The stability of Aerosil-silica dispersions is analyzed in dependence on the addition of polycations with different charge density and hydrophobic modification using the analytical centrifuge LUMiSizer. This novel centrifugal sedimentation method allows the direct calculation of the stability parameters like sedimentation velocity and prediction of the shelf life. The highly charged polycation poly (diallyl-dimethylammonium chloride) (PDADMAC) is compared with tailored cationic polyelectrolytes of equal degree of polymerization but lower and different charge density as well as various hydrophobic substitutions. The used technique allows to accelerate demixing and to quantify the stability of dispersions in a direct way. All polymers under study are able to stabilize aerosil dispersions, but the shelf life strongly depends on the polymer concentration. Typically for polycations, the stability increases with the polymer concentration whereas at low-polymer content flocculation can be detected. In this context, the behavior of PDADMAC and three cationic PVB derivatives is similar, but, whereas the stability of PDADMAC containing dispersions decreases at higher polymer concentrations, PVB derivatives are effective stabilizers at hi-her concentrations too. The highest increase of the stability with increasing polymer concentration is obtained with the ampholytic terpolymer TP that has the lowest cationic charge. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 696-704, 2009