Physicochemical properties of cationic polyelectrolytes: poly(allylamine hydrochloride) (PAH), poly(ethylene imine) (PEI), and poly(dimethyldiallylammonium chloride) (PDDA), having molar mass of 70,000, 75,000, and 120,000, respectively, were examined and compared. The bulk characteristics comprised the diffusion coefficient and electrophoretic mobility determined as a function of pH (3.5-9) and ionic strengths (10(-4) M to 0.15 M NaCl). These measurements allowed one to determine the amount of electrokinetic charge of the polyelectrolyte molecules and their isoelectric points. On the other hand, formation of poIyelectrolyte monolayers on mica and their properties were investigated using the in situ streaming potential method. Additionally, using this method, the stability of monolayers, evaluated via desorption kinetic measurements, was determined. The investigations showed that PAH molecules form the most stable monolayers, which can be used as supporting layers for particle deposition and multilayer formation. (C) 2013 Elsevier Inc. All rights reserved.