Rheological characterization of bimodal colloidal dispersions

In order to investigate the effect of the particle size distribution on the rheological properties of concentrated colloidal dispersions both steady-state shear and oscillatory measurements have been performed on well-characterized bimodal dispersions of sterically stabilized PMMA particles. Replacing a minor amount of large particles by small ones in a concentrated dispersion, keeping the total effective volume fraction constant, decreases the viscosity quite drastically. On the other hand, replacing a small amount of small particles by big ones hardly effects the viscosity at all. This behavior can be attributed to the deformability of the stabilizing polymer layer. A procedure is proposed to calculate the limiting viscosities in a bimodal colloidal dispersion starting from the characteristics of the monodisperse systems. A good agreement has been obtained between the calculated values and the experimental results. The linear viscoelastic properties of the concentrated dispersions have been investigated by means of oscillatory measurements. The plateau values of the storage modulus for the bimodal dispersions decrease with an increasing fraction of the coarse particles. By substituting the bimodal dispersion by an equivalent monodisperse system the storage modulus can be superimposed on the values for the monodisperse suspensions when plotted as a function of the mean interparticle distance.