Alumina diffusivities

Scheme 11.9c represents array of crystals, in which the pores are formed by vacancies among crystals. Typical representative is porous alumina. Diffusion rate of macromolecules within stracture of this material is likely hindered and separation efficiency is low. 

Notice in Table XVIII-1 a value for the self-diffusion of Ni on Ni(lll) measured using radioactive Ni. More gross processes can occur. Supported Ni crystallites (on alumina) may show spreading and wetting phenomena due to complex interactions with the substrate [146]. 

The noble metal thermocouples, Types B, R, and S, are all platinum or platinum-rhodium thermocouples and hence share many of the same characteristics. Metallic vapor diffusion at high temperatures can readily change the platinum wire calibration, hence platinum wires should only be used inside a nonmetallic sheath such as high-purity alumina. 

Selective Toluene Disproportionation. Toluene disproportionates over ZSM-5 to benzene and a mixture of xylenes. Unlike this reaction over amorphous sihca—alumina catalyst, ZSM-5 produces a xylene mixture with increased -isomer content compared with the thermodynamic equihbtium. Chemical modification of the zeohte causing the pore diameter to be reduced produces catalysts that achieve almost 100% selectivity to -xylene. This favorable result is explained by the greatly reduced diffusivity of 0- and / -xylene compared with that of the less bulky -isomer. For the same reason, large crystals (3 llm) of ZSM-5 produce a higher ratio of -xyleneitotal xylenes than smaller crystahites (28,57). 

The slurry process requires less coating component. The latter is suspended in a vehicle, eg, lacquer or water, and is painted onto the substrate. The coated part is heated in an alumina retort containing a layer of activator at the bottom. The coating component forms a haHde and is deposited onto and diffused into the substrate. Slurry processes can be either activated or nonactivated. In the latter case, development of the coating reHes purely on diffusion without the possible benefits of vapor deposition. 

The support needs to be iaert, which explains the choice of a-Al O most metal oxides, including transition aluminas, cataly2e unselective oxidation. The catalyst has a low surface area, about 1 m /g, and large pores to minimise the influence of intraparticle diffusion, which would reduce the selectivity. 

Chromizing. The other principal method of obtaining a chromium-rich surface on steel is by chromizing (29). The material to be treated is embedded in a mixture of ferrochromium powder, a chromium halide, alumina, and sometimes NH Cl. The chromium is diffused in by a furnace... 

Diffusion within the largest cavities of a porous medium is assumed to be similar to ordinary or bulk diffusion except that it is hindered by the pore walls (see Eq. 5-236). The tortuosity T that expresses this hindrance has been estimated from geometric arguments. Unfortunately, measured values are often an order of magnitude greater than those estimates. Thus, the effective diffusivity D f (and hence t) is normally determined by comparing a diffusion model to experimental measurements. The normal range of tortuosities for sihca gel, alumina, and other porous solids is 2 < T < 6, but for activated carbon, 5 < T < 65. 

Azobenzene [103-33-3] M 182.2, m 68", pK 2.48. Ordinary azobenzene is nearly all in the transform. It is partly converted into the cw-form on exposure to light [for isolation see Hartley J Chem Soc 633 1938, and for spectra of cis- and /ran5-azobenzenes, see Winkel and Siebert Chem Ber 74B 6707947]. trans-Azobenzene is obtained by chromatography on alumina using 1 4 benzene/heptane or pet ether, and crystd from EtOH (after refluxing for several hours) or hexane. All operations should be carried out in diffuse red light or in the dark. 

Indeed, for operation at temperatures above 1 000°C (now required of advanced aircraft turbine blading materials) it appears that reliance must be placed on alumina as the protective layer, partly because in high velocity oxidising gas streams volatility of CrO, leads to appreciable loss of scale by the oxidation of the CrjO, layer, and partly because alumina is inherently a much better diffusion barrier. 

The transition from non-protective internal oxidation to the formation of a protective external alumina layer on nickel aluminium alloys at 1 000-1 300°C was studied by Hindam and Smeltzer . Addition of 2% A1 led to an increase in the oxidation rate compared with pure nickel, and the development of a duplex scale of aluminium-doped nickel oxide and the nickel aluminate spinel with rod-like internal oxide of alumina. During the early stages of oxidation of a 6% A1 alloy somewhat irreproducible behaviour was observed while the a-alumina layer developed by the coalescence of the rodlike internal precipitates and lateral diffusion of aluminium. At a lower temperature (800°C) Stott and Wood observed that the rate of oxidation was reduced by the addition of 0-5-4% A1 which they attributed to the blocking action of internal precipitates accumulating at the scale/alloy interface. At higher temperatures up to 1 200°C, however, an increase in the oxidation rate was observed due to aluminium doping of the nickel oxide and the inability to establish a healing layer of alumina. 

The second stage in the carburisation process, that of carbon ingress through the protective oxide layer, is suppressed by the development of alumina or silica layers as already discussed and in some cases protective chromia scales can also form. Diffusion and solubility of carbon in the matrix has been shown by Schnaas et to be a minimum for binary Fe-Ni alloys with a nickel content of about 80<7o, and Hall has shown that increasing the nickel content for the nickel-iron-2S<7o-chromium system resulted in lower rates of carburisation (Fig. 7.54). 

Microprobe studies of pack-chromised iron (Cr powder, alumina, CrCl, mixture) shows that the surface Cr concentration builds up with time to 95% in 20 h at 1 300 K ", and that the diffusion coefficient for Cr in a-phase is very concentration dependent. The growth of carbides during pack-chromising and during gas-vanadising have been studied. 

Johnson et al. (J5) have used the hydrogenation of a-methylstyrene catalyzed by palladium-alumina in powder form in agitated vessels. The physical diffusion of hydrogen through the liquid is the rate-controlling step. The total resistance of this transfer consisted of two separate resistances, one in the liquid adjoining the bubbles and another in the liquid adjoining the suspended solid particles. 

A hydrocarbon is cracked using a silica-alumina catalyst in the form of spherical pellets of mean diameter 2.0 mm. When the reactant concentration is 0.011 kmol/m3, the reaction rate is 8.2 x 10"2 kmol/(m3 catalyst) s. If the reaction is of first-order and the effective diffusivity De is 7.5 x 10 s m2/s, calculate the value of the effectiveness factor r). It may be assumed that the effect of mass transfer resistance in the. fluid external Lo the particles may be neglected. 

Other refractory oxides that can be deposited by CVD have excellent thermal stability and oxidation resistance. Some, like alumina and yttria, are also good barriers to oxygen diffusion providing that they are free of pores and cracks. Many however are not, such as zirconia, hafnia, thoria, and ceria. These oxides have a fluorite structure, which is a simple open cubic structure and is particularly susceptible to oxygen diffusion through ionic conductivity. The diffusion rate of oxygen in these materials can be considerable. 

As described in the previous section, the silica-alumina catalyst covered with the silicalite membrane showed exceUent p-xylene selectivity in disproportionation of toluene [37] at the expense of activity, because the thickness of the sihcahte-1 membrane was large (40 pm), limiting the diffusion of the products. In addition, the catalytic activity of silica-alumina was not so high. To solve these problems, Miyamoto et al. [41 -43] have developed a novel composite zeohte catalyst consisting of a zeolite crystal with an inactive thin layer. In Miyamoto s study [41], a sihcahte-1 layer was grown on proton-exchanged ZSM-5 crystals (silicalite/H-ZSM-5) [42]. The silicalite/H-ZSM-5 catalysts showed excellent para-selectivity of >99.9%, compared to the 63.1% for the uncoated sample, and independent of the toluene conversion. 

Alumina, present in the gamma modification, is the most suitable high surface area support for noble metals. The y-Al203 in washcoats typically has a surface area of 150-175 m g However, at high temperatures y-alumina transforms into the alpha phase, and stabilization to prevent this is essential. Another concern is the diffusion of rhodium into alumina, which calls for the application of diffusion barriers. 

Porous materials, such as silica and alumina, have thermal diffusion lengths of approximately 10 m, which is much less than the typical thickness of pressed discs. The small thermal diffusion length gives photoacoustic spectroscopy a larger dynamic range than transmission methods when applied to powdered samples. An additional advantage is the ease of sample preparation, since photoacoustic spectroscopy uses powdered samples with no special preparation required. 

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