The relative wettability of oil and water on solid surfaces is generally governed by a complex competition of molecular interaction forces acting in such three-phase systems. Herein, we experimentally demonstrate how the adsorption of in nature abundant divalent Ca2+ cations to solid-liquid interfaces induces a macroscopic wetting transition from finite contact angles (≈10°) with to near-zero contact angles without divalent cations. We developed a quantitative model based on DLVO theory to demonstrate that this transition, which is observed on model clay surfaces, mica, but not on silica surfaces nor for monovalent K+ and Na+ cations is driven by charge reversal of the solid-liquid interface. Small amounts of a polar hydrocarbon, stearic acid, added to the ambient decane synergistically enhance the effect and lead to water contact angles up to 70° in the presence of Ca2+. Our results imply that it is the removal of divalent cations that makes reservoir rocks more hydrophilic, suggesting a generalizable strategy to control wettability and an explanation for the success of so-called low salinity water flooding, a recent enhanced oil recovery technology.
The hydrophobicity of a particle surface can be tuned by the addition of surfactants that change the surface free energy for their attachment to a liquid interface. In this work, we report an experimental study where the wettability properties of silica nanoparticles are modified by the adsorption of alkyltrimethylammonium surfactants (C n TAB, n ¼ 12, 16) on the surface of the particles. We have pointed out that the wettability of the complexes is controlled by an intricate balance of electrostatic and hydrophobic interactions between the particle surface and the surfactant. These interactions play an important role in the structure of the surfactant-particle nanocomposite interfacial layer.
We have studied foams stabilised by surfactant-decorated nanoparticles adsorbed at the bubble surfaces. We show that the controlled compression of a single bubble allows one to understand the coarsening behavior of these foams. When bubbles are compressed, the particles become tightly packed in the surface layer. They lose their mobility, and the interface becomes solid-like when the jammed state is reached. Further compression leads to interfacial buckling characterised by crumpled surfaces. We find that the surface concentration of particles at which the jamming and the buckling transitions occur are independent of the surfactant concentration. This is a surprising feature. It suggests that the surfactants are mandatory to help the particles adsorb at the interface and that they change the equilibrium surface concentration of the decorated particles. But they do not affect the surface properties once the particles are adsorbed. We measured the compression elastic modulus of the surface in the jammed state and found it to be compatible with the Gibbs condition for which the spontaneous dissolution of bubbles is arrested. Due to this effect, the coarsening process of a foam composed of many close-packed bubbles occurs in two steps. In the first step, coarsening is slow and coalescence of the bigger bubbles is observed. In the second step, a number of very small bubbles remains, which exhibit crumpled surfaces and are stable over long times. This suggests that foam coarsening is arrested once the smallest bubbles become fully covered after the initial shrinking step.
Many physical properties of concentrated dispersions of immiscible fluids are captured by the concept of an osmotic pressure, which measures how much energy is required to deform the bubbles or drops upon compaction. This pressure has a strong impact on the flow and drainage behavior of dispersions.Nevertheless, theoretical models describing its variation with the volume fraction f of the continuous phase are so far available only in the limits of low or high f and experimental data are scarce. We report an experimental study of osmotic pressure in foams and emulsions, showing how the effects of f, disorder, grain size, polydispersity and interfacial tension can all be captured by a single law which satisfies previously established theoretical constraints. Building on this result, we propose the first equation which accurately describes the variation of the volume fraction with the height of a fluid dispersion under gravity.
We address the rheology of assemblies of surfactant-decorated silica nanoparticles irreversibly adsorbed at the gas/liquid interface. Positively charged surfactant molecules (such as CTAB) bind to silica nanoparticle surfaces, and the resulting particle-surfactant complexes adsorb at gas/liquid interfaces. The surfactant molecules control the wettability of such decorated nanoparticles and their adsorption. The interparticle forces can be tuned by changing the surfactant concentration Cs. Increasing Cs, in addition to a decrease of the particles wettability, leads to an increase of the area fraction of particles at the interface. Oscillatory shear measurements (strain- and frequency-sweep) have been performed. Here, we explore the effect of the surfactant concentration Cs. At high enough Cs, the interface is highly packed, and an overall solidlike response is observed, with 2D glass properties.
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