Polyelectrolyte/Surfactant Mixtures: A Pathway to Smart Foams

This review deals with liquid foams stabilized by polyelectrolyte/surfactant (PS) complexes in aqueous solution. It briefly reviews all the important aspects of foam physics at several scales, from interfaces to macroscopic foams, needed to understand the basics of these complex systems, focusing on those particular aspects of foams stabilized by PS mixtures. The final section includes a few examples of smart foams based on PS complexes that have been reported recently in the literature. These PS complexes open an opportunity to develop new intelligent dispersed materials with potential in many fields, such as oil industry, environmental remediation, and pharmaceutical industry, among others. However, there is much work to be done to understand the mechanism involved in the stabilization of foams with PS complexes. Understanding those underlying mechanisms is vital to successfully formulate smart systems. This review is written in the hope of stimulating further work in the physics of PS foams and, particularly, in the search for responsive foams based on polymer-surfactant mixtures.Fil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina. Universidad Nacional del Sur. Departamento de Física; Argentin

Reaction Kinetics in the Production of Pd Nanoparticles in Reverse Microemulsions: Effect on Particle Size

In the synthesis of metallic nanoparticles in microemulsions, we hypothesized that particle size is mainly controlled by the reaction rate. Thus, the changes observed on the particle sizes as reaction conditions, such as concentrations, temperature, type of surfactant used, etc., are varied should not be correlated directly to the modification of those conditions but indirectly to the changes they produce on the reaction rates. By means of time resolved UV-vis spectroscopy, we measured the reaction rates in the production of Pd nanoparticles inside microemulsions at different reactant concentrations, keeping all the other parameters constant. The measured reaction rates were then correlated with the particle sizes measured by transmission electron microscopy (TEM). We found that nanoparticle size increases linearly as the reaction rates increases, independently of the actual reactant concentrations. We proposed that the kinetics is controlled mainly by the diffusion of the reducing agent through the surfactant monolayer covering the microemulsion membrane. With this model, we predicted that particle size should depend indirectly, via the reaction kinetics, on the micelle radius (v0 ~ r^-3), the water volume (v0~vw^3) and the total microemulsion volume (v0~vT^-3), and temperature (Arrhenius). Some of these predictions were explored in this article.Fil: Sánchez Morales, Jhon Freddy. Universidad Nacional del Sur. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Sanchez, Miguel Dario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina. Universidad Nacional del Sur. Departamento de Física; ArgentinaFil: Ritacco, Hernán Alejandro. Universidad Nacional del Sur. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentin

Production of Pd nanoparticles in microemulsions: Effect of reaction rates on the particle size

In the synthesis of metallic nanoparticles in microemulsions, we hypothesized that the particle size is controlled by the reaction rate and not by the microemulsion size. Thus, the changes observed in the particle sizes as reaction conditions, such as concentrations, temperatures, the type of surfactant used, etc., are varied which should not be correlated directly to the modification of these conditions but indirectly to the changes they produce in the reaction rates. In this work, the microemulsions were formulated with benzene and water as continuous and dispersed phases, respectively, using n-dodecyltrimethylammonium bromide (DTAB) and n-octanol as the surfactant and cosurfactant. Using time-resolved UV-vis spectroscopy, we measured the reaction rates in the production of palladium (Pd) nanoparticles inside the microemulsions at different reactant concentrations and temperatures, keeping all the other parameters constant. The measured reaction rates were then correlated with the particle sizes measured by transmission electron microscopy (TEM). We found that the nanoparticle size increases linearly as the reaction rate increases, independently of the actual reactant concentration or temperature. We proposed a simple model for the observed kinetics where the reaction rate is controlled mainly by the diffusion of the reducing agent. With this model, we predicted that the particle size should depend indirectly, via the reaction kinetics, on the micelle radius, the water volume and the total microemulsion volume. Some of these predictions were indeed observed and reported in the literature.Fil: Sánchez Morales, Jhon Freddy. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Sanchez, Miguel Dario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Falcone, Ruben Dario. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; ArgentinaFil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentin

Polarity studies of single polyelectrolyte layers in polyelectrolyte multilayers probed by steady state and life time doxorubicin fluorescence

Hypothesis: Polarity in polyelectrolyte multilayers (PEMs) may vary from the inner to the top layers of the film as the charge compensation of the layers is more effective inside the PEMs than in outer layers. Doxorubicin hydrochloride (DX) is used here to sense polarity at the single polyelectrolyte level inside PEMS. Experimental: DX is complexed electrostatically to a polyanion, either polystyrene sulfonate (PSS) or polyacrylic acid (PAA) and assembled at selected positions in a multilayer of the polyanion and polyally lamine hydrochloride (PAH) as polycation. Local polarity in the layer domain is evaluated through changes in the intensity ratio of the first to second band of spectra of DX (I1/I2 ratio) by steady state flu orescence, and by Lifetime fluorescence. Findings: PAH/PSS multilayers, show a polarity similar to water with DX/PSS as top layer, decreasing to I1/ I2 ratios similar to organic solvents as the number of polyelectrolyte layers assembled on top increases. For PAH/PAA multilayers, polarity values reflect a more polar environment than water when DX/PAA is the top layer, remaining unaltered by the assembly of polyelectrolyte layers on top. Results show that different polar environments may be present in a PEM when considering polarity at the single layer level.Fil: Martinelli, Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina. Centro de Investigación Cooperativa en Biomateriales; EspañaFil: Tasca, Elisamaria. Centro de Investigación Cooperativa en Biomateriales; España. Università degli Studi di Roma "La Sapienza"; ItaliaFil: Andreozzi, Patrizia. Università degli Studi di Firenze; Dipartimento di Chimica “Ugo Schiff”; Italia. Centro de Investigación Cooperativa en Biomateriales; EspañaFil: Libertone, Sara. Centro de Investigación Cooperativa en Biomateriales; EspañaFil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Giustini, Mauro. Università degli Studi di Roma "La Sapienza"; Italia. Università degli Studi di Firenze; Dipartimento di Chimica “Ugo Schiff” ; ItaliaFil: Moya, Sergio Enrique. Centro de Investigación Cooperativa en Biomateriales; España. Università degli Studi di Roma "La Sapienza"; Itali

Adsorption Kinetics of a Cationic Surfactant Bearing a Two-Charged Head at the Air-Water Interface

We studied the dynamics of adsorption at the air-water interface of a cationic surfactant bearing two charges, Gemini 12-2-12, at concentrations below and above the critical micelle concentration (cmc). We used maximum bubble pressure and Wilhelmy plate techniques in order to access all time scales in the adsorption process. We found that the adsorption dynamics are controlled by diffusion at the initial stage of the adsorption process (milliseconds) and it is kinetically controlled by an electrostatic barrier (minute) approaching the equilibrium surfactant surface concentration. Between these two extremes, we found several relaxation phenomena, all following exponential decays with characteristic times spanning from one to hundreds of seconds. By means of time-resolved surface potential measurements, we show that these processes involve charge redistribution within the interfacial region. The surface tension data are analyzed and interpreted in the framework of the free energy approach.Fil: Fernández Leyes, Marcos Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Gimenez Reyes, Santiago Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Cuenca, Victor Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Sánchez Morales, Jhon Freddy. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentin

The aqueous Triton X-100 – dodecyltrimethylammonium bromidemicellar mixed system. Experimental results and thermodynamic analysis

The micellization process of the aqueous mixed system triton X-100 (TX100) – dodecyltrimethylammonium bromide (DTAB) has been studied with a battery of techniques: surface tension, static and dynamic light scattering and ion-selective electrodes. Results have been also analysed with two thermodynamic procedures: the Regular Solution Theory or Rubingh's model and the recently developed Equation Oriented Mixed Micellization Model (EOMMM). For α DTAB ≤ 0.40 (α DTAB : total molar fraction of the system without considering the water), the micelles are predominantly TX100 with scarce solubilized DTA + ions, with TX100 acting as a nearly ideal solvent. In the range 0.50 ≤ α DTAB ≤ 0.75, it seems that none of the components acts as a solvent. Above α DTAB ≈ 0.75 there are noticeable changes in the size and electrophoretic mobility of the micelles. These phenomena have been interpreted in the light of the thermodynamic results and literature on some TX100-ionic surfactant mixtures. The case under study is an almost ideal but very asymmetric mixed surfactants system, what is very interesting in view of the very different nature and structures of the components.Fil: Serafini, Patricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Fernández Leyes, Marcos Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Sánchez Morales, Jhon Freddy. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Pereyra, Romina Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Schulz, Erica Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Durand, Guillermo Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Schulz, Pablo Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentin

Electro-optic Kerr effect in the study of mixtures of oppositely charged colloids. The case of polymer-surfactant mixtures in aqueous solutions

In this review I highlight a very sensitive experimental technique for the study of polymer-surfactant complexation: The electro-optic Kerr effect. This review does not intend to be exhaustive in covering the Kerr Effect nor polymer-surfactant systems, instead it aims to call attention to an experimental technique that, even if applied in a qualitative manner, could give very rich and unique information about the structures and aggregation processes occurring in mixtures of oppositely charged colloids. The usefulness of electric birefringence experiments in the study of such systems is illustrated by selected results from literature in hope of stimulating the realization of more birefringence experiments on similar systems. This review is mainly aimed at, but not restricted to, researchers working in polyelectrolyte-surfactant mixtures in aqueous solutions, Kerr effect is a powerful experimental tool that could be used in the study of many systems in diverse areas of colloidal physics.Fil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentin

Complexity and self-organized criticality in liquid foams. A short review

This short review deals with the work done on liquid foams within the framework of the physics of complexity. It aims to stimulate new theoretical and experimental work on foam dynamics as complex dynamical systems. In particular, it examines these systems in relation to Self-Organized Criticality (SOC), for which foams could be used as an accessible experimental model system.Fil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentin

Interfacial microrheology: Particle tracking and related techniques

Microrheology offers several advantages over traditional macroscopic rheology: the use of very small samples, the possibility of studying heterogeneous samples and the broad range of frequency that can be explored. In this paper the study of the microrheology of fluid interfaces is reviewed, with special emphasis on particle tracking techniques. We comment the main results and the assumptions of the different approaches for describing the hydrodynamics of a particle trapped at a surfactant or polymer monolayer. © 2010 Elsevier Ltd.Fil: Ortega, Francisco. Universidad Complutense de Madrid; EspañaFil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Complutense de Madrid; EspañaFil: Rubio, Ramón G.. Universidad Complutense de Madrid; Españ

Evidence of the influence of adsorption kinetics on the internal reorganization of polyelectrolyte multilayers

X-ray reflectivity and adsorption kinetics of two different polyelectrolyte multilayers have been studied for polyelectrolyte multilayers (PEMs) composed of poly(diallyldimethyl ammonium chloride) (PDADMAC) and poly(sodium 4-styrenesulfonate) (PSS) polyelectrolyte pair and of poly(allylamine hydrochloride) (PAH) and PSS. The two characteristic times that describe the adsorption kinetics were found to be related to the X-ray reflectivity results, and their dependence on the number of adsorbed layers is depends on the growth mechanisms (linear or superlinear) of the films. Therefore, it has been concluded that there is a correlation between the adsorption kinetics and the internal structure of the films. The time allowed for the adsorption of each polyelectrolyte controls the extension of the interdiffusion within the multilayer, and therefore whether the film is formed by stratified layers or it has a uniform structure except for the first and last layers. While the roughness of the (PDADMAC + PSS)n films strongly depends on the adsorption time, it is almost independent of it for the (PAH + PSS)n multilayer. This behavior correlates with that of the longest characteristic time of the adsorption kinetics.Fil: Guzmán, Eduardo. Universidad Complutense de Madrid; EspañaFil: Ritacco, Hernán Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Sur; ArgentinaFil: Ortega, Francisco. Universidad Complutense de Madrid; EspañaFil: Rubio, Ramón G.. Universidad Complutense de Madrid; Españ