Forces between Colloidal Particles in Aqueous Solutions Containing Monovalent and Multivalent Ions

The present article provides an overview of the recent progress in the direct force measurements between individual pairs of colloidal particles in aqueous salt solutions. Results obtained by two different techniques are being highlighted, namely with the atomic force microscope (AFM) and optical tweezers. One finds that the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) represents an accurate description of the force profiles even in the presence of multivalent ions, typically down to distances of few nanometers. However, the corresponding Hamaker constants and diffuse layer potentials must be extracted from the force profiles. At low salt concentrations, double layer forces remain repulsive and may become long ranged. At short distances, additional short range non-DLVO interactions may become important. Such an interaction is particularly relevant in the presence of multivalent counterions.Comment: Submitted on 30th of May 2016 as invited article to Curr. Opinion Colloid Interf. Sci. Edited by W. Ducker and P. Claesson. 15 Pages, 7 Figures 82 reference

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

Forces between Silica Particles in Isopropanol Solutions of 1:1 Electrolytes

Interactions between silica surfaces across isopropanol solutions are measured with colloidal probe technique based on atomic force microscope. In particular, the influence of 1:1 electrolytes on the interactions between silica particles is investigated. A plethora of different forces are found in these systems. Namely, van der Waals, double-layer, attractive non-DLVO, repulsive solvation, and damped oscillatory interactions are observed. The measured decay length of the double-layer repulsion is substantially larger than Debye lengths calculated from nominal salt concentrations. These deviations are caused by pronounced ion pairing in alcohol solutions. At separation below 10 nm, additional attractive and repulsive non-DLVO forces are observed. The former are possibly caused by charge heterogeneities induced by strong ion adsorption, whereas the latter originate from structuring of isopropanol molecules close to the surface. Finally, at increased concentrations the transition from monotonic to damped oscillatory interactions is uncovered

A Simple Method to Determine Critical Coagulation Concentration from Electrophoretic Mobility

Critical coagulation concentration (CCC) is a key parameter of particle dispersions, since it provides the threshold limit of electrolyte concentrations, above which the dispersions are destabilized due to rapid particle aggregation. A computational method is proposed to predict CCC values using solely electrophoretic mobility data without the need to measure aggregation rates of the particles. The model relies on the DLVO theory; contributions from repulsive double-layer forces and attractive van der Waals forces are included. Comparison between the calculated and previously reported experimental CCC data for the same particles shows that the method performs well in the presence of mono and multivalent electrolytes provided DLVO interparticle forces are dominant. The method is validated for particles of various compositions, shapes, and sizes

Microstructural analysis of Bulk Molding Compounds and correlation with the flexural strength

In this study, the influence of the glass fiber (GF) content on the microstructure and flexural strength of bulk molding compounds (BMCs) is investigated. Three sets of BMCs with different weight fractions of GF (5/10/12.5 wt%) were commercially prepared and compression molded into test specimens. The microstructure of the composites was analysed by scanning electron microscopy and further quantitatively characterized by Voronoi analysis in order to define the degree of the fiber distribution homogeneity. The experimental results were compared to the modelled microstructures. The results revealed that the fiber distribution in the composite with 5 wt% of GF is considered as the most homogeneous. Through the obtained microstructural descriptors, the fiber weight content and their distribution were correlated to the flexural strength of BMCs. The flexural strength was the highest for the composite with 10 wt% of GF

Surfactant mediated particle aggregation in nonpolar solvents

The aggregation behavior of particles in nonpolar media is studied with time-resolved light scattering. At low surfactant concentrations particles are weakly charged and suspensions are not stable. The suspensions become progressively more stable with increasing surfactant concentration as particles become more highly charged. At high concentrations the particles become neutralized and aggregation is again fast. The theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) is able to predict the stability ratios quantitatively by using the experimentally measured surface charges, screening lengths and van der Waals forces

Overview of DLVO Theory

The DLVO theory represents an important framework to model interactions in aqueous colloidal suspensions and the respective aggregation rates. The theory assumes that the interaction forces can be well approximated by a superposition of van der Waals and double layer forces. In an symmetric system or in the case of homoaggreagtion, van der Waals forces are attractive and double layer forces repulsive. When one deals with asymmetric systems and heteroaggregation, the situation is can be more complex. While van der Waals forces are normally attractive, the double layer forces can be attractive, repulsive, or both. Moreover, effects of charge regulation can become important. DLVO theory is further capable to describe experimental situations relatively well. In some cases, this theory can describe interaction forces as well as aggregation rate constants quantitatively. Deviations may persist, however, especially at higher salt levels. These details are subject of current research

Measuring slow heteroaggregation rates in the presence of fast homoaggregation

Homoaggregation and heteroaggregation involving amidine and sulfate latex particles in the presence of the anionic surfactant octyl sulfate (OS) is studied by light scattering. This surfactant causes a charge reversal of the amidine particles. This reversal induces a rapid homoaggregation near the charge reversal point. In the presence of the same surfactant, the sulfate particles remain negatively charged and stable. The heteroaggregation process is probed in mixed suspensions of amidine and sulfate latex particles with multi-angle time-resolved dynamic light scattering. This technique allows differentiating between the contributions of homoaggregation and heteroaggregation, and permits to measure the heteroaggregation rate. By optimally choosing the sizes of the particles, one can optimize the contrast and extract heteroaggregation stability ratio over a wide range. The heteroaggregation rate is fast at low OS concentrations, where the two particles are oppositely charged. This rate slows down at higher OS concentrations due to double layer repulsion between the negatively charged particles. However, the onset of this slow heteroaggregation occurs at lower OS concentrations than for homoaggregation. The reason for this shift is that the double layer repulsion between two OS-decorated amidine particles is weaker than between one sulfate particle and one OS-decorated amidine particle. These measurements compare favorably with calculations with the theory by Derjaguin, Landau, Verwey, and Overbeek (DLVO). These calculations suggest that constant potential boundary conditions are more appropriate than the ones of constant charge. In the system studied, the present light scattering technique permits to extract heteroaggregatio

Schulze-Hardy rule revisited

The classical Schulze-Hardy rule suggests that the critical coagulation concentration (CCC) decreases as the inverse sixth power of the counterion valence. While this dependence can be derived from the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO), this derivation relies on unrealistic assumptions. In particular, one cannot assume that the electrolytes are symmetric, since one normally works with the better soluble asymmetric electrolytes. For such electrolytes, however, it is essential to distinguish between multivalent counterions and coions. For multivalent counterions, one must consider their strong tendency towards adsorption to the oppositely charged substrates, which leads to low charge densities. In this situation, the CCC increases with the surface charge density, inducing the strong decrease of the CCC with valence. For multivalent coions, the substrates are typically highly charged. In this case, the CCC decreases with increasing ionic valence and is in fact inversely proportional to the valence. This dependence is referred to as the inverse Schulze-Hardy rule