Tetraethylorthosilicates

Another important recent advance is the development of the CVD of Si02 from tetraethylorthosilicate (TEOS) and ozone (see Ch. 11). This deposition reaction is becoming prominent for the many production advantages it provides. ]... 

A recent competitor to CVD in the planarization of silicon dioxide is the sol-gel process, where tetraethylorthosilicate is used to form spin-on-glass (SOG) films (see Appendix). This technique produces films with good dielectric properties and resistance to cracking. Gas-phase precipitation, which sometimes is a problem with CVD, is eliminated. 

Enichem made one of the most important steps forward in the development of general heterogeneous oxidation catalysts in the early 1990s with the commercialization of titanium silicate (TS-1) catalysts. TS-1 has a structure similar to ZSM-5 in which the aluminium has been replaced by titanium it is prepared by reaction of tetraethylorthosilicate and tetra-ethylorthotitanate in the presence of an organic base such as tetrapropy-lammonium hydroxide. This catalyst is especially useful for oxidation reactions using hydrogen peroxide (Scheme 4.11), from which the only byproduct is water, clean production of hydroquinone being one of the possibilities. 

Two kinds of solution were prepared in advance. Solution A was a water solution containing an Si source, which was obtained by hydrolyzing metal alkoxide (tetraethylorthosilicate, TEOS) with a dilute tetrapropylammoniumhydroxide (TPA-OH)/water solution at room temperature. The molar ratio of Si to the template was 3. In peparation of ZSM-S zeolite nanoerystals, aluminium isopropoxide as an A1 source and sodium chloride were added into solution A. Solution B was an oi mic solution containing surfectant Nonionie surfactants, poljraxyethylene (15) cxslylether (C-15), polyoxyethylene (15) nonylphenylether (NP-15), and polyoxyethylene (15) oleylether (O-15), and ionic surfoctnnts, sodium bis(2-ethylhexyl) sulfosucdnate (AOT) and... 

Some elucidation of the mechanism of elastomer reinforcement is being obtained by precipitating chemically-generated fillers into network structures rather than blending badly agglomerated filler particles into elastomers prior to their cross-linking. This has been done for a variety of fillers, for example, silica by hydrolysis of organosilicates, titania from titanates, alumina from aluminates, etc. [85-87], A typical, and important, reaction is the acid- or base-catalyzed hydrolysis of tetraethylorthosilicate ... 

Kinetic and Mass Spectroscopic Investigations of Plasma Induced Deposition of Silicion Dioxide from Tetraethylorthosilicate and Oxygen... 

Fig. 1. Mass spectra of Tetraethylorthosilicate at a discharge current density of 0.314 mA/cm2, ionisation potential 60 eV...

MCM-41 spheres were prepared modifying the procedure reported by Grim et. al. [9], using n-hexadecyltrimethylammonium bromide (Ci6TMABr) as surfactant template. Reactant molar ratio was 1 TEOS 0,3 C TMABr 0,129 NH3 144 H20 58 EtOH with pH about 9. The surfactant (Ci6TMABr) was dissolved into the mixture of distilled water, NH3 and EtOH tetraethylorthosilicate ([C2H50]4Si, TEOS) was then added to the surfactant solution and stirred for 2 hours at room temperature. 

American scientists prepared the organo-silica sol-gel membranes60 and demonstrated in a single layer format for pH measurement and multiple-layer format for both C02 and NH3. The sensors used a hydroxypyrenetrisulfonic acid (HPTS) as the indicator immobilizes in a base-catalyzed sol-gel containing poly(dimethyl)siloxane, aminopropyl-triethoxysilane (APTES) and tetraethylorthosilicate (TEOS). This indicator gel was over coated with a hydrophobic sol-gel to reduce cross reactivity to pH when either carbon dioxide or ammonia were examined. 

It is possible to modify the matrix hydrophilicity-lipophilicity balance (HLB) by using different alkyl-modified trialkoxysilanes as co-reagents with tetraethylorthosilicate (TEOS), to greatly alter (reduce) the release rate of heparin, as then water access to the entrapped drug is considerably reduced (Figure 2.10).4... 

Figure 4.23 Synthesis space diagram for a ternary system composed of tetraethylorthosilicate (TEOS), cetyltrimethylammonium bromide (CTAB), and sodium hydroxide (H, hexagonal phase [MCM-41] C, cubic phase [MCM-48] L, lamellar phase [MCM-50] H20/Si02 = 100, reaction temperature 100°C, reaction time 10 days). (Reprinted from Science, Vol. 267, A. Firouzi, D. Kumar, L.M. Bull, T. Besier, R Sieger, Q. Huo, S.A. Walker, J.A. Zasadzinski, C. Glinka, J. Nicol, D.l. Margolese, G.D. Stucky, B.F. Chmelka, Cooperative Organization of Inorganic-Surfactant and Biomimetic Assemblies, pp. 1138-1143. Copyright 1995. With permission of AAAS.)...

Hybrid membranes composed of poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS), synthetised via hydrolysis and a co-condensation reaction for the pervaporation separation of water-isopropanol mixtures has also been reported [32], These hybrid membranes show a significant improvement in the membrane performance for water-isopropanol mixture separation. The separation factor increased drastically upon increasing the crosslinking (TEOS) density due to a reduction of free volume and increased chain stiffness. However, the separation factor decreased drastically when PVA was crosslinked with the highest amount of TEOS (mass ratio of TEOS to PVA is 2 1). The highest separation selectivity is found to be 900 for PVA TEOS (1.5 1 w/w) at 30°C. For all membranes, the selectivity decreased drastically up to 20 mass % of water in the feed and then remained almost constant beyond 20 mass %, signifying that the separation selectivity is much influenced at lower composition of water in the feed. 

A recent paper [69] presents a new type of PVA hybrid membrane prepared by hydrolysis followed by condensation of a PVA and a tetraethylorthosilicate (TEOS) mixture, which shows a significant performace in water-acetic acid mixture separation. The highest separation selectivity (1116) with a flux of 3.33xft)"2 kg m"2 h"1 at 30 °C for 10% mass of water in the feed has ben obtained by using the membrane containing 1 2 mass ratio of PVA and TEOS. The performance of these membranes was explained on the basis of a reduction of free volume and a decrease of the hydrophylic character owning to the formation of... 

Several groups used sol-gel transition to immobilize the beads packed in a capillary. For example, Dulay et al. [102] packed a slurry of ODS beads in tetraethylorthosilicate solution and heated it to 100 °C to achieve the sol-gel transition and create the monolithic structure shown in Fig. 17. This technology is extremely sensitive and even a small deviation from the optimal conditions leads to cracks in the monoliths and a rapid deterioration in the column performance. However, even the best efficiency of 80,000 plates/m achieved with these column was relatively low. Henry et al. modified the original procedure and increased the efficiencies to well over 100,000 plates/m [103,104]. 

Figure 1. Scheme for the liquid crystalline templating mechanism proposed by Kresge et al 1 for synthesis of mesoporous silica MCM-41. Formation of a hexagonal array of cylindrical micelles possibly mediated by silicate anions followed by condensation of the silicate anions from the silicate source (tetraethylorthosilicate) leads to templated framework structure. Calcination or extraction of the template produces hexagonally ordered mesoporous silica. 

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