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C. J. Brinker and G. W. Scherer, Sol-Gel Science - The Physics and Chemistry of Sol-Gel Processing, New York, Academic Press, 1990. Sol-gel chemistry http://www.psrc.usm.edu/mauritz/solgel.ht ml The Sol-gel gateway http://www.solgel.com
The Sol-Gel process allows to synthesize ceramic materials of high purity and homogeneity by a process occurs in liquid solution of organometallic precursors (TMOS, TEOS, Zr(IV)-Propoxide, Ti(IV)Butoxide, etc. ), which, by means of hydrolysis and condensation reactions, lead to the formation of a new phase (SOL). M-O-R + H2O M-OH + R-OH (hydrolysis) M-OH + HO-MM-O-M + H2O (water condensation) M-O-R + HO-M M-O-M + R-OH (alcohol condensation) (M = Si, Zr, Ti)
The SOL is made of solid particles of a diameter of few hundred of nm suspended in a liquid phase. Then the particles condense in a new phase (GEL) in which a solid macromolecule is immersed in a liquid phase (solvent). Drying the GEL by means of low temperature treatments (25-100 C), it is possible to obtain porous solid matrices (XEROGELs). The fundamental property of the solgel process is that it is possible to generate ceramic material at a temperature close to room temperature. Therefore such a procedure opened the possibility of incorporating in these glasses soft dopants, such as fluorescent dye molecules and organic chromophores.
Xerogel, Aerogel
Organic/Inorganic
Ceramics, Glass
Porous Materials
Condensation
Hydrolysis
(8) Olation and (9) Oxolation
Positive Charge
Negative Charge
Silica Dissolves
10
12
pH
Gel Process
Supercritical Drying
Monolithic Aerogels
Hydrophobic Surface
Applications of Aerogel
Thermal Insulation Acoustic Insulation Catalyst Support Optical applications Nuclear Waste Storage Filler for paints or others low dielectric constant materials Batteries
Hydrolysis: The reaction of a metal alkoxide (M-OR) with water, forming a metal hydroxide (M-OH). Condensation: A condensation reaction occurs when two metal hydroxides (M-OH + HO-M) combine to give a metal oxide species (M-O-M). The reaction forms one water molecule. Sol: A solution of various reactants that are undergoing hydrolysis and condensation reactions. The molecular weight of the oxide species produced continuously increases. As these species grow, they may begin to link together in a three-dimensional network. Gel Point: The point in time at which the network of linked oxide particles spans the container holding the Sol. At the gel point the Sol becomes an Alcogel. Alcogel (wet gel): At the gel point, the mixture forms a rigid substance called an alcogel. The alcogel can be removed from its original container and can stand on its own. An alcogel consists of two parts, a solid part and a liquid part. The solid part is formed by the three-dimensional network of linked oxide particles. The liquid part (the original solvent of the Sol) fills the free space surrounding the solid part. The liquid and solid parts of an alcogel occupy the same apparent volume. Supercritical fluid: A substance that is above its critical pressure and critical temperature. A supercritical fluid possesses some properties in common with a liquids (density, thermal conductivity) and some in common with gases. (fills its container, does not have surface tension). Aerogel: What remains when the liquid part of an alcogel is removed without damaging the solid part (most often achieved by supercritical extraction). If made correctly, the aerogel retains the original shape of the alcogel and at least 50% (typically >85%) of the alcogel's volume. Xerogel: What remains when the liquid part of an alcogel is removed by evaporation, or similar methods. Xerogels may retain their original shape, but often crack. The shrinkage during drying is often extreme (~90%) for xerogels.
Although they initially have been worked out by chemists from the sol-gel scientific community today hybrids are elaborated by researchers coming from a variety of disciplines, polymers chemists, solid state chemists, catalysis, materials researchers e Each of these communities elaborate hybrids using their own too specific disciplinary methods and more important their own raw materials. It is not seldom to see that a polymerist will work out an hybrid system having an emphasis on the polymer side of the hybrid, using even pre-formed polymers, capped oligomers etc. Sol-gel and inorganic chemists will preferably use as precursors, silicon or metal alkoxides or even inorganic building units such as clusters or nanoparticles. They can also use lamellar inorganic compounds as host for organic components. Many names have been given to these materials: Ceramers, Polycerams, Ormosils o Ormocers. However it is now commonly accepted that a molecular approach for the synthesis of hybrids reflects better the wide opportunities offered by this compounded chemistry.
Organo(alkox y)silanes and metal alkoxides serving as precursors for sol-gelderived materials.
Cross-linking of inorganic clusters or nanoparticles via photochemically induced polymerization of (meth)acrylic functional groups.
xerogels prepared from fluoroaromatics 1 to 5 (from left to right) and APS or MAPS in TEOS
Commercial magnifying lens(PMMA) euipped with an abrasion resistant, UV cured hybrid coating