Derjaguin

Classic nucleation theory must be modified for nucleation near a critical point. Observed supercooling and superheating far exceeds that predicted by conventional theory and McGraw and Reiss [36] pointed out that if a usually neglected excluded volume term is retained the free energy of the critical nucleus increases considerably. As noted by Derjaguin [37], a similar problem occurs in the theory of cavitation. In binary systems the composition of the nuclei will differ from that of the bulk... 

Here we consider the total interaction between two charged particles in suspension, surrounded by tlieir counterions and added electrolyte. This is tire celebrated DLVO tlieory, derived independently by Derjaguin and Landau and by Verwey and Overbeek [44]. By combining tlie van der Waals interaction (equation (02.6.4)) witli tlie repulsion due to the electric double layers (equation (C2.6.lOI), we obtain... 

At the junction of the adsorbed film and the liquid meniscus the chemical potential of the adsorbate must be the resultant of the joint action of the wall and the curvature of the meniscus. As Derjaguin pointed out, the conventional treatment involves the tacit assumption that the curvature falls jumpwise from 2/r to zero at the junction, whereas the change must actually be a continuous one. Derjaguin put forward a corrected Kelvin equation to take this state of affairs into account but it contains a term which is difficult to evaluate numerically, and has aroused little practical interest. 

B. V. Derjaguin, in Proceedings of the Second International Congress on Surface Activity. II, p. 154, Butterworths, London (1957). 

The combined effect of van der Waals and electrostatic forces acting together was considered by Derjaguin and Landau (5) and independently by Vervey and Overbeek (6), and is therefore called DLVO theory. It predicts that the total interaction energy per unit area, also known as the effective interface potential, is given by V(f) = ( ) + dl ( )- absence of externally imposed forces, the equiHbrium thickness of the Hquid film... 

DLVO Theory. The overall stabiUty of a particle dispersion depends on the sum of the attractive and repulsive forces as a function of the distance separating the particles. DLVO theory, named for Derjaguin and Landau (11) and Verwey and Overbeek (12), encompasses van der Waals attraction and electrostatic repulsion between particles, but does not consider steric stabilization. The net energy, AGp between two particles at a given distance is the sum of the repulsive and attractive forces ... 

Two kinds of barriers are important for two-phase emulsions the electric double layer and steric repulsion from adsorbed polymers. An ionic surfactant adsorbed at the interface of an oil droplet in water orients the polar group toward the water. The counterions of the surfactant form a diffuse cloud reaching out into the continuous phase, the electric double layer. When the counterions start overlapping at the approach of two droplets, a repulsion force is experienced. The repulsion from the electric double layer is famous because it played a decisive role in the theory for colloidal stabiUty that is called DLVO, after its originators Derjaguin, Landau, Vervey, and Overbeek (14,15). The theory provided substantial progress in the understanding of colloidal stabihty, and its treatment dominated the colloid science Hterature for several decades. 

To account for some of the shortcomings of the JKR theory, Derjaguin and coworkers [19] developed an alternative theory, known as the DMT theory. According to the DMT theory, the attractive force between the surfaces has a finite range and acts outside the contact zone, where the surface shape is assumed to be Hertzian and not deformed by the effect of the interfacial forces. The predictions of the DMT theory are significantly different compared to the JKR theory. 

Bradley [29,30] and, independently, Derjaguin [31] were the first to recognize that a particle, under the influence of adhesion forces, could act like a Hertzian... 

By combining Hertz s contact theory (Eq. 1) and with Hamaker s functional form for the attractive force (Eq. 17), the Derjaguin model takes the form... 

By combining Eqs. 1, 20, and 22, the Derjaguin model, once again, takes the form... 

Johnson, Kendall and Roberts used an energy-based contact mechanics approach to understand particle adhesion. In their theory, they deviated from the earlier Derjaguin and Krupp models by assuming that tensile stresses are present... 

As indicated, an implicit assumption of the JKR theory is that there are no interactions outside the contact radius. More specifically, the energy arguments used in the development of the JKR theory do not allow specific locations of the adhesion forces to be determined except that they must be associated with the contact line where the two surfaces of the particle and substrate become joined. Adhesion-induced stresses act at the surface and not a result of action-at-a-distance interatomic forces. This results in a stress singularity at the circumference of the contact radius [41]. The validity of this assumption was first questioned by Derjaguin et al. [42], who proposed an alternative model of adhesion (commonly referred to as the DMT theory ). Needless to say, the predictions of the JKR and DMT models are vastly different, as discussed by Tabor [41]. 

Hertzian mechanics alone cannot be used to evaluate the force-distance curves, since adhesive contributions to the contact are not considered. Several theories, namely the JKR [4] model and the Derjaguin, Muller and Torporov (DMT) model [20], can be used to describe adhesion between a sphere and a flat. Briefly, the JKR model balances the elastic Hertzian pressure with attractive forces acting only within the contact area in the DMT theory attractive interactions are assumed to act outside the contact area. In both theories, the adhesive force is predicted to be a linear function of probe radius, R, and the work of adhesion, VFa, and is given by Eqs. 1 and 2 below. 

Muller, V.M., Yushchenko, V.S. and Derjaguin, B.V., General theoretical consideration of... 

An issue, at present unresolved, is that Derjaguin, Muller and Toporov [24,25] have put forward a different analysis of the contact mechanics from JKR. Maugis has described a theory which comprehends both the theories as special cases [26]. 

Derjaguin, B.V. and Landau, L., 1941. The stability of strongly charged lyophobic sols and the adhesion of strongly charged particles in solutions of electrolytes. Acta Physicochim, UPSS, 14, 633-662. 

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