Synergistic Polymer-Surfactant-Complex Mediated Colloidal Interactions and Deposition.

Total internal reflection microscopy (TIRM) is used to directly, sensitively, and simultaneously measure colloidal interactions, dynamics, and deposition for a broad range of polymer-surfactant compositions. A deposition state diagram containing comprehensive information about particle interactions, trajectories, and deposition behavior is obtained for polymer-surfactant compositions covering four decades in both polymer and surfactant concentrations. Bulk polymer-surfactant phase behavior and surface properties are characterized to provide additional information to interpret mechanisms. Materials investigated include cationic acrylamide-acrylamidopropyltrimonium copolymer (AAC), sodium lauryl ether sulfate (SLES) surfactant, silica colloids, and glass microscope slides. Measured colloid-substrate interaction potentials and deposition behavior show nonmonotonic trends vs polymer-surfactant composition and appear to be synergistic in the sense that they are not easily explained as the superposition of single-component-mediated interactions. Broad findings show that at some compositions polymer-surfactant complexes mediate bridging and depletion attractions that promote colloidal deposition, whereas other compositions produce electrosteric repulsion that deters colloidal deposition. These findings illustrate mechanisms underlying colloid-surface interactions in polymer-surfactant mixtures, which are important to controlling selective colloidal deposition in multicomponent formulation applications.

Interactions between silica particles in the presence of multivalent coions.

Forces between charged silica particles in solutions of multivalent coions are measured with colloidal probe technique based on atomic force microscopy. The concentration of 1 : z electrolytes is systematically varied to understand the behavior of electrostatic interactions and double-layer properties in these systems. Although the coions are multivalent the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory perfectly describes the measured force profiles. The diffuse-layer potentials and regulation properties are extracted from the forces profiles by using the DLVO theory. The dependencies of the diffuse-layer potential and regulation parameter shift to lower concentration with increasing coion valence when plotted as a function of concentration of 1 : z salt. Interestingly, these profiles collapse to a master curve if plotted as a function of monovalent counterion concentration.

Interactions between charged particles with bathing multivalent counterions: experiments vs. dressed ion theory.

We compare the recent experimentally measured forces between charged colloidal particles, as well as their effective surface potentials (surface charge) in the presence of multivalent counterions in a bathing monovalent salt solution, with the predictions of the dressed ion theory of strongly charged colloidal systems. The benchmark for comparison is provided by the DLVO theory and the deviations from its predictions at small separations are taken as an indication of the additional non-DLVO attractions that can be fitted by an additional phenomenological exponential term. The parameters characterizing this non-DLVO exponential term as well as the dependencies of the effective potential on the counterion concentration and valency predicted by the dressed ion theory are well within the experimental values. This suggests that the deviations from the DLVO theory are probably caused by ion correlations as formalized within the dressed ion theory.

Interplay between Depletion and Double-Layer Forces Acting between Charged Particles in Solutions of Like-Charged Polyelectrolytes.

Direct force measurements between negatively charged silica particles in the presence of a like-charged strong polyelectrolyte were carried out with an atomic force microscope. The force profiles can be quantitatively interpreted as a superposition of depletion and double-layer forces. The depletion forces are modeled with a damped oscillatory profile, while the double-layer forces with the mean-field Poisson-Boltzmann theory for a strongly asymmetric electrolyte, whereby an effective valence must be assigned to the polyelectrolyte. This effective valence is substantially smaller than the bare valence due to ion condensation effects. The unusual aspect of the electrical double layer in these systems is the exclusion of the like-charged polyelectrolyte from the vicinity of the surface, leading to a strongly nonexponential diffuse ionic layer that is dominated by counterions and has a well-defined thickness. As the oscillatory depletion force sets in right after this layer, this condition can be used to predict the phase of the oscillatory depletion force.

Forces between silica particles in the presence of multivalent cations.

Forces between negatively charged silica particles in aqueous electrolyte solutions were measured with the colloidal probe technique based on the atomic force microscope (AFM). The present study focuses on the comparison of monovalent and multivalent counterions, namely K(+), Mg(2+), and La(3+). The force profiles can be well described with the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) down to distances of about 4 nm. At smaller distances, the forces become strongly repulsive due to additional non-DLVO repulsion. In the presence of La(3+), one observes an additional attractive force with a range of about 1 nm at intermediate salt concentrations. This force is probably related to ion-ion correlations, but could also be influenced by surface charge heterogeneities or charge fluctuation forces.

Dispersion forces acting between silica particles across water: influence of nanoscale roughness.

Force profiles between pairs of silica particles in concentrated aqueous solutions of a monovalent salt are measured using atomic force microscopy (AFM). Under such conditions, the double layer forces are negligible, and the profiles are dominated by van der Waals dispersion forces at larger distances. Heat treatment of the particles strongly influences the strength of dispersion forces. The dispersion force between the particles heated at 1200 °C was strongly attractive, and was characterized by a Hamaker constant of 2.4 × 10-21 J. This value is in good agreement with the current best theoretical estimate of the Hamaker constant for silica across water. For untreated particles, however, the dispersion force is much weaker and the Hamaker constant is 7 × 10-23 J. The Hamaker constant can be continuously tuned by adjusting the heating temperature between 1000 and 1200 °C. Such substantial variations of the Hamaker constant are caused by moderate differences in surface roughness on the nanoscale. The root mean square (RMS) of the roughness correlates inversely with the Hamaker constant, whereby the particles treated at 1200 °C have an RMS value of 0.63 nm, while the untreated particles have an RMS value of 2.5 nm. Other effects that could influence the Hamaker constant, such as changes in the degree of crystallinity, porosity, and shape of the particles, could be excluded.

Direct force measurements between silica particles in aqueous solutions of ionic liquids containing 1-butyl-3-methylimidazolium (BMIM).

Direct force measurements between silica particles were carried out using the colloidal probe technique, which is based on an atomic force microscope (AFM). The forces were investigated in aqueous solutions of ionic liquids (ILs) containing 1-butyl-3-methylimidazolium (BMIM) cations and chloride, dicyanamide, and thiocyanate as anions up to concentrations of about 1 M. The results were compared with the simple electrolyte KCl. ILs behave similar to the simple electrolyte at low concentrations, as the ILs dissociate fully into ions, and they lead to repulsive double layer forces. At higher concentrations, attractive van der Waals forces set in, but they are enhanced in the presence of ILs by additional attractive force, whose strength depends on the type of IL. This additional attraction probably originates from the interaction of adsorbed IL layers.