Elena Blanco

Magnetically Responsive Pickering Foams

We introduce a new class of Pickering foams which can be manipulated using a magnetic field. These foams are stabilized by a mixture of magnetic and nonmagnetic particles. They exhibit excellent stability in the absence of a magnetic field, but can be rapidly destroyed on demand with the application of a threshold field. We characterize their stability in the absence of a magnetic field by measuring the rate of water drainage from the foam as a function of time. We also correlate their collapse behavior under a magnetic field to the foam liquid fraction, as well as the concentration of magnetic particles in the foam. This novel system can be used to study the properties of Pickering foams, and has potential applications in noncontact defoaming processes.

Stability and Viscoelasticity of Magneto-Pickering Foams

We have developed a new class of bistable Pickering foams, which can remain intact for weeks at room temperature but can be destroyed rapidly and on-demand with the use of a magnetic field. Such responsive foam systems can find application in various industrial and environmental processes that require controlled defoaming. These foams are stabilized by particles of hypromellose phthalate (HP-55) and contain oleic acid-coated carbonyl iron particles embedded in the HP-55 matrix. The complex behavior of these foams arises from several factors: a robust anisotropic particle matrix, the capacity to retain a high amount of water, as well as an age-dependent response to an external field. We report how the structure and viscoelastic properties of the foams change with time and affect their collapse characteristics. The evolution of foam properties is quantified by measuring the rate of liquid drainage from the foam as well as the rate of bubble growth in the foam with respect to time elapsed (in the absence of a magnetic field). We also evaluate the time necessary for foam collapse in magnetic fields as a function of magnetic particle content. A decreasing liquid volume fraction in the foam during aging leads to an increase in the elasticity and rigidity of the foam structure. These data allow us to identify a transition time separating two distinct stages of foam development in the absence of field. We propose different mechanisms which control foam collapse for each stage in a magnetic field. The stiffening of foam films between air bubbles with age plays a key role in distinguishing between the two destabilization regimes.

Effect of alkyl chain asymmetry on catanionic mixtures of hydrogenated and fluorinated surfactants

In this work we studied and compared the physicochemical properties of the catanionic mixtures cetyltrimethyl-ammonium bromide-sodium dodecanoate, cetyltrimethyl-ammonium bromide-sodium perfluorodacanoate, octyltrimethylammonium bromide-sodium perfluorodacanoate and cetyltrimethyl-ammonium bromide-sodium octanoate by a combination of rheological, transmission electron microscopy (TEM) and polarized optical microscopy measurements. The binary mixtures of the surfactants have been analyzed at different mixed ratios and total concentration of the mixture. Mixtures containing a perfluorinated surfactant are able to form lamellar liquid crystals and stable spontaneous vesicles. Meanwhile, system containing just hydrogenated surfactants form hexagonal phases or they are arranged in elongated aggregates.

Phase behavior of semifluorinated catanionic mixtures: Head group dependence and spontaneous formation of vesicles

Hexadecyltrimethylammonium bromide (C(16)TAB)-sodium perfluorooctanoate (C(8)FONa) and hexadecylpyridynium bromide (C(16)PyB)-C(8)FONa catanionic semifluorinated mixtures have been studied by conductivity, dynamic light scattering (DLS), cryo-transmission electron microscopy (cryo-TEM) and polarizing microscopy. The regular solution theory, applicable for a limited fluorinated molar ratio, does not predict long-range electrostatic interactions. The results are consistent with the fact that in the hydrogenated-rich region the interaction is attractive in both catanionic mixtures. The systems containing pyridinium headgroups were of the stronger interaction. A transition from micelles was found in both mixtures as a function of fluorinated molar ratio. Special attention was devoted to the effect of the head group in the system properties. The information related with the mean vesicle radius measured by DLS was compared with the vesicle size distribution as well as the elastic properties of the bilayer measured with cryo-TEM.

Counterion effect on the solution and thermodynamic properties of lithium perfluoroalkanoates

The isotherms of conductivity of lithium perfluorooctanoate and perfluoroundecanoate were measured and the critical micelle concentration, cmc, degree of ionization of the micelles, β, determined in a range of temperatures above the Krafft point. The thermodynamic parameters, Gibbs free energy, , enthalpy , and entropy of micelle formation, were determined from a proposed thermodynamic model. Apparent molar volume and the apparent molar adiabatic compressibility for both surfactants have been calculated over a wide concentration range from density and ultrasound velocity measurements. Positive deviations of the apparent molar volume from the Debye–Hückel limiting law in dilute solutions indicate the existence of premicellar aggregation. Changes in the slope of adiabatic compressibility of lihium perfluoroundecanoate from positive to negative have been interpreted in terms of solute solvent interactions. Dynamic surface tension measurements allow us to calculated diffusion coefficients, areas and aggregation numbers. These values are discussed comparing the corresponding sodium compounds.

Langmuir Monolayers of a Hydrogenated/Fluorinated Catanionic Surfactant: From the Macroscopic to the Nanoscopic Size Scale

Langmuir monolayers of the hydrogenated/fluorinated catanionic surfactant cetyltrimethylammonium perfluorooctanoate at the air/water interface are studied at room temperature. Excess Gibbs energies of mixing, DeltaG(E), as well as transition areas and pressures, were obtained from the surface pressure-area isotherm. The DeltaG(E) curve indicates that tail-tail interactions are more important than head-head interactions at low pressures and vice versa. Atomic force microscopy and molecular dynamics simulations allowed a fine characterization of the monolayer structure as a function of the area per molecule at mesoscopic and nanoscopic size scales, respectively. A combined analysis of the techniques allow us to conclude that electrostatic interactions between the ionic head groups are dominant in the monolayer while hydrophobic parts are of secondary importance. Overall, results obtained from the different techniques complement to each other, giving a comprehensive characterization of the monolayer.

Organic–inorganic patchy particles as a versatile platform for fluid-in-fluid dispersion stabilisation

We present a new class of organic-inorganic patchy particles for the efficient stabilization of Pickering foams and emulsions. Using solvent-based heterogeneous precipitation, we decorate inorganic silica particles with discrete domains of water insoluble plant protein (zein). By varying the extent of protein coverage on the silica surface, we tune the pH-dependent interactions of the particles and the interfaces. We observe an optimum foam stabilization, which is attributed to the creation of a slightly positive low effective surface potential from positively charged protein patches and the negatively charged silica surface. The effect of surface coverage on foam stability is in line with the predicted low interfacial potential of the patchy particles in water, which determines the energy of particle adsorption. In emulsions, the increase of the protein amount on the silica particles causes a progressive bridging of the oil droplets into a close-packing configuration due to gelation of the protein patches. Protein-based organic-inorganic surface heterogeneous particles represent a new versatile platform for the stabilization of fluid-in-fluid dispersions and as precursors for the assembly of advanced functional materials.

Dissolution behaviour of ferric pyrophosphate and its mixtures with soluble pyrophosphates: Potential strategy for increasing iron bioavailability.

Ferric pyrophosphate (FePP) is a widely used iron source in food fortification and in nutritional supplements, due to its white colour, that is very uncommon for insoluble Fe salts. Although its dissolution is an important determinant of Fe adsorption in human body, the solubility characteristics of FePP are complex and not well understood. This report is a study on the solubility of FePP as a function of pH and excess of pyrophosphate ions. FePP powder is sparingly soluble in the pH range of 3-6 but slightly soluble at pH<2 and pH>8. In the presence of pyrophosphate ions the solubility of FePP strongly increases at pH 5-8.5 due to formation a soluble complex between Fe(III) and pyrophosphate ions, which leads to an 8-10-fold increase in the total ionic iron concentration. This finding is beneficial for enhancing iron bioavailability, which important for the design of fortified food, beverages, and nutraceutical products.