces, aerogels can be formed by lyophilization. Depending on the concentration of the fibers and the temperature to freeze the material, the properties such as porosity of the final aerogel will be affected.
In 1931, to develop the first aerogels, Kistler used a process known as supercritical drying which avoids a direct phase change. By increasing the temperature and pressure he forced the liquid into a supercritical fluid state where by dropping the pressure he could instantly gasify and remove the liquid inside the aerogel, avoiding damage to the delicate three-dimensional network. While this can be done with ethanol, the high temperatures and pressures lead to dangerous processing conditions. A safer, lower temperature and pressure method involves a solvent exchange. This is typically done by exchanging the initial aqueous pore liquid for a CO2-miscible liquid such as ethanol or acetone, then onto liquid carbon dioxide, and then bringing the carbon dioxide above its critical point. A variant on this process involves the direct injection of supercritical carbon dioxide into the pressure vessel containing the aerogel. The result of either process exchanges the initial liquid from the gel with carbon dioxide, without allowing the gel structure to collapse or lose volume.