Armando Maestro

Ion adsorption-induced wetting transition in oil-water-mineral systems

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.

Polymer-surfactant systems in bulk and at fluid interfaces.

The interest of polymer-surfactant systems has undergone a spectacular development in the last thirty years due to their complex behavior and their importance in different industrial sectors. The importance can be mainly associated with the rich phase behavior of these mixtures that confers a wide range of physico-chemical properties to the complexes formed by polymers and surfactants, both in bulk and at the interfaces. This latter aspect is especially relevant because of the use of their mixture for the stabilization of dispersed systems such as foams and emulsions, with an increasing interest in several fields such as cosmetic, food science or fabrication of controlled drug delivery structures. This review presents a comprehensive analysis of different aspects related to the phase behavior of these mixtures and their intriguing behavior after adsorption at the liquid/air interface. A discussion of some physical properties of the bulk is also included. The discussion clearly points out that much more work is needed for obtaining the necessary insights for designing polymer-surfactant mixtures for specific applications.

Molecular Weight Dependence of the Shear Rheology of Poly (methyl methacrylate) Langmuir Films: A Comparison between Two Different Rheometry Techniques

The surface shear rheology of Langmuir monolayers of poly(methyl methacrylate) (PMMA) has been studied as a function of polymer concentration (Gamma) and molecular weight (N). Two different rheology techniques were used, one based on free damped oscillations of a ring with a sharp edge and the other based on a forced oscillation of a biconical disk. Both instruments were used in the oscillatory mode at comparable oscillation frequency and amplitude, which gave access to the viscoelastic shear modulus (S). The two instruments, working in different viscosity ranges, provide complementary and mutually compatible data. The results obtained for four PMMA samples of molecular weight between 8x10(3) and 2.7x10(5) g.mol(-1) show powerlike behavior as S approximately Gamma10 and S approximately N4. These strong dependences suggest a structural scenario based on the 2D percolation of the polymer pancakes.

Particle and Particle-Surfactant Mixtures at Fluid Interfaces: Assembly, Morphology, and Rheological Description

We report here a review of particle-laden interfaces. We discuss the importance of the particle’s wettability, accounted for by the definition of a contact angle, on the attachment of particles to the fluid interface and how the contact angle is strongly affected by several physicochemical parameters. The different mechanisms of interfacial assembly are also addressed, being the adsorption and spreading the most widely used processes leading to the well-known adsorbed and spread layers, respectively. The different steps involved in the adsorption of the particles and the particle-surfactant mixtures from bulk to the interface are also discussed. We also include here the different equations of state provided so far to explain the interfacial behavior of the nanoparticles. Finally, we discuss the mechanical properties of the interfacial particle layers via dilatational and shear rheology. We emphasize along that section the importance of the shear rheology to know the intrinsic morphology of such particulate system and to understand how the flow-field-dependent evolution of the interfacial morphology might eventually affect some properties of materials such as foams and emulsions. We dedicated the last section to explaining the importance of the particulate interfacial systems in the stabilization of foams and emulsions.

Adsorption of β-casein-surfactant mixed layers at the air-water interface evaluated by interfacial rheology.

This work presents a detailed study of the dilational viscoelastic moduli of the adsorption layers of the milk protein β-casein (BCS) and a surfactant at the liquid/air interface, over a broad frequency range. Two complementary techniques have been used: a drop profile tensiometry technique and an excited capillary wave method, ECW. Two different surfactants were studied: the nonionic dodecyldimethylphosphine oxide (C12DMPO) and the cationic dodecyltrimethylammonium bromide (DoTAB). The interfacial dilational elasticity and viscosity are very sensitive to the composition of protein-surfactant mixed adsorption layers at the air/water interface. Two different dynamic processes have been observed for the two systems studied, whose characteristic frequencies are close to 0.01 and 100 Hz. In both systems, the surface elasticity was found to show a maximum when plotted versus the surfactant concentration. However, at frequencies above 50 Hz the surface elasticity of BCS + C12DMPO is higher than the one of the aqueous BCS solution over most of the surfactant concentration range, whereas for the BCS + DoTAB it is smaller for high surfactant concentrations and higher at low concentrations. The BCS-surfactant interaction modifies the BCS random coil structure via electrostatic and/or hydrophobic interactions, leading to a competitive adsorption of the BCS-surfactant complexes with the free, unbound surfactant molecules. Increasing the surfactant concentration decreases the adsorbed proteins. However, the BCS molecules are rather strongly bound to the interface due to their large adsorption energy. The results have been fitted to the model proposed by C. Kotsmar et al. ( J. Phys. Chem. B 2009 , 113 , 103 ). Even though the model describes well the concentration dependence of the limiting elasticity, it does not properly describe its frequency dependence.

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate)

Summary This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers.

Tuning Interfacial Properties and Processes by Controlling the Rheology and Structure of Poly(N-isopropylacrylamide) Particles at Air/Water Interfaces

By combining controlled experiments on single interfaces with measurements on solitary bubbles and liquid foams, we show that poly( N-isopropylacrylamide) (PNIPAM) microgels assembled at air/water interfaces exhibit a solid to liquid transition changing the temperature, and that this is associated with the change in the interfacial microstructure of the PNIPAM particles around their volume phase transition temperature. We show that the solid behaves as a soft 2D colloidal glass, and that the existence of this solid/liquid transition offers an ideal platform to tune the permeability of air bubbles covered by PNIPAM and to control macroscopic foam properties such as drainage, stability, and foamability. PNIPAM particles on fluid interfaces allow new tunable materials, for example foam structures with variable mechanical properties upon small temperature changes.

Charge Control And Wettability Alteration At Solid-liquid Interfaces

Most solid surfaces acquire a finite surface charge upon exposure to aqueous environments due to desorption and/or adsorption of ionic species. The resulting electrostatic forces play a crucial role in many fields of science, including colloidal stability, self-assembly, wetting, and biophysics as well as technology. Enhanced oil recovery is an example of a large scale industrial process that hinges in many respects on these phenomena. In this paper, we present a series of experiments illustrating fundamental aspects of low salinity water flooding in well-defined model systems. We show how pH and ion content of the water phase as well as the presence of model polar components (fatty acids) in the oil phase affect the wettability (i.e. contact angle distribution) of oil-water-rock systems. Specifically, we discuss high resolution atomic force microscopy (AFM) experiments demonstrating the preferential adsorption of multivalent cations to mineral surfaces such as mica and gibbsite. Cation adsorption leads to increased and in some cases reversed surface charge at thesolid-liquid interface. In the case of charge reversal, the adsorption process can trigger a wetting transition from complete water wetting in ambient oil (i.e. zero water contact angle) in the absence to partial wetting in the presence of divalent cations. While already dramatic for pure alkanes as base oil, adding fatty acids to the oil phase enhances the effect of divalent ions on the oil-water-rock wettability even more. In this case, contact angle variations of more than 70° can be observed as a function of the salt concentration. This enhancement is caused by the deposition of a thin film of fatty acid on the solid surface. AFM as well as surface plasmon resonance spectroscopy measurement in a microfluidic continuous flow cell directly demonstrate that adsorbed Ca ions promote secondary adsorption of acidic components from the oil phase. The combination of the effects discussed provides a rational scenario explaining many aspects of the success of low salinity water flooding.

Physico-chemical foundations of particle-laden fluid interfaces

Abstract.Particle-laden interfaces are ubiquitous nowadays. The understanding of their properties and structure is essential for solving different problems of technological and industrial relevance; e.g. stabilization of foams, emulsions and thin films. These rely on the response of the interface to mechanical perturbations. The complex mechanical response appearing in particle-laden interfaces requires deepening on the understanding of physico-chemical mechanisms underlying the assembly of particles at interface which plays a central role in the distribution of particles at the interface, and in the complex interfacial dynamics appearing in these systems. Therefore, the study of particle-laden interfaces deserves attention to provide a comprehensive explanation on the complex relaxation mechanisms involved in the stabilization of fluid interfaces.Graphical abstract

Nonaffine deformation and tunable yielding of colloidal assemblies at the air-water interface.

Silica nanoparticles trapped at the air–water interface form a 2D solid state with amorphous order. We propose a theoretical model to describe how this solid-like state deforms under a shear strain ramp up to and beyond a yielding point which leads to plastic flow. The model accounts for all the particle-level and many-body physics of the system: nonaffine displacements, local connectivity and its evolution in terms of cage-breaking, and interparticle interactions mediated by the particle chemistry and colloidal forces. The model is able to reproduce experimental data with only two non-trivial fitting parameters: the relaxation time of the cage and the viscous relaxation time. The interparticle spring constant contains information about the strength of interparticle bonding which is tuned by the amount of surfactant that renders the particles hydrophobic and mutually attractive. This framework opens up the possibility of quantitatively tuning and rationally designing the mechanical response of colloidal assemblies at the air–water interface. Also, it provides a mechanistic explanation for the observed non-monotonic dependence of yield strain on surfactant concentration.