Rheology of Disperse Systems

The rheology of disperse systems is an important processing parameter. Being able to characterize and manipulate the flow behavior of dispersions one can ensure their optimal performance. Waterborne automotive coatings, for example, should exhibit a distinct low-shear viscosity necessary to provide good leveling but to avoid sagging at the same time. Then, a strong degree of shear thinning is needed to guarantee good pumpand sprayability. The rheological properties of dispersions, especially at high solids content, are complex and strongly dependent on the applied forces and flow kinematics. Adding particles does not simply increase the viscosity of the liquid as a result of the hydrodynamic disturbance of the flow; it also can be a reason for deviation from Newtonian behavior, including shear rate dependent viscosity, elasticity, and time-dependent rheological behavior or even the occurrence of an apparent yield stress. In colloidal systems particle interactions play a crucial role. Depending on whether attractive or repulsive interactions dominate, the particles can form different structures that determine the rheological behavior of the material. In the case of attractive particle interactions loose flocs with fractal structure can be formed, immobilizing part of the continuous phase. This leads to a larger effective particle volume fraction and, correspondingly, to an increase in viscosity. Above a critical volume fraction a sample-spanning network forms, which results in a highly elastic, gel-like behavior, and an apparent yield stress. Shear-induced breakup and recovery of floc structure leads to thixotropic behavior. Electrostatic or steric repulsion between particles defines an excluded volume that is not accessible by other particles. This corresponds to an increase in effective volume fraction and accordingly to an increase in viscosity. Crystalline or gel-like states occur at particle concentrations lower than the maximum packing fraction. Characterization of the microstructure and flow properties of dispersions is essential for understanding and controlling their rheological behavior. In this chapter we first introduce methods and techniques for standard rheological tests and then characterize the rheology of hard sphere, repulsive, and attractive particles. The effect of particle size distribution on the rheology of highly concentrated