Silicon alkoxide

Employing silicon alkoxides, the hydrolysis has to be catalyzed by the addition of an acid or a base, and an excess of water is often used. Employing zirconium alkoxides, the hydrolysis reaction proceeds much faster than the condensation so that the product is obtained as a precipitate rather than a gel. 

Silicon alkoxide groups, 455 Silicon-containing polymers, 450-460 Silicon-methoxy bonds, hydrolysis of,... 

It was shown (1-3) that the silicon alkoxide solutions become spinnable when an acid is used as catalyst and the water content of the starting solution is small at less than 4 or 5 in the water to silicon alkoxide molar ratio. Recently, it has been found that this rule for the possibility of drawing fibers is only valid for the solutions reacted in the open system and no spinnability is found in the solutions reacted in the closed system (4). It has also been found that the addition of very large amounts of acid to the starting solution produces relatively large round-shaped particles, preventing the occurrence of spinnability (4). These will be discussed in the first half of this paper. 

It has been shown that the spinnability occurs in the silicon alkoxide solution when an acid is used as catalyst and the water content is small at less than 4 in the water to metal alkoxide ratio. 

Because of the role of precursor structure on film processing behavior (consolidation, densification, crystallization behavior), the reaction pathways are typically biased through the use of the catalyst, which is simply an acid or a base. This steers the reaction toward an electrophilic or nucleophilic attack of the M—OR bond.1,63 Hydrolysis sensitivity of singly or multiply hydrolyzed silicon alkoxides is also influenced by the catalyst, which contributes to the observed variations in oligomer length and structure. Figure 2.3b illustrates... 

The hydrolytic polycondensation of silicon alkoxides of general formula Si(OR)4 or R/ Si(OR)4 , where the non-reactive organofunc-tional group R acts as a network modifier, is carried out in the presence of dopant molecules resulting in the formation of highly porous, reactive organosilicates whose applications span many traditional domains of chemistry. 

Silica-based materials obtained by the sol-gel process are perhaps the most promising class of functional materials capable to meet such a grand objective. In the sol-gel process liquid precursors such as silicon alkoxides are mixed and transformed into silica via hydrolytic polycondensation at room temperature. Called soft chemitry or chimie douce, this approach to the synthesis of glasses at room temperature and pressure and in biocompatible conditions (water, neutral pH) has been pioneered by Livage and Rouxel in the 1970s, and further developed by Sanchez, Avnir, Brinker and Ozin. 

Normally, the organic groups of ORMOSIL are located at the cage interface. The hydrolysis of organosilanes is slower compared to fully hydrolysable silicon alkoxides, and the slowly generated R-Si(OH)3... 

Figure 4.9 Silicon alkoxides adhere to steel surfaces by chemical binding to surface hydroxyls (left) resulting in strong adhesion of a ballast paint (right). (Reproduced from ref. 12, with permission.)...

Biological species such as enzymes, whole cells, antibodies and even bacteria can all be successfully entrapped in silica sol-gel matrices, often with enhancement of activity with respect to the free biologicals. In these cases, the process is adapted to eliminate toxic alcohols which are typically released in conventional sol-gel processes based on the hydrolysis of silicon alkoxides. Two such methods are the use of silicon alkoxide... 

Hybrid polymer silica nanocomposites formed from various combinations of silicon alkoxides and polymers to create a nanoscale admixture of silica and organic polymers constitute a class of composite materials with combined properties of polymers and ceramics. They are finding increasing applications in protective coatings (Figure 7.1), optical devices, photonics, sensors and catalysis.1... 

Generally, two common methods, the Stober method and the reverse microemulsion method are used for synthesis of silica nanoparticles. As derivatives of a sol-gel process, both methods involve hydrolysis of a silicon alkoxide precursor to form a hydroxysilicate followed by polycondensation of the hydroxysilicate to form a silica nanoparticle [44]. 

The Stober method is also known as a sol-gel method [44, 45], It was named after Stober who first reported the sol-gel synthesis of colloid silica particles in 1968 [45]. In a typical Stober method, silicon alkoxide precursors such as tetramethylorthosili-cate (TMOS) and tetraethylorthosihcate (TEOS), are hydrolyzed in a mixture of water and ethanol. This hydrolysis can be catalyzed by either an acid or a base. In sol-gel processes, an acidic catalyst is preferred to prepare gel structure and a basic catalyst is widely used to synthesize discrete silica nanoparticles. Usually ammonium hydroxide is used as the catalyst in a Stober synthesis. With vigorous stirring, condensation of hydrolyzed monomers is carried out for a certain reaction time period. The resultant silica particles have a nanometer to micrometer size range. 

The Stober method can be used to form core-shell silica nanoparticles when a presynthesized core is suspended in a water-alcohol mixture. The core can be a silica nanoparticle or other types of nanomaterials [46, 47]. If the core is a silica nanoparticle, before adding silicon alkoxide precursors, the hydroxysilicates hydrolyzed from precursors condense by the hydroxide groups on the surface of the silica cores to form additional layers. If the core is a colloid, surface modification of the core might be necessary. For example, a gold colloid core was modified by poly (vinylpyrrolidone) prior to a silica layer coating [46]. 

The size of silica nanoparticles affects their physical, chemical, electronic, and optical properties. Proper size of silica nanoparticles is crucial for design of silica-based nanomaterials. In Stober methods, the size of silica nanoparticles is adjusted by changing the type of organic solvent, the amount of silicon alkoxide, and the... 

The amorphous silica matrixes are porous network structures that allow other species to penetrate [44]. Thus, the doped dye molecules have the ability to react with targets. However, the reaction kinetics is significantly different than the molecules in a bulk solution. In the synthesis of DDSNs, commonly used silicon alkoxides including TEOS and TMOS have tetrahedron structures, which allow compact polycondensation. As a result, the developed silica nanomatrix can be very dense. The small pore sizes provide limited and narrow pathways for other species to diffuse into the silica matrix. 

Niwa, M-, S. Kato, T. Hattori and Y. Murikami. 1984. Fine control of the pore opening size of zeolite mordenite by chemical vapor deposition of silicon alkoxide. J.C.S. Faraday Trans. 180 3135-45. 

---