Introduction

The preceding chapters address interactions between colloidal particles dispersed in pure liquid or electrolyte solution. The hydrodynamic and dispersion forces depend only on the bulk properties of the individual phases, i.e. the viscosity and the dielectric permittivities. Electrostatic forces arising from the surface charges, however, are accompanied by free electrolyte. The associated electric fields distribute these additional species non-uniformly in the surrounding fluid, thereby producing a spatially varying osmotic pressure. Electrostatic interactions between particles alter these ion distributions, affecting the electric and pressure fields and generating an interparticle force.

We now consider another component commonly present in colloidal systems, soluble polymer. In many ways, the phenomena and the theoretical treatment resemble those for electrostatics. The interactions between polymer and particle generate non-uniform distributions of polymer throughout the solution. Particle–particle interactions alter this equilibrium distribution, producing a force whose sign and magnitude depend on the nature of the particle–polymer interaction. The major difference from the ionic solutions lies in the internal degrees of freedom of the polymer, which necessitate detailed consideration of the solution thermodynamics.

The reasons for adding soluble polymer to colloidal dispersions are several. The earliest known role, as stabilizer, aids or preserves the dispersion through adsorption of the macromolecule onto the surfaces of the particles to produce a strongly repulsive interaction. Homopolymers achieve this by adsorbing to particles non-specifically at multiple points along their backbone, while block or graft copolymers adsorb irreversibly at one end with the other remaining in solution (Napper, 1983).

Introduction

In the preceding chapters we have examined the response of colloidal particles to interactions with one another in a quiescent fluid, to interactions with large collectors while being convected by the fluid, and to imposed forces due to electric fields, gravity, or concentration gradients. In each case, equilibrium or non-equilibrium, static or dynamic, the interparticle forces and the resulting suspension microstructure play key roles. Now we consider the stresses and the non-equilibrium microstructure generated in a flowing suspension when the velocity varies spatially on a scale large with respect to the size of the particles.

A Newtonian incompressible liquid is characterized by a linear relation between the stress tensor and the rate-of-strain tensor, with the constant of proportionality being the viscosity. Polymeric liquids are well known for their non-Newtonian behavior including shear-rate-dependent viscosities, elasticity manifested in recoil upon the cessation of flow, solid-like fracture during extrusion, and a variety of secondary flow phenomena. Colloidal suspensions also depart from Newtonian behavior. They often behave as solids requiring a finite stress, the yield stress, before deforming continuously as a liquid. The contrast with the polymeric liquids reflects the fundamentally different microstructures. Both microstructures deform under stress, but macromolecular systems can recover from strains of several hundred per cent because the restoring force increases with the degree of deformation. The interparticle forces governing the microstructure in colloidal dispersions generally have a short range and the magnitude decreases with increasing separation, providing no mechanism for recovery beyond strains of a few per cent.

Introduction

Microscopic observations of colloidal particles in the nineteenth century revealed their tendency to form persistent aggregates through collisions induced by Brownian motion, clearly indicating an attractive interparticle force. Identification of its origin, however, awaited the quantitative descriptions of van der Waals forces between molecules developed in the 1920s (Israelachvili, 1985). This development prompted Kallman & Willstätter (1932) and Bradley (1932) to realize the summation over pairs of molecules in interacting particles would yield a long-range attraction.

Subsequently, de Boer (1936) and Hamaker (1937) performed explicit calculations of dispersion forces between colloidal particles by assuming the intermolecular forces to be strictly pairwise additive. Although approximate, this theory captures the essence of the phenomenon. The attraction arises because local fluctuations in the polarization within one particle induce, via the propagation of electromagnetic waves, a correlated response in the other. The associated free energy decreases with decreasing separation. Phase shifts introduced at large separations by the finite velocity of propagation reduce the degree of correlation, and, therefore, the magnitude of the attraction. Although the intermolecular potential decays rapidly on the molecular scale, the cumulative effect is a long-range interparticle potential that scales on the particle size.