Solid-liquid interfacial energy

Since it is relatively easy to transfer molecules from bulk liquid to the surface (e.g. shake or break up a droplet of water), the work done in this process can be measured and hence we can obtain the value of the surface energy of the liquid. This is, however, obviously not the case for solids (see later section). The diverse methods for measuring surface and interfacial energies of liquids generally depend on measuring either the pressure difference across a curved interface or the equilibrium (reversible) force required to extend the area of a surface, as above. The former method uses a fundamental equation for the pressure generated across any curved interface, namely the Laplace equation, which is derived in the following section. 

The change from methyl-to ethyl-substituted siloxanes (9->ll) yields a considerable surface tension increase. Again, this behavior is mainly due to an increase of the Lifshitz-van der Waals portion Considering the data for the interfacial tension solid/liquid and its portions the energy difference between methyl and ethyl groups at interfaces becomes even more transparent. For the methylated liquid 9 the donor-acceptor portion not accompanied by a significant portion. Ethyl groups make siloxanes less flexible [12] and cause a considerable portion. 

Molecular dynamics and density functional theory studies (see Section IX-2) of the Lennard-Jones 6-12 system determine the interfacial tension for the solid-liquid and solid-vapor interfaces [47-49]. The dimensionless interfacial tension ya /kT, where a is the Lennard-Jones molecular size, increases from about 0.83 for the solid-liquid interface to 2.38 for the solid-vapor at the triple point [49], reflecting the large energy associated with a solid-vapor interface. 

One remarkably simple yet seemingly robust outcome of Turnbull s experiments was his empirical finding that the solid-liquid interfacial free energy was... 

In liquid-phase sintering, densification and microstmcture development can be assessed on the basis of the liquid contact or wetting angle, ( ), fonned as a result of the interfacial energy balance at the solid-liquid-vapour intersection as defined by the Young equation ... 

Figure C2.11.8. An illustration of the equilibrium contact (i.e. wetting) angle, ( ), fonned by the balance of interfacial energies for or a liquid (sessile) drop on a flat solid surface.

The phenomenon of wetting of a solid by a liquid depends on the surfaces and interfacial energies. When a liquid droplet is in contact with an ideally smooth solid surface, as shown schematically in Fig. 9, according to the Young s equation [72], the contact angle (6) of the liquid is given by... 

The solid-liquid interfacial energy is related to the solid surface energy through... 

The Good-Girifalco theory [77-82] was originally formulated to make an attempt to correlate the solid-liquid interfacial tension to the solid surface energy and the liquid surface tension through an interaction parameter, basic formulation of the theory is ... 

Considering a solid-liquid system, this relationship may be combined with the well-known Young s equation to eliminate the interfacial free energy. Hence,... 

In the absence of specific interactions of the receptor - ligand type the change in the Helmholtz free energy (AFadj due to the process of adsorption is AFads = yps - ypi - Ysi, where Yps, YPi and ys, are the protein-solid, protein-liquid and solid-liquid interfacial tensions, respectively [5], It is apparent from this equation that the free energy of adsorption of a protein onto a surface should depend not only of the surface tension of the adhering protein molecules and the substrate material but also on the surface tension of the suspending liquid. Two different situations are possible. 

Stability may be inherent or induced. In the latter case, the original system is in a condition of metastable or neutral eouilibrium. External influences which induce instability in a dispersion on standing are changes in temperature, volume, concentration, chemical composition, and sediment volume. Applied external influences consist of shear, introduction of a third component, and compaction of the sediment. Interfacial energy between solid and liquid must be minimized, if a dispersion is to be truly stable. Two complementary stabilizing techniques are ionic and steric protection of the dispersed phase. The most fruitful approach to the prediction of physical stability is by electrical methods. Sediment volumes bear a close relation to repulsion of particles for each other. 

In terms of the two-phase system which comprises dispersions of solids in liquids, the minimum energy requirement is met if the total interfacial energy of the system has been minimized. If this requirement has been met, chemically, the fine state of subdivision is the most stable state, and the dispersion will thus avoid changing physically with time, except for the tendency to settle manifest by all dispersions whose phases have different densities. A suspension can be stable and yet undergo sedimentation, if a true equilibrium exists at the solid-liquid interface. If sedimentation were to be cited as evidence of instability, no dispersion would fit the requirements except by accident—e.g., if densities of the phases were identical, or if the dispersed particles were sufficiently small to be buoyed up by Brownian movement. 

The interfacial barrier theory is illustrated in Fig. 15A. Since transport does not control the dissolution rate, the solute concentration falls precipitously from the surface value, cs, to the bulk value, cb, over an infinitesimal distance. The interfacial barrier model is probably applicable when the dissolution rate is limited by a condensed film absorbed at the solid-liquid interface this gives rise to a high activation energy barrier to the surface reaction, so that kR kj. Reaction-controlled dissolution is somewhat rare for organic compounds. Examples include the dissolution of gallstones, which consist mostly of cholesterol,... 

The average interfacial energy between the solid and liquid forms of a given element is generally lower than ys8 and cr1, e.g. 0.093 and 0.24 J m-2 for A1 and Pt. For materials which change coordination number upon melting ysl is larger. 

The distribution of the liquid is determined by the interfacial energy between the liquid and the solid matrix relatively to the grain boundary energy. An example is shown in Figure 6.11 (a), where an important characteristic of grain boundaries, the... 

---