Interactions involving charged particles in the presence of multivalent ions are relevant in wide-range of phenomena, including condensation of nucleic acids, cement hardening, or water treatment. Here, we study such interactions by combining direct force measurements with atomic force microscopy (AFM) and aggregation studies with time-resolved light scattering for particles originating from the same colloidal suspension for the first time. Classical DLVO theory is found to be only applicable for monovalent and divalent ions. For ions of higher valence, charge inversion and additional non-DLVO attractive forces are observed. These attractive forces can be attributed to surface charge heterogeneities, which leads to stability ratios that are calculated from direct force measurements to be higher than the experimental ones. Ion-ion correlations are equally important as they induce the charge inversion in the presence of trivalent or tetravalent ions, and they enhance the surface charge heterogeneities. Such heterogeneities therefore play an essential role in controlling interactions in particle suspensions containing multivalent ions.

Direct force measurements between oppositely charged latex particles in aqueous electrolyte solutions were carried out with a multiparticle colloidal probe technique based on atomic force microscopy. Force profiles between two dissimilarly charged surfaces can be only described when charge regulation effects are taken into account, while constant charge or constant potential boundary conditions are inappropriate. Surface potentials and regulation parameters are determined from force data obtained in symmetric systems with the Poisson-Boltzmann theory and constant regulation approximation. The resulting quantities are used to predict the force profiles in asymmetric systems, and good agreement between theory and experiment is found. These findings show that charge regulation is important to quantify double-layer forces in asymmetric systems.

Direct force measurements between negatively charged colloidal latex particles of a diameter of 1 μm were carried out in aqueous solutions of various inorganic monovalent and multivalent cations with the multiparticle colloidal probe technique based on the atomic force microscope (AFM). The observed force profiles were rationalized within the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). In the presence of monovalent and divalent cations, this theory was capable to describe the force profiles correctly down to distances of a few nm. At shorter distances, however, a strong non-DLVO attraction was identified. For more highly charged cations, an additional and more long-ranged non-DLVO attractive force is observed, and it was interpreted by surface charge heterogeneities. On the basis of these force profiles, the aggregation rates, which were independently measured by light scattering, can be predicted relatively well. The main conclusion of this study is that, in the present system, direct force measurements do capture the principal interactions driving aggregation in colloidal suspensions.

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Long chain sodium polyacrylate polymers in dilute aqueous solution respond extremely sensitive to the addition of small, stoichiometric amounts of Ca2+ ions. Essential features of this response are a considerable shrinking of the coil dimensions and an additional sensitivity of the coil dimensions toward a change in temperature. To reveal details of this shrinking process, the conformational changes in response to the addition of alkaline earth cations at two different temperatures are investigated by means of light and neutron scattering and by AFM on the same samples, respectively. Partially collapsed coils at 15 °C were further shrunken and modified in shape by increasing the temperature to 30 °C. The scattering curves from the intermediates at 30 °C could successfully be interpreted with a pearl necklace model, which includes a low amount of pearls per polymer separated by 80 nm from each other. AFM investigations of adsorbed chains confirm the drastic conformational changes inferred to the system with the temperature increase by 15 °C. The results are considered to be one of the rare direct evidence for a pearl-necklace-like intermediate along the coil-to-globule transition of polyelectrolyte chains.

Interactions between negatively charged latex particles in the presence of cationic linear poly(ethylene imine) (LPEI) were studied with atomic force microscopy (AFM) and electrophoresis. Forces were measured directly with the recently developed multiparticle colloidal probe technique, which permits colloidal particles to attach to the cantilever in aqueous dispersions in situ and ensures a large surface area during experiment. It was observed that the forces vary from repulsive to attractive and back to repulsive with increasing polymer dose. The repulsive forces are due to overlap of the diffuse layers around charged surfaces. The attractive forces are independent of the ionic strength and the molecular mass of the polymer and can be rationalized in terms of classical van der Waals interactions. Additional electrostatic attractive forces due to patch-charge heterogeneities observed in other particle-polyelectrolyte systems are absent here. Their absence indicates that the adsorbed layer of LPEI has a high lateral homogeneity.

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Forces between individual colloidal particles can be measured with the atomic force microscope (AFM), and this technique permits the study of interactions between surfaces across aqueous solutions in great detail. The most relevant forces are described by the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, and they include electrostatic double-layer and van der Waals forces. In symmetric systems, the electrostatic forces are repulsive and depend strongly on the type and concentration of the salts present, while van der Waals forces are always attractive. In asymmetric systems, the electrostatic force can become attractive as well, even when involving neutral surfaces, while in rare situations van der Waals forces can become repulsive too. The enormous sensitivity of the double layer forces on additives present is illustrated with oppositely charged polyelectrolytes, which may induce attractions or repulsions depending on their concentrations.