In materials science, the sol-gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon and titanium. The process involves conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers. Typical precursors are metal alkoxides.
- 1 Stages in the process
- 2 Particles and polymers
- 3 Polymerization
- 4 Sono-Ormosil
- 5 Nanomaterials
- 6 Applications
- 7 Mechanics of gelation
- 8 References
- 9 Further reading
- 10 External links
Stages in the process
In this chemical procedure, the 'sol' (or solution) gradually evolves towards the formation of a gel-like diphasic system containing both a liquid phase and solid phase whose morphologies range from discrete particles to continuous polymer networks. In the case of the colloid, the volume fraction of particles (or particle density) may be so low that a significant amount of fluid may need to be removed initially for the gel-like properties to be recognized. This can be accomplished in any number of ways. The simplest method is to allow time for sedimentation to occur, and then pour off the remaining liquid. Centrifugation can also be used to accelerate the process of phase separation.
Removal of the remaining liquid (solvent) phase requires a drying process, which is typically accompanied by a significant amount of shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel. The ultimate microstructure of the final component will clearly be strongly influenced by changes imposed upon the structural template during this phase of processing.
Afterwards, a thermal treatment, or firing process, is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via final sintering, densification and grain growth. One of the distinct advantages of using this methodology as opposed to the more traditional processing techniques is that densification is often achieved at a much lower temperature.
The precursor sol can be either deposited on a substrate to form a film (e.g., by dip coating or spin coating), cast into a suitable container with the desired shape (e.g., to obtain monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres). The sol-gel approach is a cheap and low-temperature technique that allows for the fine control of the product’s chemical composition. Even small quantities of dopants, such as organic dyes and rare earth elements, can be introduced in the sol and end up uniformly dispersed in the final product. It can be used in ceramics processing and manufacturing as an investment casting material, or as a means of producing very thin films of metal oxides for various purposes. Sol-gel derived materials have diverse applications in optics, electronics, energy, space, (bio)sensors, medicine (e.g., controlled drug release), reactive material and separation (e.g., chromatography) technology.
The interest in sol-gel processing can be traced back in the mid-1800s with the observation that the hydrolysis of tetraethyl orthosilicate (TEOS) under acidic conditions led to the formation of SiO2 in the form of fibers and monoliths. Sol-gel research grew to be so important that in the 1990s more than 35,000 papers were published worldwide on the process.
Particles and polymers
The sol-gel process is a wet-chemical technique used for the fabrication of both glassy and ceramic materials. In this process, the sol (or solution) evolves gradually towards the formation of a gel-like network containing both a liquid phase and a solid phase. Typical precursors are metal alkoxides and metal chlorides, which undergo hydrolysis and polycondensation reactions to form a colloid. The basic structure or morphology of the solid phase can range anywhere from discrete colloidal particles to continuous chain-like polymer networks.
The term colloid is used primarily to describe a broad range of solid-liquid (and/or liquid-liquid) mixtures, all of which contain distinct solid (and/or liquid) particles which are dispersed to various degrees in a liquid medium. The term is specific to the size of the individual particles, which are larger than atomic dimensions but small enough to exhibit Brownian motion. If the particles are large enough, then their dynamic behavior in any given period of time in suspension would be governed by forces of gravity and sedimentation. But if they are small enough to be colloids, then their irregular motion in suspension can be attributed to the collective bombardment of a myriad of thermally agitated molecules in the liquid suspending medium, as described originally by Albert Einstein in his dissertation. Einstein concluded that this erratic behavior could adequately be described using the theory of Brownian motion, with sedimentation being a possible long-term result. This critical size range (or particle diameter) typically ranges from tens of angstroms (10−10 m) to a few micrometres (10−6 m).
- Under certain chemical conditions (typically in base-catalyzed sols), the particles may grow to sufficient size to become colloids, which are affected both by sedimentation and forces of gravity. Stabilized suspensions of such sub-micrometre spherical particles may eventually result in their self-assembly—yielding highly ordered microstructures reminiscent of the prototype colloidal crystal: precious opal.
- Under certain chemical conditions (typically in acid-catalyzed sols), the interparticle forces have sufficient strength to cause considerable aggregation and/or flocculation prior to their growth. The formation of a more open continuous network of low density polymers exhibits certain advantages with regard to physical properties in the formation of high performance glass and glass/ceramic components in 2 and 3 dimensions.
In either case (discrete particles or continuous polymer network) the sol evolves then towards the formation of an inorganic network containing a liquid phase (gel). Formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution.
In both cases (discrete particles or continuous polymer network), the drying process serves to remove the liquid phase from the gel, yielding a micro-porous amorphous glass or micro-crystalline ceramic. Subsequent thermal treatment (firing) may be performed in order to favor further polycondensation and enhance mechanical properties.
With the viscosity of a sol adjusted into a proper range, both optical quality glass fiber and refractory ceramic fiber can be drawn which are used for fiber optic sensors and thermal insulation, respectively. In addition, uniform ceramic powders of a wide range of chemical composition can be formed by precipitation.
A well studied alkoxide is silicon tetraethoxide, or tetraethyl orthosilicate (TEOS). The chemical formula for TEOS is given by Si(OC2H5)4, or Si(OR)4, where the alkyl group R = C2H5. Alkoxides are ideal chemical precursors for sol-gel synthesis because they react readily with water. The reaction is called hydrolysis, because a hydroxyl ion becomes attached to the silicon atom as follows:
- Si(OR)4 + H2O → HO-Si(OR)3 + R-OH
Depending on the amount of water and catalyst present, hydrolysis may proceed to completion to silica:
- Si(OR)4 + 2 H2O → SiO2 + 4 R-OH
Complete hydrolysis often requires an excess of water and/or the use of a hydrolysis catalyst such as acetic acid or hydrochloric acid. Intermediate species including [(OR)2–Si-(OH)2] or [(OR)3–Si-(OH)] may result as products of partial hydrolysis reactions. Early intermediates result from two partially hydrolyzed monomers linked via a siloxane [Si–O–Si] bond:
- (OR)3–Si-OH + HO–Si-(OR)3 → [(OR)3Si–O–Si(OR)3] + H-O-H
- (OR)3–Si-OR + HO–Si-(OR)3 → [(OR)3Si–O–Si(OR)3] + R-OH
By definition, condensation liberates a small molecule, such as water or alcohol. This type of reaction can continue to build larger and larger silicon-containing molecules by the process of polymerization. Thus, a polymer is a huge molecule (or macromolecule) formed from hundreds or thousands of units called monomers. The number of bonds that a monomer can form is called its functionality. Polymerization of silicon alkoxide, for instance, can lead to complex branching of the polymer, because a fully hydrolyzed monomer Si(OH)4 is tetrafunctional (can branch or bond in 4 different directions). Alternatively, under certain conditions (e.g., low water concentration) fewer than 4 of the OR or OH groups (ligands) will be capable of condensation, so relatively little branching will occur. The mechanisms of hydrolysis and condensation, and the factors that bias the structure toward linear or branched structures are the most critical issues of sol-gel science and technology. This reaction is favored in both basic and acidic conditions.
Sonication is an efficient tool for the synthesis of polymers. The cavitational shear forces, which stretch out and break the chain in a non-random process, result in a lowering of the molecular weight and poly-dispersity. Furthermore, multi-phase systems are very efficient dispersed and emulsified, so that very fine mixtures are provided. This means that ultrasound increases the rate of polymerisation over conventional stirring and results in higher molecular weights with lower polydispersities. Ormosils (organically modified silicate) are obtained when silane is added to gel-derived silica during sol-gel process. The product is a molecular-scale composite with improved mechanical properties. Sono-Ormosils are characterized by a higher density than classic gels as well as an improved thermal stability. An explanation therefore might be the increased degree of polymerization.
In the processing of fine ceramics, the irregular particle sizes and shapes in a typical powder often lead to non-uniform packing morphologies that result in packing density variations in the powder compact. Uncontrolled flocculation of powders due to attractive van der Waals forces can also give rise to microstructural inhomogeneities. 
Differential stresses that develop as a result of non-uniform drying shrinkage are directly related to the rate at which the solvent can be removed, and thus highly dependent upon the distribution of porosity. Such stresses have been associated with a plastic-to-brittle transition in consolidated bodies, and can yield to crack propagation in the unfired body if not relieved.
In addition, any fluctuations in packing density in the compact as it is prepared for the kiln are often amplified during the sintering process, yielding inhomogeneous densification. Some pores and other structural defects associated with density variations have been shown to play a detrimental role in the sintering process by growing and thus limiting end-point densities. Differential stresses arising from inhomogeneous densification have also been shown to result in the propagation of internal cracks, thus becoming the strength-controlling flaws.
It would therefore appear desirable to process a material in such a way that it is physically uniform with regard to the distribution of components and porosity, rather than using particle size distributions which will maximize the green density. The containment of a uniformly dispersed assembly of strongly interacting particles in suspension requires total control over particle-particle interactions. Monodisperse colloids provide this potential.
Monodisperse powders of colloidal silica, for example, may therefore be stabilized sufficiently to ensure a high degree of order in the colloidal crystal or polycrystalline colloidal solid which results from aggregation. The degree of order appears to be limited by the time and space allowed for longer-range correlations to be established. Such defective polycrystalline structures would appear to be the basic elements of nanoscale materials science, and, therefore, provide the first step in developing a more rigorous understanding of the mechanisms involved in microstructural evolution in inorganic systems such as sintered ceramic nanomaterials.
The applications for sol gel-derived products are numerous. For example, scientists have used it to produce the world’s lightest materials and also some of its toughest ceramics. One of the largest application areas is thin films, which can be produced on a piece of substrate by spin coating or dip coating. Protective and decorative coatings, and electro-optic components can be applied to glass, metal and other types of substrates with these methods. Cast into a mold, and with further drying and heat-treatment, dense ceramic or glass articles with novel properties can be formed that cannot be created by any other method. Other coating methods include spraying, electrophoresis, inkjet printing or roll coating.
Thin films and fibers
With the viscosity of a sol adjusted into a proper range, both optical and refractory ceramic fibers can be drawn which are used for fiber optic sensors and thermal insulation, respectively. Thus, many ceramic materials, both glassy and crystalline, have found use in various forms from bulk solid-state components to high surface area forms such as thin films, coatings and fibers.
Ultra-fine and uniform ceramic powders can be formed by precipitation. These powders of single and multiple component compositions can be produced on a nanoscale particle size for dental and biomedical applications. Composite powders have been patented for use as agrochemicals and herbicides. Powder abrasives, used in a variety of finishing operations, are made using a sol-gel type process. One of the more important applications of sol-gel processing is to carry out zeolite synthesis. Other elements (metals, metal oxides) can be easily incorporated into the final product and the silicate sol formed by this method is very stable.
Another application in research is to entrap biomolecules for sensory (biosensors) or catalytic purposes, by physically or chemically preventing them from leaching out and, in the case of protein or chemically-linked small molecules, by shielding them from the external environment yet allowing small molecules to be monitored. The major disadvantages are that the change in local environment may alter the functionality of the protein or small molecule entrapped and that the synthesis step may damage the protein. To circumvent this, various strategies have been explored, such as monomers with protein friendly leaving groups (e.g. glycerol) and the inclusion of polymers which stabilize protein (e.g. PEG).
Other products fabricated with this process include various ceramic membranes for microfiltration, ultrafiltration, nanofiltration, pervaporation and reverse osmosis. If the liquid in a wet gel is removed under a supercritical condition, a highly porous and extremely low density material called aerogel is obtained. Drying the gel by means of low temperature treatments (25-100 °C), it is possible to obtain porous solid matrices called xerogels. In addition, a sol-gel process was developed in the 1950s for the production of radioactive powders of UO2 and ThO2 for nuclear fuels, without generation of large quantities of dust.
Macroscopic optical elements and active optical components as well as large area hot mirrors, cold mirrors, lenses and beam splitters all with optimal geometry can be made quickly and at low cost via the sol-gel route. In the processing of high performance ceramic nanomaterials with superior opto-mechanical properties under adverse conditions, the size of the crystalline grains is determined largely by the size of the crystalline particles present in the raw material during the synthesis or formation of the object. Thus a reduction of the original particle size well below the wavelength of visible light (~500 nm) eliminates much of the light scattering, resulting in a translucent or even transparent material.
Furthermore, results indicate that microscopic pores in sintered ceramic nanomaterials, mainly trapped at the junctions of microcrystalline grains, cause light to scatter and prevented true transparency. it has been observed that the total volume fraction of these nanoscale pores (both intergranular and intragranular porosity) must be less than 1% for high-quality optical transmission. I.E. The density has to be 99.99% of the theoretical crystalline density.
Mechanics of gelation
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In a static sense, the fundamental difference between a liquid and a solid is that the solid has elastic resistance against a shearing stress while a liquid does not. Thus, a simple liquid will not typically support a transverse acoustic phonon, or shear wave. Gels have been described by Born as liquids in which an elastic resistance against shearing survives, yielding both viscous and elastic properties. It has been shown theoretically that in a certain low-frequency range, polymeric gels should propagate shear waves with relatively low damping. The distinction between a sol (solution) and a gel therefore appears to be understood in a manner analogous to the practical distinction between the elastic and plastic deformation ranges of a metal. The distinction lies in the ability to respond to an applied shear force via macroscopic viscous flow. 
In a dynamic sense, the response of a gel to an alternating force (oscillation or vibration) will depend upon the period or frequency of vibration. As indicated here, even most simple liquids will exhibit some elastic response at shear rates or frequencies exceeding 5 x 106 cycles per second. Experiments on such short time scales probe the fundamental motions of the primary particles (or particle clusters) which constitute the lattice structure or aggregate. The increasing resistance of certain liquids to flow at high stirring speeds is one manifestation of this phenomenon. The ability of a condensed body to respond to a mechanical force by viscous flow is thus strongly dependent on the time scale over which the load is applied, and thus the frequency and amplitude of the stress wave in oscillatory experiments.
The structural relaxation of a viscoelastic gel has been identified as primary mechanism responsible for densification and associated pore evolution in both colloidal and polymeric silica gels. Experiments in the viscoelastic properties of such skeletal networks on various time scales require a force varying with a period (or frequency) appropriate to the relaxation time of the phenomenon investigated, and inversely proportional to the distance over which such relaxation occurs. High frequencies associated with ultrasonic waves have been used extensively in the handling of polymer solutions, liquids and gels and the determination of their viscoelastic properties. Static measurements of the shear modulus have been made, as well as dynamic measurements of the speed of propagation of shear waves, a measurement which then yields the dynamic modulus of rigidity. Dynamic Light Scattering (DLS) techniques have been utilized in order to monitor the dynamics of density fluctuations through the behavior of the autocorrelation function near the point of gelation.
Tanaka, et al., emphasize that the discrete and reversible volume transitions which occur in partially hydrolyzed acrylimide gels can be interpreted in terms of a phase transition of the system consisting of the charged polymer network, hydrogen (counter)ions and liquid matrix. The phase transition is a manifestation of competition among the three forces which contribute to the osmotic pressure in the gel:
- The positive osmotic pressure of (+) hydrogen ions
- The negative pressure due to polymer-polymer affinity
- The rubber-like elasticity of the polymer network
The balance of these forces varies with change in temperature or solvent properties. The total osmotic pressure acting on the system is the sum osmotic pressure of the gel. It is further shown that the phase transition can be induced by the application of an electrical field across the gel. The volume change at the transition point is either discrete (as in a first-order Ehrenfest transition) or continuous (second order Ehrenfest analogy), depending on the degree of ionization of the gel and on the solvent composition.
The gel is thus interpreted as an elastic continuum which deforms when subjected to externally applied shear forces, but is incompressible upon application of hydrostatic pressure. This combination of fluidity and rigidity is explained in terms of the gel structure: that of a liquid contained within a fibrous polymer network or matrix by the extremely large friction between the liquid and the fiber or polymer network. Thermal fluctuations may produce infinitesimal expansion or contraction within the network, and the evolution of such fluctuations will ultimately determine the molecular morphology and the degree of hydration of the body.
Quasi-elastic light scattering offers direct experimental access to measurement of the wavelength and lifetimes of critical fluctuations, which are governed by the viscoelastic properties of the gel. It is reasonable to expect a relationship between the amplitude of such fluctuations and the elasticity of the network. Since the elasticity measures the resistance of the network to either elastic (reversible) or plastic (irreversible) deformation, the fluctuations should grow larger as the elasticity declines. The divergence of the scattered light intensity at a finite critical temperature implies that the elasticity approaches zero, or the compressibility becomes infinite, which is the typically observed behavior of a system at the point of instability. Thus, at the critical point, the polymer network offers no resistance at all to any form of deformation.
The rate of relaxation of density fluctuations will be rapid if the restoring force, which depends upon the network elasticity, is large—and if the friction between the network and the interstitial fluid is small. The theory suggests that the rate is directly proportional to the elasticity and inversely proportional to the frictional force. The friction in turn depends upon both the viscosity of the fluid and the average size of the pores contained within the polymer network.
Thus, if the elasticity is inferred from the measurements of the scattering intensity, and the viscosity is determined independently (via mechanical methods such as ultrasonic attenuation) measurement of the relaxation rate yields information on the pore size distribution contained within the polymer network, e.g large fluctuations in polymer density near the critical point yield large density differentials with a corresponding bimodal distribution of porosity. The difference in average size between the smaller pores (in the highly dense regions) and the larger pores (in regions of lower average density) will therefore depend upon the degree of phase separation which is allowed to occur before such fluctuations become thermally arrested or "frozen in" at or near the critical point of the transition.
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