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Aerogels

1. Introduction Aerogels designate dried gels with a very high relative pore volume. These are versatile materials that are synthesized in a first step by low-temperature traditional sol-gel chemistry. However, while in the final step most wet gels are often dried by evaporation to produce so-called xerogels, aerogels are dried by other techniques, essentially supercritical drying. As a result, the dry samples eep the very unusual porous texture which they had in the wet stage. !n general these dry solids have very low apparent densities, large specific surface areas, and in most cases they exhibit amorphous structures when examined by "-ray diffraction #"$%& methods. !n addition, they are metastable from the point of view of their thermodynamic properties. 'onsequently, they often underta e a structural evolution by chemical transformation, when aged in a liquid medium and(or heat treated. As aerogels combine the properties of being highly divided solids with their metastable character, they can develop very attractive physical and chemical properties not achievable by other means of low temperature soft chemical synthesis. !n other words, they form a new class of solids showing sophisticated potentialities for a range of applications. The particularly interesting properties of aerogels arise from the extraordinary flexibility of the sol-gel processing, coupled with original drying techniques. The wet chemistry is not basically different for ma ing xerogels and aerogels. This common basis has been extensively detailed in recent boo s ) . 'ompared to traditional xerogels, the originality of aerogels comes from the technique used to evacuate the liquid. 'onventionally, the term *aerogels* has been used to designate gels dried under supercritical conditions. +ore recently, materials dried by other techniques such as freeze-drying, produce materials initially nown as cryogels, now also termed aerogels. However, such an extension can be argued. !t can only be ,ustified if the pores actually occupy a very high percentage of a

sample volume, e.g., above -./, although no official definition exists. All materials that can be synthesized as wet gels by the sol-gel process can then be dried by the supercritical method to obtain aerogels. 0ew properties based upon the very open texture of these materials ma e them outstanding for some applications. To cite a few examples, aerogels can indeed contribute to high added value technical solutions for domestic applications such as in buildings double window glazing as transparent thermal super-insulators or for more restricted applications demanding a high degree of technology in space exploration and electronics. !n any case, a stri ing difference appears between two classes of compounds1 on one hand those wet gel monoliths which can be dried to aerogel monoliths without crac ing, on the other hand those wet gels which can only be obtained as fluffy aerogel powders after supercritical drying. The former categories comprise mostly silica or the silicates where silica is a ma,or component, organic polymeric aerogels, and carbon aerogels derived from these organic aerogels. 2or other oxides, monolithicity with a mechanical resistance sufficient for easy handling has not really been achieved. 2or instance, aluminaactually boehmite Al3#3H&-monolithic gels have been made by 4oldas.5 6ut these are xerogels dried by evaporation, which therefore underta e a significant contraction during drying and reach a dry specific pore volume #78./& much lower than silica aerogel monoliths. !n what follows, we therefore first summarize very briefly the chemistry of sol-gel processing, simply to stress out the main chemical differences between silica, carbon, and organic polymers on one hand, the other oxides on the other. II. Sol-Gel Processing 9ol-:el processing designates a type of solid materials synthesis procedure, performed in a liquid and at low temperature #typically T ; ).. '&. As previously mentioned, the physics and chemistry involved in sol-gel synthesis has been detailed in many review

papers as well as in boo s.<,= The solids which were addressed were then exclusively inorganic1 mostly oxides or hydroxides, formed by chemical transformation of chemical solutes termed precursors. The solid is formed as the result of a polymerization process which involves the establishment of +-3H-+ or +-3-+ bridges between the metallic atoms + of the precursor molecules. 9uch transformations are the equivalent of the polymerization process well- nown to occur in organic chemistry and which consists of the establishment of direct bonds between the carbon atoms of organic precursors. Actually, the traditional division between inorganic and organic chemistry has been such that, during a long time, these two fields of sol-gel science were addressed by quite different groups of chemists, with virtually no contact between them. +ore recently, these two fields of chemistry have begun to merge with the development of hybrid organic-inorganic gels. - +oreover, supercritical drying could be applied with reasonably good success to ma e monoliths, not only of silicates, but also of organic polymers. $egarding inorganic gels, that is to say mostly oxides, independent solid colloidal particles #i.e., nanoparticles with a size below a micrometer& are often formed, in a first step of the process. >ach colloidal particle has a more or less densely cross-lin ed internal structure, as illustrated in 2igure )a. !t is usually easy to maintain such particles in a dispersed state in the solvent, in which case a colloidal suspension also termed a sol is obtained. !n a second step, these colloidal particles can be made to lin with each other, while they are still in the solvent, so as to build a threedimensional open grid, termed a gel #2igure )b&. Hydrophilic colloidal solutions are formed of colloidal particle that remain separated because of electrical charges on their surface and in the surrounding solution. These charges create repelling forces which prohibit coagulation of the colloidal particle. The point at which the hydrogel formation, called gelation, occurs depends on the micelle concentration, temperature, ionic strength of the solution and especially the pH. The overall process produces a reticulate, metastable polymer with an open structure in which the primary number units are held together by either chemical bonds, hydrogen
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bonds, dipole forces or van der ?aals interactions. This framewor includes almost all the solvent. The gelation time ranges from a few minutes to a ).. h and the density of the hydrogel increases with increasing concentration of the original salts in the solution and with the gelation rate. The homogeneity of the hydrogel depends on the solubility of the reagents in the solvent used, the sequence of addition of reactants, the temperature and the pH. The transformation of a sol to a gel constitutes the gelation process, and the gels which are obtained are then termed colloidal gels. 3n the other hand, it is also quite possible to directly form some gels from rather linear polymer formed from a precursor solution, without the intermediate occurrence of individual particles. ?hen this occurs, the gels are termed polymeric gels.

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%ue to the possibility obtaining highsurfacearea solids with

homogeneous compositions and controlled porosity, sol@gel methods have been widely employed for the synthesis of micro and mesoporous materials. There are three strategies that enable control of pore size 1 9olvent-templating of the silica framewor . #Aerogel, "erogel& The preparation of hybrid organic-inorganic membranes followed by extraction or pyrolysis of the organic constituents that serve as micropore templates. 9urface derivatization of pre-formed pore networ s with welldefined molecular species.
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A. Inorganic Gels The first inorganic gels accidentally synthesized by chemists were silica gels made by >belmen in )A=8. 5A 6ut natural gels of an organic nature are common in the living world. As an example, the eye vitrea is a natural gel. 3verall, gels are materials at the border between organic, inorganic, and biological chemistry. Aerogels, which are only at the beginning of their development, are certainly among the most amazing of these new materials because they can retain, in the dry state, the very open type of networ which they had in the wet state. The first precursors used in sol-gel processing were metallic salts +" n in which a metal + is lin ed to some number n of anions ". !n solution in aqueous solvents, these precursors are present as ionic species in which the metal atoms exist as solvated cations +BH53C0 zD. The reactions to form sol particles and gels comprise hydrolysis reactions which replace H53 groups by 3H ones with loss of protons and, condensation reactions leading to the construction of +-3H-+ *ol* bridges or +-3-+ *oxo* bridges with elimination of water molecules. 9everal concurrent mechanisms have been proposed for these reactions. 2or instance, an H53 ligand can first be replaced by an 3H- one by direct substitution. A proton exchange mechanism through transition hydrogen bonds according to eq ) proposed by Eivage et al.,) similar to that occurring in the ionization of water itself, is also possible. 0ext, various condensation reactions can lead to the formation of ol bridges or oxo bridges, as in the reaction mechanism in eq 5.)

3verall, a model termed the partial charge model was proposed by Eivage et al.,) as a development of the electronic transfer concept developed by 9anderson.5- This model ma es it possible to establish rather satisfying numerical predictions on the complexes formed in solution. !t relies on the building of transition states by nucleophilic or electrophilic attac s, followed by redistribution of the electronic cloud #i.e., modification of the polarity of each bond& among all the atoms in a given transition state. As a result, the partial charge as well as the electronegativity of each atom in this transition state are modified. ?hen a group of near neighbor atoms in the transition state reaches an added partial charge which is an integer #e.g., -), ., or D), etc.&, this group of atoms becomes electronically *self sufficient*, and it separates as a leaving group. A leaving group can be an anion, a cation, or a neutral molecule such as H53 when the added partial charge #5 H D 3& reaches .. 2or silica gels, an important inorganic precursor was sodium metasilicate 0a59i3<, also termed water-glass, which reacts with an acid such as H'l according to reactions similar to eq <1

As indicated by this reaction, a salt is produced, which must be eliminated by tedious dialysis. This synthesis method was first used by Fistler to produce the first aerogels. <. As water-glass is cheap, an industrial process based on this precursor was developed for some time by 6A92.<) The main inconvenience of these precursors is that, most frequently, they require water as the solvent, followed by dialysis to eliminate the foreign ions. This does not give much flexibility in ad,usting the hydrolysis and condensation reaction rates at the desired level, hence, to tailor the texture of a gel. The use of metallic salts as sol-gel precursors has recently seen a renewed interest with the use of organic solutions, in which an organic, slow *proton scavenger* is dissolved. <5 The metallic salt must be in its hydrated form, e.g., 'r#03 <&<G-H53. The solvent can be ethanol, and the slow proton scavenger can be propylene oxide

or an epoxide #e.g., ),5-epoxybutane, ),5 epoxypentane, 5,<epoxy#propyl&benzene, trimethylene oxide, glycidol, epichlorohydrin, epibromohydrin&. The hydrated cation B+#H 53&0CzD must be acidic, so that a slow deprotonation reaction occurs with the proton scavenger. The protonated scavenger underta es an irreversible ring-opening reaction with the metal salt anion, while the solvated cation transforms to aquo-hydroxo species B+#3H&x#H53&0-xC#z-x&D which underta e condensation reactions later on. 0ice wet gel monoliths can in this way be obtained with 'r, 2e, Al, Hr, and other cations.<5 The second generation of precursors, which are now largely used, are al oxides +#3$&n. These chemicals are compounds formed by combination of a metal + with an al oxide group 3$, where $ designates an al yl group. They are characterized by the existence of +-3 polar covalent bonds in their molecules. !n practice, they are often available as more or less small polymerized complexes, often in solution in their parent alcohol. Their transformation is carried out in an organic solvent and water becomes a reactant added in controlled proportion. The sol-gel reactions in which they participate are hydrolysis reactions #eq =&, which lead to the replacement of 3$ ligands by 3H ones, followed by condensation reactions similar to those occurring with metal salts. B. Chemical Differences between Silica and Other O ides Sol-Gel Chemistr! The mechanisms of hydrolysis reactions depend on nucleophilic chemical attac s on the metal +, ) which depends on the partial positive electronic charge D carried out by +. +any metal atoms such Al, Hr, and Ti carry a positive partial charge of significant magnitude, e.g., 7..8I and ..8< in Hr#3>t& = and Ti#3>t&=, where >t designates an ethyl group. Hence, the nucleophilic attac of 3 atoms from water molecules, which carry a negative partial charge , is easy. 6oth the hydrolysis and condensation reactions of these precursors are fast, so that it becomes difficult to experimentally measure them separately. 3verall, with these precursors, it is necessary to globally reduce the gelation inetics #hydrolysis plus condensation& to obtain gels. +oreover, the oligomers #i.e.,

polymers with a relatively small number of metal atoms&, which are progressively formed as a result of hydrolysis and condensation reactions, are relatively pac ed clusters, such as the Al )< intermediate cluster from which all alumina gels are derived.

9ilicon precursors, mostly al oxides 9i#3$& =, constitute an important exception which explains that they have been much more extensively studied than precursors of other metals +. !n these al oxides, $ often is an al yl 'H< group, so that the precursor is termed tetramethoxysilane, or T+39, or an ethyl '5HI, in which case the precursor is termed tetraethoxysilane, or T>39. This exception comes from the fact that 9i atoms carry a reduced partial positive charge, e.g., D ..<5 in 9i#3>t&=. Hence, the global gelation inetics of 9i#3$&= al oxides can be very slow. The hydrolysis and condensation reactions of 9i al oxides therefore need to be catalyzed, either with bases which carry strong negative charges #e.g., 3H-, but also strong Eewis bases such as 2 - ions& or with acids #e.g., HD& which carry a strong positive charge and are able to attac the 3# -& atoms from the al oxy groups 3$ lin ed to the metal +. !n practice, the relative magnitudes of the hydrolysis and condensation rates are sufficiently slow to be independently controlled. 3verall, silica gels with a texture closer to the polymeric gels of organic chemistry are obtained when the hydrolysis rate is faster than the condensation rate, which requires the addition of an acid catalyst or proton donor. 3n the other hand, proton acceptors, i.e., bases, accelerate condensation reactions faster than hydrolysis, which favors the formation of denser colloidal silica particles and colloidal gels. The
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ability to control these inetics has important consequences regarding the adaptation of silica chemistry for a given type of aerogel application, as this is discussed in the related sections. A general flowchart for a complete sol-gel process is shown in the 2igure. After gelation, the wet gel can optionally be aged in its mother liquor, or in another solvent, and washed. Then it must be dried. C. Su"ercritical Dr!ing The traditional drying technique, at the origin of the label *aerogel*, is supercritical drying. This type of drying prevents the formation a liquid-vapor meniscus which recedes during the emptying of the pores in the wet gels. As this meniscus is due to the surface tension of the liquid, a capillary pressure gradient is built in the pore walls, which is able to collapse most part of the pore volume. To avoid this event, it is necessary to annihilate the liquid surface tension and one convenient way to do so is to transform this liquid in a supercritical fluid with a null surface tension. 9upercritical evacuation of the liquid-phase impregnating the porous volume of the wet gel permits the recovery of a ind of *dry solid image* of the wet material. This drying procedure releases the porous texture quite intact by avoiding the pore collapse phenomenon. D. Insulating Pro"ertie

The

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above figure shows typical order of magnitude of the thermal conductivity of silica aerogel compared to other insulating materials, for ). mm thic slabs #. Chemistr! of $!dro"hobicit! A second quality is required in order to be used in a sustainable manner, i.e, silica aerogels must exhibit good hydrophobic properties with time on stream. 3ne pertinent method to reach this goal is to co-gel some silicon precursor containing at least one nonpolar chemical group, such as a 'H<-9i bond, with the normal silicon precursor. Hydrophobic aerogels were synthesized from methyltrimethoxysilane #+T+9& and T+39 by hydrolysis in basic conditions followed by supercritical drying in methanol. !n these high-temperature drying conditions, the aerogel surface was dehydrated, and these authors found that aerogels made from more 5./ +T+9 would float on water and hence were hydrophobic. However, for a higher proportion of +T+9, the condensation degree of silica was reduced. As the hydrolysis and condensation rates of +T+9 are much lower than those of T+39, a quasi two-step gelation process was achieved. !ndeed, as this was well shown by HJsing et al., this particular gelation occurs in two-steps1 first, the T+39 reacts and then the +T+9 is grafted through the silanol surface groups of the gel giving surface 9i-.-9i-'H< functions.).K The methyl groups in +T+9 could also be replaced by other types of functionalities with similar hydrophobization and gel structure results.).K The hydrophobization of silica aerogels with +T+9 can be summarized by the reaction scheme.

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A""lications Thermal !nsulation, Acoustic !nsulation, 'atalyst 9upport, 3ptical applications, 0uclear ?aste 9torage, 2iller for paints or others, low dielectric constant materials, 6atteries. References

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Eivage, L.M Henry, +.M 9anchez, '. 9ol-:el 'hemistry of Transition +etal 3xides. Prog. Solid State Chem. 1&'', 18, 5I-. 5. 4oldas, 6. >. J. Mater. Sci. 1&(), 10, )AI8. <. 6rin er, '. L.M 9cherer, :. ?. Sol-Gel Science. The Physiscs and Chemistry of Sol-Gel Processing, Academic Nress, 0ew 4or , )--.. =. Nierre, A. '. ntrod!ction to Sol-Gel Processing, Fluwer, 6oston, )--A. I. Chemistry of Aerogels and Their Appli ations Alain C. Pierre and Grard M. Pajonk Chem. Rev. 2002, 102, 4243!4265

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