Gel-sol phases

Sols arc dispersions of colloidal particles in a liquid. Colloids arc nanoscaled entities dispersed in a fluid. Gels are viscoelastic bodies that have interconnected pores of submicrometric dimensions. A gel typically consists of at Icasl two phases, a solid network that entraps a liquid phase. Sol-gel technology is the preparation of ceramic, glass, or composite materials by the preparation of a sol, gelation of the sol. and removal of the solvent. 

In general, hydrolysis inside the water droplets of a W/0 microemulsion occurs more than an order of magnitude faster than in typical single-phase sol-gel solution at the same concentration, as a result of the high local water concentration. 

Considerable interest in preparation of oriented films such as in the review by Brinker is apparent [11]. Much of the work involves gas phase preparation from methods like chemical vapor deposition (CVD). However, solution phase sol-gel methods were also recently used in many studies. Heterogeneous nucleation and growth on preorganized modified substrates takes away the need to use single crystals. Hydrothermal alteration routes were also summarized [11]. 

Liquid phase Sol-gel, liquid-precursor route polycrystalUne PolycrystalUne 0.5-1 pm for each coating Economical polycrystalUne parameters, corrosive salts, post-thermal treatment usually necessary Various precursors possible, very thin films, low... 

The definition above is a particularly restrictive description of a nanocrystal, and necessarily limits die focus of diis brief review to studies of nanocrystals which are of relevance to chemical physics. Many nanoparticles, particularly oxides, prepared dirough die sol-gel niediod are not included in diis discussion as dieir internal stmcture is amorjihous and hydrated. Neverdieless, diey are important nanoniaterials several textbooks deal widi dieir syndiesis and properties [4, 5]. The material science community has also contributed to die general area of nanocrystals however, for most of dieir applications it is not necessary to prepare fully isolated nanocrystals widi well defined surface chemistry. A good discussion of die goals and progress can be found in references [6, 7, 8 and 9]. Finally, diere is a rich history in gas-phase chemical physics of die study of clusters and size-dependent evaluations of dieir behaviour. This topic is not addressed here, but covered instead in chapter C1.1, Clusters and nanoscale stmctures, in diis same volume. 

Production of net-shape siUca (qv) components serves as an example of sol—gel processing methods. A siUca gel may be formed by network growth from an array of discrete coUoidal particles (method 1) or by formation of an intercoimected three-dimensional network by the simultaneous hydrolysis and polycondensation of a chemical precursor (methods 2 and 3). When the pore Hquid is removed as a gas phase from the intercoimected soHd gel network under supercritical conditions (critical-point drying, method 2), the soHd network does not coUapse and a low density aerogel is produced. Aerogels can have pore volumes as large as 98% and densities as low as 80 kg/m (12,19). 

L. E. Erancis, Sol-Gel Processing, Perovskite Phase Development and Properties ofKelaxor-Based Thin-EajerFerroelectrics, Ph.D. dissertation. University of Illinois, Urbana, 1991. 

An inorganic membrane can be prepared by various methods such as sol-gel, phase separation and leaching.2,3 The sol-gel process is considered the most practical method among those used to prepare inorganic membrane. Sol-gel processing is a simple technology in principle but requires considerable effort to become of practical use. The advantage of this... 

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. 

Tian et al. [56] have studied poly(G-caprolactone)-silica and Sengupta et al. [57] have investigated nylon 66-silica hybrid systems and have observed that the phase separation started when Si/H20 mole ratio is increased above 2 and the resultant hybrid films become opaque. Gao [11] has reported similar observations on sol-gel-derived ionomeric polyethylene-silica system. A wide range of literatures is not available on this topic of mbber-silica hybrid nanocomposites, though Bandyopadhyay et al. [34,35] have reported the hybrid formation with different TEOS/H2O mole ratios from ACM and ENR and also demonstrated detailed structure-property correlation in these systems. The hybrids have been prepared with 1 1, 1 2, 1 4, 1 6, 1 8, and 1 10 TEOS/H2O mole ratios. Figure 3.14 shows the morphology of the ACM-silica hybrid composites prepared from different TEOS/H2O mole ratios. 

The most important nanomaterial synthesis methods include nanolithography techniques, template-directed syntheses, vapor-phase methods, vapor-liquid-solid (VLS) methods, solution-liquid-solid (SLS) approaches, sol-gel processes, micelle, vapor deposition, solvothermal methods, and pyrolysis methods [1, 2]. For many of these procedures, the control of size and shape, the flexibility in the materials that can be synthesized, and the potential for scaling up, are the main limitations. In general, the understanding of the growth mechanism of any as-... 

There are a variety of routes currently utilized to fabricate a wide range of hollow capsules of various compositions. Among the more traditional methods are nozzle reactor processes, emnlsion/phase-separation procednres (often combined with sol-gel processing), and sacrificial core techniques [78], Self-assembly is an elegant and attractive approach for the preparation of hollow capsules. Vesicles [79,80], dendrimers [81,82], and block hollow copolymer spheres [83,84] are all examples of self-assembled hollow containers that are promising for the encapsnlation of various materials. 

Sol-gel techniques have been successfidly applied to form fuel cell components with enhanced microstructures for high-temperature fuel cells. The apphcations were recently extended to synthesis of hybrid electrolyte for PEMFC. Although die results look promising, the sol-gel processing needs further development to deposit micro-structured materials in a selective area such as the triple-phase boundary of a fuel cell. That is, in the case of PEMFC, the sol-gel techniques need to be expanded to form membrane-electrode-assembly with improved microstructures in addition to the synthesis of hybrid membranes to get higher fuel cell performance. 

Nanocrystals titania was prepared by sol-gel method. X-ray diffraction result is shown in Figure 1, all samples were anatase phase. Based on Sherrer s equation, these samples had crystallite sizes about 7 nm. From XRD results, it indicated that titania samples showed the similar of crystallinity because the same ordering in the structure of titania particles make the same intensity of XRD peaks. 

In the one phase region, when the sample was seen to flow easily, it was said that the system was still a sol. When the meniscus was seen not to deform under it own weight, the system was considered a gel. The sol-gel transition was taken at the onset of meniscus deformation when the tube is held horizontal. Syneresis and precipitation were detected by the presence of water at the gel surface or by the existence of large turbid aggregates which could be centrifugated. 

The sol-gel transition has been determined visually, with calcium and copper, for different pectins under different external conditions. As shown in Figure 5 for sample C44 the homogeneous gel phase is situated between the two transition lines. The extension of this phase was found to depend mainly on the DE, temperature and nature of the cation. With calcium the amount of cation required to get a gel increased with the degree of esterification and above 50% it became impossible to get a gel [8]. 

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