Silica shape

Drying. The drying step for large shapes is critical. Extremely large fireclay and silica shapes are sometimes allowed to dry on a temperature-controlled floor heated by steam or air ducts embedded in the concrete. Smaller shapes are generally dried in a tunnel dryer. The ware is placed on cars that enter the cold end and exit at the hot end. 

Figure 15.4 SEM images showing diverse mesoporous silica shapes and patterns produced by surfactant templating (a) rope, (b) toroid, (c) discoid, (d) pinwheel, (e) wheel, (f) gyroid, (g) bagel, (h) shell, (i) knot, (j) clock, (k) eccentric 1 and (1) eccentric (reproduced by permission from Macmillan Publishers Ltd).

FIGURE 17.22 Microblown silica shape formed on oxidized SiC. 

Figure 17.22 shows a microblown silica shape formed on SiC. What gas do you think would be formed at the Si02/SiC interface and lead to the shape shown Would the gas be different at different temperatures ... 

Replication techniques are available for transforming complex silica shapes into the corresponding shapes of various polymers. Ihe process can also be extended in the opposite direction, by converting the silica into silicon. Specifically, a low-temperature reduction process has been developed to convert three-dimensional nanostructured silica micro-assemblies into microporous nanocrystalline silicon replicas. Such materials could be useful in a variety of applications, including sensors and biomedical devices. 

Anotlier important modification metliod is tire passivation of tire external crystallite surface, which may improve perfonnance in shape selective catalysis (see C2.12.7). Treatment of zeolites witli alkoxysilanes, SiCl or silane, and subsequent hydrolysis or poisoning witli bulky bases, organophosphoms compounds and arylsilanes have been used for tliis purjDose [39]. In some cases, tire improved perfonnance was, however, not related to tire masking of unselective active sites on tire outer surface but ratlier to a narrowing of tire pore diameters due to silica deposits. 

The discrepancy between the pore area or the core area on the one hand and the BET area on the other is proportionately larger with silica than with alumina, particularly at the higher degrees of compaction. The fact that silica is a softer material than alumina, and the marked reduction In the BET area of the compact as compared with that of the loose material, indicates a considerable distortion of the particles, with consequent departure of the pore shape from the ideal of interstices between spheres. The factor R for cylinders (p. 171), used in the conversion to pore area in the absence of a better alternative, is therefore at best a crude approximation. 

An outstanding feature of the adsorption of water vapour on silica is its sensitivity to the course and subsequent treatment of the silica sample, in particular the temperature to which it has been heated. Figure 5.15 shows the strong dependence of the isotherm for a particular silica gel on the temperature of its heat treatment the isotherm is progressively lowered as the temperature increases, especially above 400°C, and the shape changes from Type II for the lower temperatures to Type III for 600°C, 800°C and 1000°C. 

As pointed out earlier (Section 3.5), certain shapes of hysteresis loops are associated with specific pore structures. Thus, type HI loops are often obtained with agglomerates or compacts of spheroidal particles of fairly uniform size and array. Some corpuscular systems (e.g. certain silica gels) tend to give H2 loops, but in these cases the distribution of pore size and shape is not well defined. Types H3 and H4 have been obtained with adsorbents having slit-shaped pores or plate-like particles (in the case of H3). The Type I isotherm character associated with H4 is, of course, indicative of microporosity. 

Vitreous silica is used for gas-heated or electrically heated devices ia various shapes, eg, as a tube or muffle because of its electrical resistivity, impermeabihty, and low expansion. In its simplest form, an electric-resistance furnace consists of a vitreous siUca tube or pipe on which the resistance element is wound (see Furnaces, ELECTRIC). Because of its iadifference to temperature gradients, a tubular furnace of vitreous siUca maybe made to operate at different temperatures at various portions of the tube, either by arrangement of the heating elements or by cooling sections of the tube with water. Vitreous siUca pipes may be employed ia vacuum-iaduction and gas-fired furnaces (see Vacuum technology) (221). 

Mcntasty el al. [35] and others [13, 36] have measured methane uptakes on zeolites. These materials, such as the 4A, 5A and 13X zeolites, have methane uptakes which are lower than would be predicted using the above relationship. This suggests that either the zeolite cavity is more attractive to 77 K nitrogen than a carbon pore, or methane at 298 K, 3.4 MPa, is attracted more to a carbon pore than a zeolite. The latter proposition is supported by the modeling of Cracknel et al. [37, 38], who show that methane densities in silica cavities will be lower than for the equivalent size parallel slit shaped pore of their model carbon. Results reported by Ventura [39] for silica xerogels lead to a similar conclusion. Thus, porous silica adsorbents with equivalent nitrogen derived micropore volumes to carbons adsorb and deliver less methane. For delivery of 150 V./V a silica based adsorbent would requne a micropore volume in excess of 0.70 ml per ml of packed vessel volume. 

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