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Microemulsions with supercritical CO2 are promising alternatives for organic solvents, especially if both polar and non-polar components need to be dissolved. However, only fluorinated surfactants, which are known to be environmentally unfriendly, are appropriate to formulate well-structured microemulsions. While most approaches to increase the environmental performance of CO2-microemulsions deal with the design of new surfactants with a reduced degree of fluorination, we discovered that the partial substitution of CO2 by cyclohexane enables a considerable reduction of fluorinated surfactants. Thereby, the most efficient solubilization of the CO2/cyclohexane mixture, which turned out to be pressure-dependent, was found at a cyclohexane-to-CO2 mass ratio between 1 : 6 and 1 : 4. In order to elucidate this unexpected effect a systematic Small Angle Neutron Scattering (SANS) contrast variation study was performed. The analysis of the recorded scattering curves by the Generalized Indirect Fourier Transformation (GIFT) clearly shows that the scattering length density profiles differ considerably from CO2-microemulsions without cyclohexane. Instead of a nearly constant scattering length density, a density profile that varies systematically over half of the droplet radius was detected. These results clearly indicate that the observed efficiency boosting is caused by the formation of a depletion zone of cyclohexane close to the fluorinated amphiphilic film.
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We follow the nucleation of n-alcohols, n-propanol through n-pentanol, in two sets of supersonic nozzles having differing linear expansion rates. Combining the data from static pressure trace measurements with small-angle X-ray scattering we report the experimental nucleation rates and critical cluster sizes. For n-propanol, position resolved measurements clearly confirm that coagulation of the 2-10 nm size (radius) droplets occurs on the time scale of the experiment but that the effect of coagulation on the results is minimal. Under the conditions of the current experiments, our results suggest that alcohols have critical clusters that range from the dimer (n-pentanol) to the hexamer (n-propanol). We then compare the experimental results with classical nucleation theory (CNT), the Girshick-Chiu variant of CNT (GC), and the mean field kinetic nucleation theory (MKNT). Both CNT and MKNT underestimate the nucleation rates by up to 5 and 7 orders of magnitude, respectively, while GC theory predicts rates within 2 orders of magnitude. Correspondingly, the critical cluster size for all alcohols is overpredicted by factors of 2-9 with agreement improving with increasing chain length. An interesting byproduct of our experiments is that we find that the coagulation rate is enhanced by a factor of 3 over the value one would calculate for the free molecule regime.
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We have generated closed-cell microcellular foams from gliadin, an abundantly available wheat storage protein. The extraction procedure of gliadin from wheat gluten, which involves only the natural solvents water and ethanol, respectively, is described with emphasis on the precipitation step of gliadin which results in a fine dispersion of mostly spherical, submicron gliadin particles composed of myriad of protein molecules. A dense packing of these particles was hydrated and subjected to an atmosphere of carbon dioxide or nitrogen in a high-pressure cell at 250 bar. Subsequent heating to temperatures close to but still below 100 °C followed by sudden expansion and simultaneous cooling resulted in closed-cell microcellular foam. The spherical gliadin templates along with the resulting foam have been analyzed by scanning electron microscope (SEM) pictures. The size distribution of the primary particles shows diameters peaked around 0.54 µm, and the final foam cell size peaks around 1.2 µm, at a porosity of about 80 %. These are the smallest foam cell sizes ever reported for gliadin. Interestingly, the cell walls of these microcellular foams are remarkably thin with thicknesses in the lower nanometer range, thus nourishing the hope to be able to reach gliadin nanofoam.
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Time-resolved small-angle neutron scattering (TR-SANS) was employed to observe temperature-induced phase transitions from the sponge (L (3) to the lamellar ( L (alpha) phase, and vice versa, in the water-oil (n -decane)-non-ionic surfactant ( C(12)E(5) system using both bulk and film contrast. Samples of different bilayer volume fractions phi and solvent viscosities eta were investigated applying various amplitudes of temperature jump DeltaT . The findings of a previous (2)H -NMR study could be confirmed, where the lamellar phase formation was determined to occur through a nucleation and growth process, while it was concluded that the L (3) -phase develops in a mechanistically different and more rapid manner involving uncorrelated passage formation. Likewise, the kinetic trends of the nucleation and growth transition (decreased transition time with increase of phi and DeltaT were witnessed once again. Additionally, NMR and SANS data that demonstrate a strong dependency of that process on solvent viscosity eta are presented. Contrariwise, it is made evident via both SANS and NMR results that the L (alpha) -to-L (3) transition time is independent (within experimental sensitivity) of the varied parameters (phi , DeltaT , eta . Unusual scattering evolution in one experiment, originating from a highly ordered lamellar phase, intriguingly hints that a major rate determining factor is the disruption of long-range order. Furthermore, the bulk contrast investigations give insight into structure peak shifts/development during the transitions, while the film contrast experiments prove the bilayer thickness to be constant throughout the phase transitions and show that there is no evidence for a change in the short-range order of the bilayer structure. The latter was considered possible, due to the different topology of the L (3) and L (alpha) phases. Lastly, an unexpected yet consistent appearance of anisotropic scattering is detected in the L (3) -to- L (alpha) transitions.
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The equilibrium microstructures in microemulsions and other self-assembled systems show complex, connected shapes such as symmetric bicontinuous spongelike structures and asymmetric bicontinuous networks formed by cylinders interconnected at junctions. In microemulsions, these cylinder network microstructures may mediate the structural transition from a spherical or globular phase to the bicontinuous microstructure. To understand the structural and statistical properties of such cylinder network microstructures as measured by scattering experiments, models are needed to extract the real-space structure from the scattering data. In this paper, we calculate the scattering functions appropriate for cylinder network microstructures. We focus on such networks that contain a high density of network junctions that connect the cylindrical elements. In this limit, the network microstructure can be regarded as an assembly of randomly oriented, closed packed network junctions (i.e., the cylinder scattering contributions are neglected). Accordingly, the scattering spectrum of the network microstructure can be calculated as the product of the junction number density, the junction form factor, which describes the scattering from the surface of a single junction, and a structure factor, which describes the local correlations of different junctions due to junction interactions (including their excluded volume). This approach is applied to analyze the scattering data from a bicontinuous microemulsion with equal volumes of water and oil. In a second approach, we included the cylinder scattering contribution in the junction form factor by calculating the scattering intensity of Y junctions to which three rods with spherical cross section are attached. The respective theoretical predictions are compared with results of neutron scattering measurements on a water-in-oil microemulsion with a connected microstructure.
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The phase behavior of C(10)E(4)-oil-water systems at constant o/w ratio and variable temperature (fish diagram) has been investigated for several homologous oil families. The temperature T( *) and surfactant concentration C( *) at the critical point were determined for 10 n-alkanes varying from C(6) to C(28) as well as for a series of alkylcyclohexanes and alkylbenzenes. On the basis of T( *), equivalent alkane carbon numbers (EACN) were assigned to nonlinear alkanes, alkylbenzenes, and alkylcyclohexanes. The consistency of the method was shown by corroborating that the EACN values of oils previously investigated with other C(i)E(j) (dibutyl ether, squalane, isopropyl myristate, and dodecylbenzene) are the same when determined with C(10)E(4). The fact that two oils of different nature but with the same EACN (i.e., the same T( *)) do not exhibit the same C( *) is discussed in terms of monomeric solubility of the surfactant in the oil (CMC(oil)).
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As triacylglycerols are the main components of natural fats and oils their solubilization in the form of emulsions or microemulsions was of great interest within the last years. However, systematic studies of their properties along the classical lines of complex fluids science are still missing. In the present paper we focus on the phase behavior, the interfacial tension and the microstructure of systems of type H(2)O/NaCl-triacylglycerol-alkylpolyglycolether (C(i)E(j)). The interfacial tension between water and oil sigma(ab) is high in a microemulsion system containing triolein. Thus, one needs high surfactant mass fractions to formulate a single-phase microemulsion. We show that this is not only true for triolein, but also for saturated long-chained triacylglycerols. The determination of the amphiphilicity factor f(a) and the calculation of the bending rigidities of the amphiphilic film confirm that despite the fact that high surfactant mass fractions and high temperatures are needed to solubilize triolein in a system of type H(2)O/NaCl-triacylglycerol-alkylpolyglycolether (C(i)E(j)), this is still a microemulsion in the narrower sense.
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Emulsiones , Tensoactivos/química , Dispersión de Radiación , Tensión SuperficialRESUMEN
The homogeneous nucleation rates for n-nonane-n-propanol vapor mixtures have been calculated as a function of vapor-phase activities at 230 K using the classical nucleation theory (CNT) with both rigorous and approximate kinetic prefactors and compared to previously reported experimental data. The predicted nucleation rates resemble qualitatively the experimental results for low n-nonane gas phase activity. On the high nonane activity side the theoretical nucleation rates are about three orders of magnitude lower than the experimental data when using the CNT with the approximate kinetics. The accurate kinetics improves the situation by reducing the difference between theory and experiments to two orders of magnitude. Besides the nucleation rate comparison and the experimental and predicted onset activities, the critical cluster composition is presented. The total number of molecules is approximated by CNT with reasonable accuracy. Overall, the classical nucleation theory with rigorous kinetic prefactor seems to perform better. The thermodynamic parameters needed to calculate the nucleation rates are revised extensively. Up-to-date estimates of liquid phase activities using universal functional activity coefficient Dortmund method are presented together with the experimental values of surface tensions obtained in the present study.
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We predict theoretically the thermodynamics and relaxation kinetics of solutions of cylindrical branched micelles. Using a recently developed theory in combination with the experimental data, we explain the unusual, inverted temperature dependence of the phase separation observed in wormlike micelles and dilute microemulsions. We extend the model to treat the temperature dependence of the relaxation kinetics and explain the observations.
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In this paper, we present a new freeze fracture method for specimen preparation for transmission electron microscopy frozen samples. We call it freeze fracture direct imaging (FFDI) because it is a hybrid of conventional freeze fracture electron microscopy (FFEM) and cryo-transmission electron microscopy (cryo-TEM), combining elements of the fracture technique with direct imaging. Like in FFEM, the sandwich method is used to prepare the sample in a protected fashion. However, after the sample is vitrified and fractured, it is not shadowed but directly imaged. The new technique avoids some experimental artifacts produced by the blotting procedure in conventional cryo-TEM. It relies, though, on occasional fractures transparent to the electrons. The advantageous features are demonstrated by a comparison between conventional cryo-TEM and FFDI micrographs of vesicular solutions. The second outstanding advantage over conventional cryo-TEM is the fact that it is now possible for the very first time to directly image oil-rich mixtures films which normally would dissolve in the cryo-medium ethane. Micrographs of pure oil and of oil-rich microemulsions clearly prove the reliability of the FFDI technique as well as its enormous potential.
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The physical behavior of the binary phase systems of the non-ionic polyoxyethylene detergent Agrimul NRE 1205 and water was investigated. This technical detergent can be used for the large-scale recovery of biomolecules in detergent based aqueous two-phase systems. The phase diagram was determined. It shows significant and unexpected differences to highly purified detergents. Very similar to neat detergents the phase diagram can be influenced by auxiliary chemicals thus shifting the entire phase diagram in general to lower temperatures. This was demonstrated by lowering the cloud-point by various additions. The concentration factor, as an important parameter of a first capture step in purification was investigated and modeled. Auxiliary chemicals, temperature change and change in detergent concentration also influence the viscosity and density of the phases. These experimental data are shown. They can help to explain the separation behavior of proteins. In large-scale separations aqueous two-phase systems are separated using disc-stack centrifuges. It is demonstrated that this is not a feasible method for detergent-based aqueous two-phase extraction and the physical reason is presented.
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Detergentes , Polietilenglicoles , Proteínas/aislamiento & purificación , Biotecnología/métodos , Fenómenos Químicos , Química Física , Viscosidad , AguaRESUMEN
We predict theoretically the gradual formation of fluctuating, connected microemulsion networks from disconnected globules as the spontaneous curvature is varied, in agreement with recent direct measurements of these topological transitions. The connectivity induced instability together with emulsification failure of the network relate the ultralow tensions and wetting transition to the changing microstructure.
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The effect of various amphiphilic block copolymers of different molar masses on the structure and phase behavior of ternary amphiphilic systems (water, oil, and nonionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic increase in the volumes of oil and water, which can be solubilized in a bicontinuous microemulsion. High-precision neutron scattering experiments with a sophisticated contrast variation technique demonstrate that the polymers form uniformly distributed mushroom conformations on the surfactant membrane. Based on these observations, we propose a universal mechanism for the swelling behavior, which is due to the variation of the membrane curvature elasticity.
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Membrana Celular/química , Emulsiones/química , Membrana Dobles de Lípidos , Modelos Químicos , Elasticidad , Aceites/química , Polímeros/química , Tensoactivos/química , Agua/químicaRESUMEN
From extensive Monte Carlo simulations of a Larson model of perfectly periodic heteropolymers (PHP) in water, a striking stiffening is observed as the period of the alternating hydrophobic and hydrophilic blocks is shortened. At short period and low temperature needlelike conformations are the stable conformations. As temperature is increased thermal fluctuations induce kinks and bends. At large periods compact oligomeric globules are observed. From the generalized Larson prescription, originally developed for modeling surfactant molecules in aqueous solutions, we find that the shorter the period is the more stretched the PHP is. This novel effect is expected to stimulate polymer synthesis and trigger research on the rheology of aqueous periodic heteropolymer solutions.
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The two-dimensional patterns in our small angle neutron scattering (SANS) experiments from rapidly moving aerosols are anisotropic. To test the kinematic theory of two-body scattering that describes the anisotropy, we conducted SANS experiments using a constant source of D2O aerosol with droplets moving at approximately 440 m/s, and varied the neutron velocity from 267 to 800 m/s. The theoretically predicted anisotropy of the laboratory scattering intensities agrees well with the experimental results. Based on an analysis of the scattering intensity in the Guinier region, we also determined the particle velocity. The results are in very good agreement with independent velocity estimates based on supersonic flow measurements.