Interfacial area composites

The chemical composition, physical stmcture, and key physical properties of a foam, namely its stabiHty and theology, are all closely interrelated. Since there is a large interfacial area of contact between Hquid and vapor inside a foam, the physical chemistry of Hquid—vapor interfaces and their modification by surface-active molecules plays a primary role underlying these interrelationships. Thus the behavior of individual surface-active molecules in solution and near a vapor interface and their influence on interfacial forces is considered here first. 

A hypothetical chemical structure in the interfacial area of the PMPPlC-treated composite [72] is shown in Fig. 10. The long-chain molecules present in PMPPIC interact with polyethylene leading to van der Waals type of interaction. 

Consequently, interpenetrating phase-separated D/A network composites, i.e. bulk heterojunction , would appear to be ideal photovoltaic materials [5]. By controlling the morphology of the phase separation into an interpenetrating network, one can achieve a high interfacial area within a bulk material. Since any point in the composite is within a few nanometers of a D/A interface, such a composite is a bulk D/A heterojunction material. If the network in a device is bicontinuous, as shown in Figure 15-26, the collection efficiency can be equally efficient. 

A quite different approach was introduced in the early 1980s [44-46], in which a dense solid electrode is fabricated which has a composite microstructure in which particles of the reactant phase are finely dispersed within a solid, electronically conducting matrix in which the electroactive species is also mobile. There is thus a large internal reactant/mixed-conductor matrix interfacial area. The electroactive species is transported through the solid matrix to this interfacial region, where it undergoes the chemical part of the electrode reaction. Since the matrix material is also an electronic conductor, it can also act as the electrode s current collector. The electrochemical part of the reaction takes place on the outer surface of the composite electrode. 

In this process, the two streams flow countercurrently through the column and undergo a continuous change in composition. At any location are in dynamic rather than thermodynamic equilibium. Such processes are frequently carried out in packed columns, in which the liquid (or one of the two liquids in the case of a liquid-liquid extraction process) wets die surface of the packing, thus increasing the interfacial area available for mass transfer and, in addition, promoting high film mass transfer coefficients within each phase. 

First, in composites with high fiber concentrations, there is little matrix in the system that is not near a fiber surface. Inasmuch as polymerization processes are influenced by the diffusion of free radicals from initiators and from reactive sites, and because free radicals can be deactivated when they are intercepted at solid boundaries, the high interfacial area of a prepolymerized composite represents a radically different environment from a conventional bulk polymerization reactor, where solid boundaries are few and very distant from the regions in which most of the polymerization takes place. The polymer molecular weight distribution and cross-link density produced under such diffusion-controlled conditions will differ appreciably from those in bulk polymerizations. 

Experimental values for several systems are given by Cornell et al. (1960), Eckert (1963), and Vital et al. (1984). A selection of values for a range of systems is given in Table 11.3. The composite mass transfer term KGa is normally used when reporting experimental mass-transfer coefficients for packing, as the effective interfacial area for mass transfer will be less than the actual surface area a of the packing. 

Molecules in the surface or interfacial region are subject to attractive forces from adjacent molecules, which result in an attraction into the bulk phase. The attraction tends to reduce the number of molecules in the surface region (increase in inter-molecular distance). Hence work must be done to bring molecules from the interior to the interface. The minimum work required to create a differential increment in surface dA is ydA, where A is the interfacial area and y is the surface tension or interfacial tension. One also refers to y as the interfacial Gibbs free energy for the condition of constant temperature, T, pression, P, and composition (n = number of moles)... 

K is the overall mass-transfer coefficient based on the liquid phase. A is the total interfacial area in the gas-liquid dispersion. C is the concentration in the liquid phase. C thus corresponds to equilibrium with the gas phase of composition y. H is the Henry coefficient for the gas. In the case of oxygen or a sparingly soluble compound, H is large and resistance to mass transfer is located in the liquid phase. 

An accurate evaluation of kxa is complicated by the heterogeneous nature and poor definition of contaminant/soil systems. Some success has been achieved in modeling mass transfer from a separate contaminant phase. During degradation these nonaqueous phase liquids (NAPLs) often dissolve under conditions where phase equilibrium is not achieved and dissolution is proportional to k a. Experimental determinations and correlations for k-p depend on interfacial area of the NAPL and liquid velocity at the interface (Geller Hunt, 1993). For adsorbed contaminants, kxa varies with soil composition and structure, concentration and age of contamination, and therefore with time. For example, slurry reactor tests indicate that the rate of naphthalene mass transfer decreases with time, with media size, and with aging of the tar prior to testing (Luthy et al., 1994). 

Kinetics of Aromatic Nitrations. The kinetics of aromatic nitrations are functions of temperature, which affects the kinetic rate constant, and of the compositions of both the acid and hydrocaibon phase. In addition, a larger interifacial area between the two phases increases the rates of nitration since the main reactions occur at or near the interface. Larger interfacial areas are oblaincd by increased agitation and by ihc proper choice of the volumetric % acid in the liquid-liquid dispersion. The viscosities and densities of the two phases and the interfacial tension between the phases are important physical properties affecting the interfacial area. 

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