Interface energy Subject

In Chapter 3 we described the structure of interfaces and in the previous section we described their thermodynamic properties. In the following, we will discuss the kinetics of interfaces. However, kinetic effects due to interface energies (eg., Ostwald ripening) are treated in Chapter 12 on phase transformations, whereas Chapter 14 is devoted to the influence of elasticity on the kinetics. As such, we will concentrate here on the basic kinetics of interface reactions. Stationary, immobile phase boundaries in solids (e.g., A/B, A/AX, AX/AY, etc.) may be compared to two-phase heterogeneous systems of which one phase is a liquid. Their kinetics have been extensively studied in electrochemistry and we shall make use of the concepts developed in that subject. For electrodes in dynamic equilibrium, we know that charged atomic particles are continuously crossing the boundary in both directions. This transfer is thermally activated. At the stationary equilibrium boundary, the opposite fluxes of both electrons and ions are necessarily equal. Figure 10-7 shows this situation schematically for two different crystals bounded by the (b) interface. This was already presented in Section 4.5 and we continue that preliminary discussion now in more detail. 

Bending moduli can in principle be obtained for two types of systems (i) extended, flat surfaces or interfaces, the subject matter of this section, and (ii) surfaces that are already strongly curved, and for which y is zero or extremely low, such as in vesicles or micro-emulsions. For instance such moduli can be inferred from shape fluctuations, from the Kerr effect (sec. 1.7.14] or from polydispersity using some scattering technique. We repeat that this type of measurement is often ambiguous because the bending contributions to the Helmholtz energy can only be estimated when all other contributions are accurately known. 

Let us now briefly mention an approach that is popular among physicists, and which comes down to correlating surface tensions to capillary waves. The underlying idea is that each fluid-fluid interface is subject to a superposition of a large number of thermal waves. The amplitudes of these waves are related to the inter-facial excess energy and the number and frequencies to the interfacial excess entropy, hence the total information obtainable yields F°, and hence y. The idea dates back to Mandelstam and has been taken up by others, including Frenkel and Buff et al. . ... 

The total interfacial free energy per unit area, consists of the sum of /o and the free energy per unit area that comes from the liquid-vapor interface. In equilibrium, one minimizes the total free energy subject to the conservation constraint — i.e., one works at fixed chemical potential. As explained in the discussion of the gas-fiquid interface in Chapter 2, the appropriate bulk free energy to minimize to find the interfacial profile is the grand potential per unit area, gs, which is written ... 

If the air is replaced by a liquid L2, immiscible with the liquid Li constituting the droplet, we find a quite analogous situation. On either side of the interface, the molecules close to the interface are subject to forces which are only partially balanced. In the same way, if we wish to increase the interfacial area, by dispersing Li in L2, for example, the energy... 

FEA has also been used to study interface adhesion between thin film and substrate under indentation. Liu et al. (2007) examined the interface delamination and buckling of thin film subjected to microwedge indentation. In their model, the interface adjoining the thin film and substrate is assumed to be the only site where cracking can occur. A traction—separation law with interface strength and interface energy as two major parameters was introduced to simulate the adhesive and failure behaviors of the interface between the film and the substrate. 

Many of the important chemical applications of ILs will occur at solid surfaces, including electrochemical processes at IL-electrode interfaces, lubrication of ILs, fabrication of IL solid electrolytes and IL solid catalysts, etc. When a solid interface is present, molecules near the interface are subject to diflferent interactions than in the bulk phase, and the free energy of a surface can often be reduced by local changes in molecular orientation, aggregation, density, or composition. Familiar examples include surface adsorption, wetting and the electrochemical double-layer structure, where dipole moments usually lie at the interface. The surfaces of ionic liquids at the solid surface show dramatic changes in local structure, which can be demonstrated using simulations and probed by a number of experimental techniques. Due to a wide variety of experimental, theoretical, and... 

A general prerequisite for the existence of a stable interface between two phases is that the free energy of formation of the interface be positive were it negative or zero, fluctuations would lead to complete dispersion of one phase in another. As implied, thermodynamics constitutes an important discipline within the general subject. It is one in which surface area joins the usual extensive quantities of mass and volume and in which surface tension and surface composition join the usual intensive quantities of pressure, temperature, and bulk composition. The thermodynamic functions of free energy, enthalpy and entropy can be defined for an interface as well as for a bulk portion of matter. Chapters II and ni are based on a rich history of thermodynamic studies of the liquid interface. The phase behavior of liquid films enters in Chapter IV, and the electrical potential and charge are added as thermodynamic variables in Chapter V. 

The interface free energy per unit area fi,u is taken to be that of a planar interface between coexisting phases. Considering a solution v /(z) that minimizes Eq. (5) subject to the boundary conditions vj/(z - oo) = - v /coex, v /(z + oo) = + vj/ oex one finds the excess free energy of a planar interface ... 

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)... 

As shown by Fowkes (1968) the interfacial energy between two phases (whose surface tensions - with respect to vacuum - are y1 and y2) is subject to the resultant force field made up of components arising from attractive forces in the bulk of each phase and the forces, usually the London dispersion forces (cf. Eq. 4.2) operating accross the interface itself. Then the interfacial tension (energy) between two phases y12 s given by... 

Chan (Chapter 6) presents a simple graphical method for estimating the free energy of EDL formation at the oxide-water interface with an amphoteric model for the acidity of surface groups. Subject to the assumptions of the EDL model, the graphical method allows a comparison of the magnitudes of the chemical and coulombic components of surface reactions. The analysis also illustrates the relationship between model parameter values and the deviation of surface potential from the Nernst equation. 

In the gas/vapour phase the dimensionless distance tj ranges from 0 to 1, where tj — 1 corresponds to the position of the interface. In the liquid phase this parameter ranges from 0 to 1 for the mass transfer film and from 0 to Le for the heat transfer film. Hence, rj = 0 corresponds to the position of the interface and rj = I and t] = Le correspond, respectively, to the boundaries of the mass and heat transfer film. The mass and energy fluxes can now be calculated by solving the differential equations (4) and (8)-(12) subject to the boundary conditions (15). Due to the non-linearities a numerical solution procedure has been used which will be discussed subsequently. 

The microductile/compliant layer concept stems from the early work on composite models containing spherical particles and oriented fibers (Broutman and Agarwal, 1974) in that the stress around the inclusions are functions of the shear modulus and Poisson ratio of the interlayer. A photoelastic study (Marom and Arridge, 1976) has proven that the stress concentration in the radial and transverse directions when subjected to transverse loading was substantially reduced when there was a soft interlayer introduced at the fiber-matrix interface. The soft/ductile interlayer allowed the fiber to distribute the local stresses acting on the fibers more evenly, which, in turn, enhanced the energy absorption capability of the composite (Shelton and Marks, 1988). 

The kineties of eleetron-transfer reactions, which is also affected by the electrode potential and the metal-water interface, is more difficult and complex to treat than the thermodynamic aspects. While the theoretical development for electron transfer kinetics began decades ago, a practical implementation for surface reactions is still unavailable. Popular transition state-searching techniques such as the NEB method are not designed to search for minimum-energy reaction paths subject to a constant potential. Approximations that allow affordable quantum chemistry calculations to get around this limitation have been proposed, ranging from the electron affinity/ionization potential matching method to heuristic arguments based on interpolations. 

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