Surface force dispersion forces

To first order, the dispersion (a-a) interaction is independent of the structure in a condensed medium and should be approximately pairwise additive. Qualitatively, this is because the dispersion interaction results from a small perturbation of electronic motions so that many such perturbations can add without serious mutual interaction. Because of this simplification and its ubiquity in colloid and surface science, dispersion forces have received the most significant attention in the past half-century. The way dispersion forces lead to long-range interactions is discussed in Section VI-3 below. Before we present this discussion, it is useful to recast the key equations in cgs/esu units and SI units in Tables VI-2 and VI-3. 

Contact angle techniques used to evaluate thin films of water-soluble collagen, with care to avoid denaturing eflFects, gave a critical surface tension approaching 40 dynes/cm (8). An anomalous nonwettability by some of the low surface-tension, dispersion-force-only liquids was evident, and this was attributed to organized water adsorbed at the surface of... 

For low energy surfaces, the dispersion force component is larger than the nondispersion force component which, however, cannot be neglected or assumed to be nonexistent. An exception is paraffin wax. The results of Table III for paraflBn confirm that ya is zero, consistent with a surface composed completely of hydrocarbon entities with no polar components. By this treatment, Tefion turns out to have a small but definite polar component of y (10). 

In the last 40 years, techniques to directly measure surface forces and force laws (force vs. separation distance between surfaces) have been developed such as the surface forces apparatus (SFA) [6] and AFM. Surface forces are responsible for the work required when two contacting bodies (such as an AFM tip in contact with a solid surface) are separated from contact to infinite distance. Although the physical origin of all relevant surface forces can be derived from fundamental electromagnetic interactions, it is customary to group these in categories based on characteristic features that dominate the relevant physical behavior. Thus, one speaks of ionic (monopole), dipole—dipole, ion—dipole interactions, electrostatic multipole forces (e.g., quadrupole), induced dipolar forces, van der Waals (London dispersive) interactions, hydrophobic and hydrophilic solvation, structural and hydration forces,... 

Heats of adsorption (AHa s). y be calculated for monolayers bound to surfaces by dispersion forces by assuming that the free energy of adsorption (per imit area of adsorbent) at p/p = 1 is given by ads = - S as Harkins [13] and Chessick [3] have done ... 

The logical next step in the process of extending the utility of theory to practical systems is to include polar molecular interactions. For this step, Fowkes suggested that the intermolecular forces contributing to surface and interfacial tensions, and subsequent phenomena such as wetting, could be broken down into independent and additive terms. For example, a polar molecule such as an ester would have two terms making up its surface tension—dispersion forces (d) and dipolar interactions (p)—so that... 

Adhesion, by its definition, depends on the ability of two unlike phases to hold themselves together across a common interface. Physical adhesion must first take place before any other bonding processes such as chemical reaction can occur, and such physical adhesion depends on the strength of intermolecular force interaction, on the area of contact and on the distance separating the atoms forming the top layer of each surface (see Dispersion forces, polar forces). When both phases are undeformable, such as with two solids that are not atomically smooth, poor adhesion results because an insufficient area of each surface is in atomic contact with the other. When one phase is deformable, such as with a liquid of low viscosity, physical adhesion takes place at all parts of the surface. Physical adhesion with a liquid in contact with a solid leads to spreading and wetting processes that now depend on the competition of adhesion forces with cohesion forces within the liquid. 

Equilibrium vapor pressure Molar heat of vaporization Surface tension Vapor pressure Viscosity Section 15.3 Dipole dipole forces Dispersion forces... 

The adsorption isotherm results from the controlled physical adsorption of a gas or vapor or solute from a solution into an activated carbon. This process of physical adsorption is the way in which the adsorptive (gas, vapor or solute) enters into the porosity. The close proximity of carbon atoms to each other, as they constitute the boundary or surface of the porosity, results in these gas adsorbate molecules being retained within the porosity. The retention is the result of enhanced van der Waals forces (dispersion forces) within the porosity. This process of physical adsorption is exceedingly dynamic. Energetically, an adsorbed state is more stable than the gaseous state of the adsorptive at 273 K and 0.1 MPa of pressure. 

In addition to the surface forces, hydrodynamic forces play an important role for the interactions in the real liquid films and colloidal dispersions. The hydrodynamic force is due to the viscous friction accompanying the expulsion of the liquid from the gap between two particles. When the particles are fluid (drops, bubbles), the fluidity of their surfaces (determined by the properties of the surfactant adsorption monolayers) can significantly... 

In this section we consider electromagnetic dispersion forces between macroscopic objects. There are two approaches to this problem in the first, microscopic model, one assumes pairwise additivity of the dispersion attraction between molecules from Eq. VI-15. This is best for surfaces that are near one another. The macroscopic approach considers the objects as continuous media having a dielectric response to electromagnetic radiation that can be measured through spectroscopic evaluation of the material. In this analysis, the retardation of the electromagnetic response from surfaces that are not in close proximity can be addressed. A more detailed derivation of these expressions is given in references such as the treatise by Russel et al. [3] here we limit ourselves to a brief physical description of the phenomenon. 

A major advance in force measurement was the development by Tabor, Win-terton and Israelachvili of a surface force apparatus (SFA) involving crossed cylinders coated with molecularly smooth cleaved mica sheets [11, 28]. A current version of an apparatus is shown in Fig. VI-4 from Ref. 29. The separation between surfaces is measured interferometrically to a precision of 0.1 nm the surfaces are driven together with piezoelectric transducers. The combination of a stiff double-cantilever spring with one of a number of measuring leaf springs provides force resolution down to 10 dyn (10 N). Since its development, several groups have used the SFA to measure the retarded and unretarded dispersion forces, electrostatic repulsions in a variety of electrolytes, structural and solvation forces (see below), and numerous studies of polymeric and biological systems. 

A thin film of hydrocarbon spread on a horizontal surface of quartz will experience a negative dispersion interaction. Treating these as 1 = quartz, 2 = n-decane, 3 = vacuum, determine the Hamaker constant A123 for the interaction. Balance the negative dispersion force (nonretarded) against the gravitational force to find the equilibrium film thickness. 

Determine the net DLVO interaction (electrostatic plus dispersion forces) for two large colloidal spheres having a surface potential 0 = 51.4 mV and a Hamaker constant of 3 x 10 erg in a 0.002Af solution of 1 1 electrolyte at 25°C. Plot U(x) as a function of x for the individual electrostatic and dispersion interactions as well as the net interaction. 

Surface waves at an interface between two innniscible fluids involve effects due to gravity (g) and surface tension (a) forces. (In this section, o denotes surface tension and a denotes the stress tensor. The two should not be coiifiised with one another.) In a hydrodynamic approach, the interface is treated as a sharp boundary and the two bulk phases as incompressible. The Navier-Stokes equations for the two bulk phases (balance of macroscopic forces is the mgredient) along with the boundary condition at the interface (surface tension o enters here) are solved for possible hamionic oscillations of the interface of the fomi, exp [-(iu + s)t + i V-.r], where m is the frequency, is the damping coefficient, s tlie 2-d wavevector of the periodic oscillation and. ra 2-d vector parallel to the surface. For a liquid-vapour interface which we consider, away from the critical point, the vapour density is negligible compared to the liquid density and one obtains the hydrodynamic dispersion relation for surface waves + s>tf. The temi gq in the dispersion relation arises from... 

The measurement of surface forces out-of-plane (nonual to the surfaces) represents a central field of use of the SFA teclmique. Besides the ubiquitous van der Waals dispersion interaction between two (mica) surfaces... 

Carbon-fluorine bonds are quite strong (slightly stronger than C—H bonds) and like polyethylene Teflon is a very stable inert material We are all familiar with the most characteristic property of Teflon its nonstick surface This can be understood by com paring Teflon and polyethylene The high electronegativity of fluorine makes C—P bonds less polarizable than C—H bonds causing the dispersion forces m Teflon to be less than those m polyethylene Thus the surface of Teflon is even less sticky than the already slick surface of polyethylene... 

Drops coalesce because of coUisions and drainage of Hquid trapped between colliding drops. Therefore, coalescence frequency can be defined as the product of coUision frequency and efficiency per coUision. The coUision frequency depends on number of drops and flow parameters such as shear rate and fluid forces. The coUision efficiency is a function of Hquid drainage rate, surface forces, and attractive forces such as van der Waal s. Because dispersed phase drop size depends on physical properties which are sometimes difficult to measure, it becomes necessary to carry out laboratory experiments to define the process mixing requirements. A suitable mixing system can then be designed based on satisfying these requirements. 

Sorption of nonionic, nonpolar hydrophobic compounds occurs by weak attractive interactions such as van der Waals forces. Net attraction is the result of dispersion forces the strength of these weak forces is about 4 to 8 kj/mol ( 1 2 kcal/mol). Electrostatic interactions can also be important, especially when a molecule is polar in nature. Attraction potential can develop between polar molecules and the heterogeneous sod surface that has ionic and polar sites, resulting in stronger sorption. 

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