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The extraction of cerium from cotton substrate, as a matrix model, using supercritical CO2 modified with phosphorus extractant and co-solvent/water in wise proportions, has been investigated. Using a recently developed isobutyl amidophosphonate extractant, the aim of this study was to emphasize how besides the usually considered operating parameters (flow rate, pressure and temperature), the efficiency of supercritical CO2 extraction of cerium depends on the concentration of cerium nitrate deposits on the substrate (between 0.27 and 261 mg gcotton−1) and on the presence and composition of co-solvent/water mixture as well. The variations of the extraction efficiency with the nature of the Ce nitrate deposits (aggregates or homogenous layers) are explained by using a deposition model confirmed using SEM and coupled with SAXS data. Extraction is promoted when Ce nitrates deposits are in the form of segregated aggregates instead of homogeneous layers. Phase equilibrium data for CO2-ethanol-amidophosphonate and CO2-isopropanol-amidophosphonate ternary systems have been measured at 40 °C and 25 MPa to investigate the benefit of using a co-solvent. Extraction experiments show that adding a co-solvent and carefully adjusting the water concentration up to 30%wt are crucial to obtain high mass extraction yields, here up to 82%.

Special Issue on Hierarchical Organization in Solvent Extraction; International audience; We consider here the extraction of metals in the form of salts transferred from an aqueous to a solvent phase. Extraction is triggered by complexation and quenched by the associated necessary reorganization of the structured solvent phase. The extraction of ions changes the relative fraction of extractant molecules that is not part of the highly curved surfactant monolayer and is dispersed molecularly in the oil, and also the polar volume fraction including co-extracted water. The free energy and corresponding microstructures of the water-poor microemulsions are modelled in the frame of the Gaussian random fields (GRF) model. The curvature frustration energy significantly contributes to the free energy of extraction. A typical example of predicted isotherm using the GRF model is compared to the classically considered supramolecular complex formation, together with a minimal Langmuir model and an explicit monomer-to-film equilibrium of amphiphilic extractant. The corresponding small-angle scattering spectra and morphology changes are shown. One implication is that selectivity between a hydrated and a non-hydrated species is concentration dependent and cannot be considered as a constant as a function of the extractant concentration.

International audience; In this article Part II, we consider the application of ienaic modeling for solvent extraction of rare earths in the case of the mixed DMDOHEMA/HDEHP extractant system. The system exhibits a synergistic extraction effect depending on the acid concentration and the extractant mole fraction, as demonstrated in the experimental article Part I. In this work, we directly compare experimental findings with theoretical predictions of the droplet model. The model considers the effective free energy of transfer as a combination of competing molecular forces, but contrary to previous micelle models that focus only on the dominant stoichiometry, it allows calculations of free energies of every possible spherical aggregate. The resulting image of the extraction process is that different behaviors can be obtained depending on the acidity and mole fraction of extractants, which are associated with different aggregation regimes in a complex free energy landscape of the system. Nevertheless, self-assembly is tuned by the extraction of all solutes, and not only the target metal cations.

International audience; In solvent extraction, the self-assembly of amphiphilic molecules into an organized structure is the phenomenon responsible for the transfer of the metal ion from the aqueous phase to the organic solvent. Despite their significance for chemical engineering and separation science, the forces driving the solute transfer are not fully understood. Instead of assuming the simple complexation reaction with predefined stoichiometry, we model synergistic extraction systems by a colloidal approach that explicitly takes into account the self-assembly resulting from the amphiphilic nature of the extractants. Contrary to the current paradigm of simple stoichiometry behind liquid–liquid extraction, there is a severe polydispersity of aggregates completely different in compositions, but similar in the free energy. This variety of structures on the nanoscale is responsible for the synergistic transfer of ions to the organic phase. Synergy can be understood as a reciprocal effect of chelation: it enhances extraction because it increases the configurational entropy of an extracted ion. The global overview of the complex nature of a synergistic mixture shows different regimes in self-assembly, and thus in the extraction efficiency, which can be tuned with respect to the green chemistry aspect.

Microemulsions, as thermodynamically stable mixtures of oil, water, and surfactant, are known and have been studied for more than 70 years. However, even today there are still quite a number of unclear aspects, and more recent research work has modified and extended our picture. This review gives a short overview of how the understanding of microemulsions has developed, the current view on their properties and structural features, and in particular, how they are related to applications. We also discuss more recent developments regarding nonclassical microemulsions such as surfactant-free (ultraflexible) microemulsions or ones containing uncommon solvents or amphiphiles (like antagonistic salts). These new findings challenge to some extent our previous understanding of microemulsions, which therefore has to be extended to look at the different types of microemulsions in a unified way. In particular, the flexibility of the amphiphilic film is the key property to classify different microemulsion types and their properties in this review. Such a classification of microemulsions requires a thorough determination of their structural properties, and therefore, the experimental methods to determine microemulsion structure and dynamics are reviewed briefly, with a particular emphasis on recent developments in the field of direct imaging by means of electron microscopy. Based on this classification of microemulsions, we then discuss their applications, where the application demands have to be met by the properties of the microemulsion, which in turn are controlled by the flexibility of their amphiphilic interface. Another frequently important aspect for applications is the control of the rheological properties. Normally, microemulsions are low viscous and therefore enhancing viscosity has to be achieved by either having high concentrations (often not wished for) or additives, which do not significantly interfere with the microemulsion. Accordingly, this review gives a comprehensive account of the properties of microemulsions, including most recent developments and bringing them together from a united viewpoint, with an emphasis on how this affects the way of formulating microemulsions for a given application with desired properties., T.Z. thanks the German Science Foundation (DFG) for providing a Mercator professorship within the International Research Training Group (IRTG) 1524 (SSNI) at the Technische Universität Berlin, as well as the Agence Nationale de la Recherche (ANR) for the LABEX “Chemisyst” grant ANR 2011-01-05 that made the long-term collaboration possible.

Solubility, extraction and stabilization of curcumin extracted from Curcuma longa are still a challenge. Either the solubility power of the extracting solvent mixture is not at its optimum or non-sustainable solvents are used or the curcumin instability against oxidation is a problem. In order to tackle these problems, we consider here a promising alternative solvent medium, which is a ternary system composed of water/sodium salicylate (an anionic, preservative hydrotrope)/ethyl acetate. The effects of the structuring of the system are also studied. The position of the new critical point and the orientation of tie-lines in the liquid/liquid area were determined and further examined via interfacial tension and diffusion ordered spectroscopy (DOSY NMR) measurements. The critical point between the mono-phasic region and the liquid/liquid area is a classical one, around which no special nano-structuring is found, in contrast to some other ternary mixtures with hydrotropes. The system was investigated in terms of its curcumin solubility and its extraction power thereof. Good extraction yields (~90% of the Soxhlet reference) could be achieved in the area of best solubility. Surprisingly, the hydrophobic curcumin shows a significant solubility in systems that contain a significant amount of water in presence of sodium salicylate. These mixtures are far from the critical point but show significant structuring. The solubility is even higher than in pure ethyl acetate. At the point of highest solubility (water/sodium salicylate/ethyl acetate 7/13/80 w/w/w) 15.48 mg of curcuminoids per g Curcuma longa are successfully extracted. The partition coefficient in the lower liquid/liquid two-phasic region was determined for a subsequent purification of curcumin by precipitation. Surprisingly, curcumin accumulates at the “oil-water” interface in the more polar phase. Sodium salicylate could be removed from the precipitated curcumin by washing it with water (no trace of sodium salicylate has been detected with NMR after the washing process). The preservative effect of salicylate against the oxidative effect of light on curcumin was found to be significant. A better stabilization of curcumin was observed far away from the critical point and was most efficient in the region, where aggregates could be detected. So, extraction, solubilization, and chemical stabilization of a light sensitive substance could be performed using an anti-oxidative hydrotrope.

Hypothesis The surfactant C8EO8CH2COOH (Akypo LF2) and its salts have a small hydrophobic and a significantly longer hydrophilic part. As a consequence, there must be a significant steric constraint, once these surfactant molecules form micelles. In addition, the partially charged headgroups should bring some additional fine-tuning via electrostatic interactions to this “essentially non-ionic” surfactant. Experiments Phase diagrams of binary mixtures of water and C8EO8CH2COOH are established over large concentration and temperature ranges, also at different pHs and in the presence of sodium and calcium ions. Surface tensions and osmotic pressures are measured to understand the systems. To evaluate the microstructures, also Dynamic Light Scattering and Small-Angle X-ray Scattering are performed. Findings Apart from the formation of coacervates at very low surfactant concentrations, spherical micelles persist over the whole concentration and temperature range and do not change in size and shape. At very high surfactant concentrations, above 60% by weight, where the headgroups are no longer fully hydrated, the standard core-shell structure of micelles vanishes and highly stabilized aggregates of 8–26 octyl chains are suspended in interdigitated polyoxyethylene layers and form an “osmotic brush”. When the acid is partially transformed to a sodium salt, the repulsion between the micelles increases, whereas bridging between micelles prevails, when the counterions are calcium cations. Remarkably, the negative charges of the headgroups are randomly distributed in the hydrophilic ethylene oxide shell. Altogether, a phase diagram without lyotropic liquid crystalline phases and an extreme shift of the cloud-point in temperature and composition is found, similar to the phase diagram of C8EO8OH already known in literature. The phase properties can be explained by the curvature and packing constraints together with the Lindemann rule applied to short hydrocarbon chains.

International audience; Producing compact monoliths of mesoporous uranium oxide that are free from surface active components and able to be wet by highly radioactive solutions is of great interest for future nuclear technologies. In this direction, metastable colloidal sols of UO2 using U(IV) as precursor and carboxylic surfactants (Polyoxyethylene(9) oleyl ether carboxylic acid C16/18:1E9COOH and Polyoxyethylene(10) lauryl ether carboxylic acid C12E10COOH) have been successfully prepared by indirect precipitation for 6 pH 8 with a molar ratio between uranium and surfactant U/S

The influence of the corrosion on the evaporation of sessile droplet of sodium chloride solution was quantitatively investigated at a relative humidity of 0%. On planar surface, sessile saline droplets evaporated in the pinned, constant contact area mode. The time of evaporation of a sessile saline droplet is much longer on iron substrate than on silicon. This is due to the initiation of corrosion phenomenon. At low and intermediate salt concentrations, the inverse of the classical Evans model is observed due to the evaporation time which is fast and the hydrodynamic flows linked to evaporation. Increasing salt concentration leads to the same evaporation rate for iron and silicon. This study shows that the conditions of evaporation will influence both the evaporation itself and the corrosion phenomenon.

Separation of rare earth compounds from water into an organic phase in practical cases requires the use of specific ion binding ligands in high concentrations. These tend to form complex liquid crystalline phases preferentially at ion-rich locations inside a pertraction membrane. They form a blocking layer above an ion concentration threshold, which is experimentally characterized. It is shown to limit the flux through the membrane, which is studied for the application of rare earth recycling, an example being the phase transfer of Nd from water into organic phase. This feedback leads to a stationary membrane permeation rate that can be modeled without any free parameters in very good agreement with experiment. The ion-specific formation and dissolution of the blocking layer, a feature found also in nature, and its control suggest further studies to enhance permeation as well as its selectivity control.

The synthesis of cerium oxalate, a reaction intermediate in the preparation of high performance ceramics, is studied in sessile droplets. We compare here the effect of alcoholic solvents with the usage of structured solvents, namely ultra-flexible microemulsions in the water-rich and oil-rich configurations. The nucleation and the growth of cerium oxalate particles are the result of local mixing by the Marangoni flow of droplets loaded with oxalic acid and cerium nitrate. The morphology of the particles is very different depending on the composition of the solvent and on the mixing process. We show that the variation of the particle morphology results from the difference of the structured solvent microphases during the precipitation process. When the precipitation occurs in a water continuous phase, usual needle-like oxalate particles precipitate. When the precipitate is formed in the dispersed phase of the emulsion, structured aggregates, as close-packed aggregates of needles, are compacted by microcapillarity effects.

International audience; Industrial-scale rare earth extraction is typically performed by liquid-liquid extraction with large amounts of solvents, acids and organophosphorus ligands. An alternative is to use these extractants in supercritical CO$_2$ (SC-CO$_2$), where the crucial operating parameter is their solubility. Different molecules with amidophosphonate backbones have been synthesized and investigated in view of improving their solubility in SC-CO$_2$ and thereby their cerium extraction capacity. The CO$_2$-philicity of these extractants was adjusted by attaching branched or linear alkyl chains with four, six and eight carbons. Using a dynamic gravimetric setup, the solubility and cerium extraction capacity of these molecules were measured to vary from 1.56 to 2.47 mmol$_{ligand}$.mol$_{CO2}$$^{-1}$ and 0.25 to 0.46 mmol$_{Ce}$.mol$_{ligand}$$^{-1}$, respectively.The two properties were correlated and in both cases the highest values were obtained with a diisobutylamine chain. Solubility measurements between 313 and 331 K and between 13 and 28 MPa shows that optimal condition is (320 K ; 28 MPa).

Understanding and Prediction of the Clouding Phenomenon by Spontaneous and Effective Packing Concepts. N2 - In this work, we show by which mechanism branching of the hydrocarbon chains influences the cloud point of nonionic, ethoxylated surfactants. The temp.-induced sepn. into a dil. and a concd. liq. phase is of liq.-gas type and can be explained by the relative probability of endcaps and branching points of the cylindrical micelles in both phases. The influence of branches on the hydrocarbon chains can be easily understood by means of spontaneous and effective packing concepts, while quantification via hydrophilic/lipophilic balance (HLB), hydrophilic-lipophilic difference (HLD), and HLD-Net Av. Curvature requires parametrization. The phase equil. above the cloud point phenomenon is equiv. to the Winsor I type phase equil., one of the five known phase equil. in ternary systems.

Small amounts of nonpolar additives can have a tremendous impact on viscosity and viscoelasticity of giant micelles and completely change macroscopic properties. The effect can be best understood with the establishment of complete salt curves by screening surfactant viscosity as a function of electrolyte concentration. From previous studies in micellar systems of sodium laureth sulfate (SLES) with fragrance molecules, two independent mechanisms could be identified, co-solvent type interactions leading to a decrease of the maximum viscosity, and co-surfactant type interactions that cause the salt curve shift to the left. Our studies here reveal two new mechanisms with different effects on the salt curve. In particular, with long-chain hydrocarbons from n-octane to n-tetradecane a right shift was observed, whereas with short-chain or cyclic hydrocarbons such as n-hexane or cyclohexane the maximum viscosity increases. The two effects are interpreted via an extension of a recently developed thermodynamic model where changes in viscosity can be rationalized by a rebalance of the relative concentration of the three co-existing microphases: endcaps, cylinders and branching points. The right shift is linked to a continuous transformation of giant micelles into microemulsions containing an internal fluid. On the other hand, viscosity at maximum scales with the generalized bending constant of the molecular film forming the three microphases of the surfactant system. The total of four proposed mechanisms of solute-surfactant interactions that can impact amplitude and position of salt curves are independent and of different origin, but they are all intimately linked to the location of the additives within the surfactant film: headgroup, micellar interface, surfactant tail region or micellar core. Further investigation will be necessary to understand the molecular driving forces that position nonpolar additives within micellar aggregates, which would be the key for successful prediction of their impact on macroscopic viscosity.

International audience; We propose the statistical thermodynamic model for the prediction of the liquid–liquid extraction efficiency in the case of rare-earth metal cations using the common bis(2-ethyl-hexyl)phosphoric acid (HDEHP) extractant. In this soft matter-based approach, the solutes are modeled as colloids. The leading terms in free-energy representation account for: the complexation, the formation of a highly curved extractant film, lateral interactions between the different extractant head groups in the film, configurational entropy of ions and water molecules, the dimerization, and the acidity of the HDEHP extractant. We provided a full framework for the multicomponent study of extraction systems. By taking into account these different contributions, we are able to establish the relation between the extraction and general complexation at any pH in the system. This further allowed us to rationalize the well-defined optimum in the extraction engineering design. Calculations show that there are multiple extraction regimes even in the case of lanthanide/acid system only. Each of these regimes is controlled by the formation of different species in the solvent phase, ranging from multiple metal cation-filled aggregates (at the low acid concentrations in the aqueous phase), to the pure acid-filled aggregates (at the high acid concentrations in the aqueous phase). These results are contrary to a long-standing opinion that liquid–liquid extraction can be modeled with only a few species. Therefore, a traditional multiple equilibria approach is abandoned in favor of polydisperse spherical aggregate formations, which are in dynamic equilibrium.

Hypothesis The formation of transient networks of giant micelles leads to a viscosity peak when salt is added to aqueous solutions of charged surfactants. It is the consequence of an increase of the packing parameter due to charge screening of the surfactant headgroups, leading to a continuous transformation of the aggregates from spherical to wormlike micelles, and finally to branched networks. It should therefore be possible to predict the macroscopic viscosity of entangled giant micelles by modelling the packing parameter at nanoscale. Experiments A thermodynamic model is presented with a minimum of adjustable parameters, where branched networks are considered to be built from three coexisting microphases: cylinders, endcaps, and junctions. We use spontaneous packing parameters, in which the whole molecular length instead of the commonly used hydrocarbon chain length is considered. Standard reference chemical potentials and subsequently the occurrence of each microphase can be explicitly derived at specific electrolyte concentrations. Effective micellar length of giant micelles can be obtained from the microphase composition and is subsequently used to calculate the viscosity. Findings The model successfully predicts position and intensity of the viscosity maximum observed in experimental salt curves of sodium laureth sulfate (SLES). The robustness of the model was further investigated for various types of added salts or fragrance oils that affect differently spontaneous packing parameters or interfacial bending energy. An excellent agreement of the simulated salt curves with experimental data was achieved.

Selectively exchanging metal complexes between emulsified water-poor microemulsions and concentrated solutions of mixed electrolytes is the core technology for strategic metal recycling. Nanostructuration triggered by solutes present in the organic phase is understood, but little is known about fluctuations of the microemulsion-water interface. We use here a modified version of an optoelectric device initially designed for air bubbles, in order to evidence resonant electrically induced surface waves of an oily droplet suspended in an aqueous phase. Resonant waves of nanometer amplitude of a millimeter-sized microemulsion droplet containing a common ion-specific extractant diluted by dodecane and suspended in a solution of rare earth nitrate are evidenced for the first time with low excitation fields (5 V/cm). From variation of the surface wave spectrum with rare earth concentration, we evidence uptake of rare-earth ions at the interface and at higher concentration the formation of a thin "crust" of liquid crystal forming at unusually low concentration, indicative of a surface induced phase transition. The effect of the liquid crystal structure on the resonance spectrum is backed up by a model, which is used to estimate crust thickness.

The theoretical description of systems with soft interfaces requires a precise definition of the interfaces that are present. Such definitions are common for interfaces of simple liquids and for surfactant assemblies like micelles, membranes, and microemulsions. Here, we focus on several possible rigorous definitions in a recently described surfactant-free microemulsion that consists of octanol, ethanol, and water, in which micelle-like aggregates are in dynamic equilibrium with the surrounding pseudo phase. We test different definitions that are based on the radial distribution functions of the components with respect to the center of these surfactant-free micelles. All definitions result in experimentally indistinguishable locations of the interface within the limits of resolution of light, X-ray, and neutron scattering experiments, since their locations differ by at most 0.4 nm, which corresponds to roughly 2-3 bond lengths.

We assemble here all available descriptions of oil-soluble surfactant aggregates with or without solutes, assumed to be located in the polar cores of reverse micelles. The presence of solutes is crucial for the formation of a well-defined interface, thus inducing a transition from a loose reverse aggregate into a more structured micelle. This transition can be followed by the concomitant decrease of the “critical aggregation concentration” (c.a.c.). The less organized state as reverse aggregates is predominant when no “nucleating” species such as water, salts, or acids are present. One way to understand this weak aggregation is a depletion driving to aggregates as pseudo-phases introduced by Tanford. Analogues coexisting pseudo-phases seem to exist: weak oil-in-water (o/w) aggregation with the so-called surfactant-free microemulsions, containing loose aggregates, and re-entrant phase diagrams presenting a lowest aggregation concentration (l.a.c.), as described in the seventies.

We study the addition of electrolytes to surfactant-free microemulsions in the domain where polydisperse pre-Ouzo aggregates are present. As in previous studies, the microemulsion is the ternary system water/ethanol/1-octanol, where ethanol acts as co-solvent. Addition of electrolytes modifies the static X-ray and neutron scattering, and dynamic light scattering patterns, as well as the position of the miscibility gap, where spontaneous emulsification occurs upon dilution with water. All observations can be rationalized considering that electrolytes are either “salting out” the ethanol, which is the main component of the interface stabilizing the aggregates, or producing charge separation via the antagonistic ion effect discovered by Onuki et al. Amphiphilic electrolytes, such as sodium dodecylsulfate or sodium dietheylhexylphosphate, induce a gradual transition towards monodisperse ionic micelles with their characteristic broad scattering “peak”. In these micelles the ethanol plays then the role of a cosurfactant. Dynamic light scattering can only be understood by combination of fluctuations of aggregate concentration due to the vicinity of a critical point and in-out fluctuations of ethanol., Open Access Komponente aus der Allianzlizenz

International audience; In the second part of this study, we analyze the free energy of transfer in the case of synergistic solvent extraction. This free energy of the transfer of an ion in dynamic equilibrium between two coexisting phases is decomposed into four driving forces combining long-range interactions with the classical complexation free energy associated with the nearest neighbors. We demonstrate how the organometallic complexation is counterbalanced by the cost in free energy related to structural change on the colloidal scale in the solvent phase. These molecular forces of synergistic extraction are driven not only by the entropic term associated with the tight packing of electrolytes in the solvent and by the free energy cost of coextracting water toward the hydrophilic core of the reverse aggregates present but also by the entropic costs in the formation of the reverse aggregate and by the interfacial bending energy of the extractant molecules packed around the extracted species. Considering the sum of the terms, we can rationalize the synergy observed, which cannot be explained by classical extraction modeling. We show an industrial synergistic mixture combining an amide and a phosphate complexing site, where the most efficient/selective mixture is observed for a minimal bending energy and maximal complexation energy.

The corrosion process induced by evaporation of sessile droplets from aqueous sodium chloride solutions on planar iron surfaces was quantitatively investigated. The spatial distribution of the salt inside the evaporating sessile droplet, which is influenced by the initial salt concentration in the droplet bulk, is correlated to the localization of the anodic and cathodic reactions at the electrolyte–metal interface over the footprint droplet area. At low salt concentration, the inverse of the classical well-accepted Evans model is observed due to the hydrodynamic flows linked to evaporation: the anode area is established near the three-phase contact line region. Increasing salt concentration leads to a more uniform pitted sessile droplet: we observed locally anodic and cathodic areas over the droplet surface at the metal–electrolyte interface, where local variations in chloride concentrations occur. In addition, the presence of corrosion products and some pits demonstrate that pitting corrosion takes place if the salt concentration reaches a threshold value, experimentally determined by an optical set-up.

International audience; The bending rigidity of small reverse aggregates involved in liquid–liquid extraction processes has been investigated by molecular dynamics simulations. Simulations of a common extractant (DMDOHEMA) with four hydrophobic chains in explicit solvent (n-heptane) and in vacuum have been performed to determine the effect of solvent penetration on film stiffness. Elastic film bending energy that is needed for mesoscopic modelling of transfer of species between complex fluids is harmonic in terms of curvature (Helfrich formalism) and the packing parameter only if the solvent is explicitly taken into account. In terms of the packing parameter of the real molecular film constituting the reverse water in oil aggregates and taking into account molecular volume, area and film thickness (that is in agreement with Tanford's model), the bending rigidity is calculated to be about 16 kBT per extractant molecule (about 40 kJ mol−1), which is smaller than the free energy of transfer from an isolated “monomer” molecule to a weak aggregate, but of the order of magnitude of the free energy of transfer used in liquid–liquid extraction processes.

For colloidal solutions containing any type of surfactant inducing the formation of locally flat interfaces, we show here that two equations of state are required to understand phase behaviour and stability: the perpendicular and the lateral equations of state. This applies to lamellar phases, locally lamellar connected or sponge phases, uni- and multilamellar vesicle phases formed by detergents, lipids, extractants and theta-shaped molecules in all solutions showing optical anisotropy.

Curious effects ranging from enzyme activity to anomalies in evapn. rates that have been known for over fifty years suggest the existence and thermodn. stability of surfactant-free micelles. Only recently, joint X-ray, light and neutron scattering expts. have demonstrated that aggregates and bulk pseudo-phases coexist in presumably normal solns., in which a water insol. component is solubilized in a certain domain of concn. of a hydrotrope component like ethanol. Nevertheless, nothing is known about the mol.-level shape and structure of such aggregates. In this work we characterize mixts. of octanol, ethanol, and water by mol. dynamics simulations. For compns. in the "pre-ouzo" region (close to the single phase stability limit) we observe micelle-like aggregates that are clearly distinct from simple crit. d. fluctuations. We define an ethanol partition in the pseudo-phase from an integral of the van der Waals dispersion energy term. From this partition, octanol-rich aggregates swollen with ethanol appear with an emerging interface. Ethanol is present in the water pseudo-phase with an exponential decay similar to the one predicted by Marcelja and Radic forty years ago., Open-Access-Komponente aus der Allinanzlizenz

Ternary mixtures of medium-chain fatty alcohols, water and a hydrotrope (such as ethanol), near the immiscibility gap, make stable single phases at constant temperature. Interestingly, in this `pre-ouzo region' these single phases consist of two distinct nanoscopic pseudo-phases, one octanol-rich and one water-rich. This domain of composition, which is known to produce strong light scattering and to separate under ultracentrifugation into two phases, has been studied using contrast variation in small-angle neutron scattering (SANS) combined with small- and wide-angle X-ray scattering (SWAXS). The existence of fatty alcohol-rich domains of well defined size of the order of 2 nm radius is proven. The scattering can be approximated by an Ornstein–Zernike function, which is close to the general expression of Choi, Chen, Sottmann & Strey [Physica B, (1998),241–243, 976–978] with vanishing quadratic Porod term. Exploitation of the relative intensities at the vanishing scattering angle in SANS demonstrates that the distribution coefficient of ethanol between the octanol-rich and the water-rich domains is close to one. WAXS of the two coexisting pseudo-phases is compared with the corresponding binary water–ethanol and octanol–ethanol samples.

International audience; Revisiting aggregation of extractant molecules into water-poor mixed reverse micelles, we propose in this paper to identify the thermodynamic origins of synergy in solvent extraction. Considering that synergistic extraction properties of a mixture of extractants is related to synergistic aggregation of this mixture, we identify here the elements at the origin of synergy by independently investigating the effect of water, acid, and extracted cations. Thermodynamic equations are proposed to describe synergistic aggregation in the peculiar case of synergistic solvent extraction by evaluating critical aggregation concentration (CAC) as well as specific interactions between extractants due to the presence of water, acid and cations. Distribution of two extractant molecules in the free extractants and in reverse micelles was assessed, leading to an estimation of the in-plane interaction parameter between extractants in the aggregates as introduced by Bergström and Eriksson (Bergström, M.; Eriksson, J. C. A Theoretical Analysis of Synergistic Effects in Mixed Surfactant Systems. Langmuir 2000, 16, 7173−7181). Based on this model, we study the N,N′-dimethyl-N,N′-dioctylhexylethoxymalonamide (DMDOHEMA) and di(2-ethylexyl) phosphoric acid (HDEHP) mixture and show that adding nitric acid enhances synergistic aggregation at the equimolar ratio of the two extractants and that this configuration can be related to a favored enthalpy of mixing.

International audience; Herein, a minimal model for the common case of W/O solubilization of badly soluble compounds present in an excess phase by reverse micellar aggregates in chemical equilibrium with its single compounds is introduced. A simple model of such liquid-liquid extractions is crucial for obtaining predictive parameter for the modelling of nuclear waste management and hydrometallurgic recycling strategies. The standard Gibbs free energy of aggregation and the concentration of the corresponding aggregate is calculated within a multiple-equilibria approach for a set of aggregate compositions of solute and amphiphilic extractant molecules. This minimal model provides potential surfaces estimating the stability of different aggregate compositions with 6.2 kJ mol−1 as a generalized bending constant. The complete concentrations of free and aggregated extractant species as well as the favored aggregation numbers, the polydispersity, the activity of the organic solvent, and the critical concentrations are captured by this thermodynamic model. An increase of the apparent critical micelle concentration for an increasing solute content in the aqueous phase is detected by this method.

International audience; Ternary solutions containing one hydrotrope (such as ethanol) and two immiscible fluids, both being soluble in the hydrotrope at any proportion, show unexpected solubilization power and allow strange but yet unexplained membrane enzyme activity.We study the system-water-octanol as a simple model of such kinds of ternary solutions. The stability of “detergentless”micelles or microemulsions in such mixtures was proposed in the pioneering works of Barden and coworkers [Smith GD, Donelan CE, Barden RE (1977) J Colloid Interface Sci 60(3):488–496 and Keiser BA, Varie D, Barden RE, Holt SL (1979) J Phys Chem 83(10):1276–1281] in the 1970s and then, neglected, because no general explanation for the observations was available. Recent direct microstructural evidence by light, X-ray, and neutron scattering using contrast variation reopened the debate. We proposehere a general principle for solubilization without conventional surfactants: balance between hydration force and entropy. This balance explains the stability of microemulsions in homogeneous ternary mixtures based on cosolvents.

International audience

This paper gives an overview of weak aggregation due to long-range molecular forces beyond the first neighbor. Such subtle self-assemblies are an important part of modern colloidal chemistry and concern organic molecules as well as inorganic electrolytes and hybrid aggregates. Diverse aspects of such colloidal aggregations, as described in this special issue, can be characterized by the effective free energy per molecule involved. We discuss here expectations about emerging knowledge in this field and predictive modeling of inorganic as well as organic colloids and hybrid aggregates. Some still open questions are also given.

The effect of adding salts to micelles made of a sugar based surfactant, n-octyl-beta-glucoside, has been investigated using small angle X-ray scattering (SAXS) and dynamic light scattering (DLS) techniques. It was shown that adding salts leads to change the outer shell hydration of the micelles i.e. where the glucose moieties are situated. No ion adsorption at the micelle surface was detected. Three regimes have been determined as a function of the ionic strength (IS): (i) at low IS (

a b s t r a c t There is a still growing interest in the recovery of rare earth elements due to their manifold industrial and technological applications. We present here a simple and effective method for the enrichment of micrometer sized La2O3 particles via microparticle stabilized foams. By using the short chain amphiphile (1-hexyl)trimethylammonium bromide (C6TAB) foam that is generated by surface modified particles only can be generated. This technique allows a more selective and specific particle transport mechanism. The results are discussed in terms of surface charges and transport mechanisms. Furthermore, the effects of particle concentration, pH and amphiphile concentration are studied and evaluated. © 2012 Elsevier B.V. All rights reserved.

International audience; We consider the class of surfactants called “extractants” since they specifically interact with some cations and are used in liquid-liquid separation processes. We review here features of water-poor reverse micelles in water/oil/ extractant systems as determined by combined structural studies including small angle scattering techniques on absolute scale. Origins of instabilities, liquid-liquid separation as well as emulsification failure are detected. Phase diagrams contain the same multi-phase domains as classical microemulsions, but special unusual features appear due to the high spontaneous curvature directed towards the polar cores of aggregates as well as rigidity of the film made by extracting molecules.

Microemulsions are stable mixtures of a polar solvent, surfactant and an unpolar solvent. Ionic liquids (ILs, i.e. salts with melting points below 100 °C) are a huge class of potentially promising solvents. We discuss here published structural or thermodynamic investigations concerning microemulsions in which one or more of the three classical components are ILs. In microemulsions IL can replace respectively the “oil”, the “surfactant” and the “water” phase. Experimental proofs of the existence and stability of microemulsions are given as well as hints at their microstructure. While the four regimes initially defined by Winsor are all accessible, most of the examples of microemulsions containing ionic liquids belong to the class of “rigid” microemulsions. Since additional solutes have characteristic distribution coefficients for each pseudo phase, IL based microemulsions may provide a useful tool for solubilization (reaction medium) and separation, thus allowing the recovery of a large variety of reaction products, but also waste. Further to a discussion of phase diagrams and thermodynamics, we will show some application examples and propose challenges for future studies, in this vast but only emerging domain.

We analyse the experimental evidence of the hydration force near phospholipid bilayers when the “solvent” is a solution of carbohydrates. Two cases must be clearly distinguished: when sugar is dissolved, depletion causes a supplementary attractive force, while in the case of sugar linked to the lipid the contact pressure increases by orders of magnitude. Attractive interaction inferred between bilayers is sometimes derived from indirect evidence, i.e. scattering, attraction between layers adsorbed, shape of phase boundary limits, and without the simultaneous determination of the osmotic compressibility. Generally, water molecules in the first hydration shell of sugar compete with water molecules bound (by more than one kT in free energy) to lipid head-groups. A general result is that the decay length of any repulsive effect remains close to 0.2 nm, even in concentrated sugar solutions. A tentative general explanation of this experimental fact is given together with consequences, such as the possibility of several types of critical points appearing in bilayer stacks. Decay length as well as effective contact pressure is considered with respect to carbohydrate activity.

We describe a parameter-free analytical model based on molecular force balance to quantitatively explain the wall thickness of silica-based mesoporous materials obtained by a sol–gel route. Simple synthesis routes were proposed 20 years ago that led to a well-developed class of porous materials with mesoscale pores (i.e., between 2 and 50 nm). The general route is a micelle-templated precipitation of silicate-based polymers. To optimize thermal stability and efficient resistance to leaching, the wall thickness must be as large as possible, whereas the microporosity has to be as low as possible. Experimental attempts to control wall thickness have appeared in more than 100 publications, but a clear general predictive model is not yet available. Here, we propose a rational evaluation of wall thickness based on molecular force balance that minimizes the free energy between adjacent micelles. The force balance takes into account the following three main uncoupled driving forces: repulsive electrostatic, repul...

Due to their amphiphilic properties, malonamide molecules in alkane are organized in reverse micelle type aggregates, composed of a polar core formed by the malonamide polar heads and the extracted solutes, and surrounded by a hydrophobic shell made up of the extractant alkyl chains. The aggregates interact with one another through an attractive potential, leading to the formation of a third phase. This occurs with the splitting of the organic phase into a light phase composed mostly of diluent, and a heavy third phase containing highly concentrated extractant and solutes. In this article, we show that the aggregation (monomer concentration, domain of stability, and attractive potential between micelles) greatly depends on the nature of the extracted solute, whereas the size of aggregate (aggregation number) is only slightly influenced by this. We describe the extraction of water, nitric acid, neodymium nitrate and uranyl nitrate. Strongly polarizable species induce consistently large attraction potentials and a small stability domain for the dispersion of nanodroplets in the solvent. Highly polarizable ions such as lanthanides or uranyl induce more long-range attractive interactions than do protons.

We show that solubilization in microemulsion droplets is best described as a combination of interfacial adsorption and internal absorption. We progressively add solute to a Winsor type I system, and simultaneously measure the amount of solute at the oil–water interface and its effect on the interfacial curvature. We determine the relationship between the effective packing parameter and the amount of solute adsorbed at the oil–water interface. For four solutes, a significant amount of oil is co-extracted with solute into the interfacial film. Moreover, we show that solubilization in microemulsions can be characterized by two physical quantities with precise meaning: (1) the increase in interfacial area per molecule of adsorbed solute and (2) the number of oil molecules co-extracted with each solute molecule into the interfacial film. To quantify these effects, we introduce the constant interfacial thickness (CIT) model. It provides a general relationship between curvature, packing and interfacial composition in oil/water/surfactant/solute mixtures. Finally, we show that these results can be used to calculate the free energy of transfer of solute and oil from the droplet core to the interface.

We show that analytical ultracentrifugation can be applied to derive full equations of state of colloids in a single sedimentation equilibrium experiment, by determination of single-phase boundaries as well as of osmotic pressure versus concentration at fixed temperatures. A continuous dependence of the osmotic pressure, over orders of magnitude between at least ∼ 10 1 and 10 4 Pa, and a wide concentration range, are determined in agreement with standard theoretical considerations. Two model experimental colloidal systems are investigated: For a well-known synthetic clay system (laponite), it is shown that two regimes-counter-ion ideal gas and interacting double layers-can easily be identified in the equation of state, whereas metastable glass- or microphase-separated gel states previously encountered in osmotic stress measurments of laponite are circumvented. For the case of rigid, single phase domotic stress measurements of laponite are circumvented. For the case of rigid, crystallized catanionic bilayers, single phase domains can be identified. Osmotic pressure results in this case disagree with results obtained using the classical osmotic stress technique, as a result of sample adhesion to the ultracentrifuge cell windows and uncertainty due to possible micromolar ion contamination.

We show that three different morphologies exist near the two-phase boundary of ternary systems containing a hydrotropic cosolvent. Based on synchrotron small- and wide-angle X-ray scattering combined with molecular dynamics, we rationalize the specific scattering signature of direct, bicontinuous, and reverse mesoscale solubilization. Surprisingly, these mesostructures are resilient toward strong acids, which are required in industrial applications. However, on a macroscopic scale, the phase boundary shifts in salting-in and salting-out in the direct and respectively reverse regime, leading to a crossing of the binodals., Ultraflexible microemulsions that contain a hydrotropic cosolvent exist in three morphologies. Stability is reinforced by concentrated sulfuric acid in the water-rich corner and weakened in the octanol-rich corner.

We show that liquid–liquid extraction can be described as the equilibrium between two pseudophases of ions: the hydrated state in the water phase and the solvation state when the ions are adsorbed on an organized interface. The extractant is considered as a potential surface where the ions can adsorb. Unlike phenomenological binding “constants”, ion extraction/stripping can be seen as the sum of Langmuir isotherms. The number of aggregated extractants in one reverse micelle in the solvent is at least equal to or higher than the number of extracting molecules complexed at a given instant to the ion to be extracted. Considering extraction equilibrium as a sum of isotherms corresponding to the different states of aggregation of extractant molecule in the solvent, the resulting constant is representative of both the efficiency of the extraction and the structure of the solution. This is a first step toward the development of predictive models for the apparent distribution coefficients.

Key issues in radiochemistry, physical chemistry of separation and chemistry of materials needed for a sustainable nuclear energy production are described. These driving questions are at the origin of the creation of the Institute of Separation Chemistry at Marcoule. Each of the domains has been described extensively in recent reports for science and technology of the French academy of Science.

Osmotic pressure is a key parameter to understand the thermodynamics and the interactions in colloidal systems. We present here four examples to demonstrate the variety of information that can be extracted from it. The equation of state, i.e. the osmotic pressure versus concentration curve, could be established using analytical ultracentrifugation in binary clay–water mixtures. This method allows a quick and efficient determination of the phase boundaries, and the equation of state shows a good agreement with a Poisson–Boltzmann model. In ternary mixtures of water–anionic surfactant–cationic surfactant, phase separation with a different partitioning of the surfactant in both phases could be evidenced. In the monophasic domains, the surface charge density of the objects could be estimated from the equation of state. In mixtures of polyelectrolytes, different behaviours of the osmotic pressure with respect to the composition could be interpreted in terms of microphase separation, or homogeneous complexation, depending on the composition in polyelectrolyte. Finally, in a colloidal dispersion of spheres coated with polyelectrolytes, three different colloid–colloid interaction regimes could be identified, depending if the polyelectrolyte shells are collapsed onto the colloid, swollen, or non-overlapping. These examples illustrate the variety of information that osmotic pressure can give in a large variety of situations, making this technique an indispensable tool for the physico-chemist.

In this overview, some new applications of micelles, vesicles and lyotropic phases used for mineralization are described. Special focus is put on cases where a complex fluid built from “stiff” structures is used as a scaffold for mineralization events in the aqueous phase. Various minerals and metals have been successfully crystallized in these templates showing that it is possible to mimic the natural vesicle archetypes in biomineralization processes, although colloidal interactions can also well over compensate the templating effect of the organic matrix.

Amphiphilic association in room-temperature ionic liquids (RT-ILs) — a “green” solvent shows analogies as well as clear differences from self-assembly in water. In this review, we summarize the known features of amphiphilic association structures in the form of micelles, microemulsions, vesicles and lyotropic liquid-crystalline phases in ionic liquids. Most of the methods making use of association to control reactivity could be developed also in RT-ILs and we give a few recently published examples of this strategy.