Experimental evidence of a transition from a sponge-like to a foam-like nanostructure in water-rich L3 phases.

HYPOTHESIS: The micrometer-sized gas bubbles of a liquid foam with a dispersed gas phase of > 74 vol% are polyhedral and surrounded by a continuous aqueous phase. The structure of a water-rich microemulsion with a water phase of > 74 vol% normally consists of oil droplets in water or is bicontinuous. We hypothesize that at these high water contents polyhedral water droplets in oil can also exist. EXPERIMENTS: We (a) carried out phase studies on the water-rich side of the phase diagram of the quaternary system water/NaCl - hexyl methacrylate - AOT, because AOT is known for its propensity to form water-in-oil structures and hexyl methacrylate can be polymerized, (b) measured the electrical conductivities and viscosities, and (c) visualized the nanostructure with freeze-fracture electron microscopy (FFEM). FINDINGS: We found narrow 1-phase regions emanating from the L3 phase of the oil-free water/NaCl - AOT system by adding small amounts of oil. In these regions the conductivities become extremely low and the viscosities are extremely high. In addition, FFEM images clearly show the foam-like nanostructure.

Formation Kinetics of Oil-Rich, Nonionic Microemulsions.

The formation kinetics of oil-rich, nonionic microemulsions were investigated along different mixing pathways using a fast stopped-flow device in combination with the new high-flux small-angle neutron spectrometer D33 (ILL, Grenoble, France). While the kinetics along most pathways were too fast to be resolved, two processes could be detected mixing brine and the binary cyclohexane/C10E5 solution. Here, too, the formation of large water-in-oil droplets was found to be faster than 20 ms and therewith faster than the accessible dead time. However, subsequently, both the disintegration of the large water-in-oil droplets (600 Å) and the uptake of water by swollen micelles (50-60 Å) could be resolved. Both processes occur on the time scale of a second. Strikingly, the total internal interface forms faster than 20 ms and does not change over time.

A Journey toward Sulfolane Microemulsions Suggested as Inert, Nonaqueous Reaction Media.

Recently, it turned out that nanostructured reaction media containing highly inert solvents as tetrahydrothiophen-1,1-dioxide (sulfolane) are beneficial for strongly oxidizing or reductive reactions. Because of their ability of solubilizing polar and nonpolar solvents with a large nanostructured interface in particular microemulsions provide such interesting reaction media. Starting from the pseudoternary microemulsion H2O-n-octane-C12E4/C12E5 (polyoxyethylene n-alkyl ether), water was successively replaced by the highly inert tetrahydrothiophen-1,1-dioxide (sulfolane). We found that an increasing sulfolane content drives the system beyond the tricritical point. Replacing the already long chain surfactants C12E4 and C12E5 by a mixture of the even longer chain surfactants C18E6 and C18E8, we were able to prepare nonaqueous sulfolane microemulsions for the first time. We also teach how in a second step the phase behavior of the hydrophilic sulfolane-n-octane-C18E8 system can be tuned at constant temperature (as required by the reaction conditions) by addition of the hydrophobic cosurfactant 1-octanol (C8E0). The change in curvature that occurs by adding 1-octanol is demonstrated measuring the size of reverse micelles by DLS. We found that the radius varies from at least 8 to 16 nm, a suitable sizes for inverse nanoreaction vessels.

Controlling the self-assembly of magnetic nanoparticles by competing dipolar and isotropic particle interactions.

Control over the self-assembly of magnetic nanoparticles (MNP) into superstructures due to different types of coupling is of interest in the development of "bottom-up" fabrication schemes. Here we realize a simple strategy for the systematic variation of particle interaction potential in magnetic nanoparticles. This is achieved by varying the effective surface potential by means of a co-surfactant introduced in the course of the synthesis process. As a consequence, the ability to form chain-like assemblies is affected by the resulting balance of attractive and repulsive forces. We use electron microscopy, electron diffraction, and light scattering methods to study a series of cobalt nanoparticles as a characteristic example of ferromagnetic MNP. We demonstrate experimentally and substantiate theoretically that the observed behavior results from a balance between magnetic dipole-dipole, steric, and electrostatic interactions.

Kinetics of pressure induced structural changes in super- or near-critical CO2-microemulsions.

CO2-microemulsions show strong pressure dependent properties. Using time-resolved SANS to investigate the kinetics of structural changes upon periodic pressure jumps of adjustable amplitude, we found that the compression-induced formation of cylinders occurs on a timescale of one second, whereas the expansion-induced disintegration into CO2 swollen spherical micelles is much faster.

Homogenous nucleation rates of n-propanol measured in the Laminar Flow Diffusion Chamber at different total pressures.

Nucleation rates of n-propanol were investigated in the Laminar Flow Diffusion Chamber. Nucleation temperatures between 270 and 300 K and rates between 10(0) and 10(6) cm(-3) s(-1) were achieved. Since earlier measurements of n-butanol and n­pentanol suggest a dependence of nucleation rates on carrier gas pressure, similar conditions were adjusted for these measurements. The obtained data fit well to results available from literature. A small positive pressure effect was found which strengthen the assumption that this effect is attributed to the carbon chain length of the n-alcohol [D. Brus, A. P. Hyvärinen, J. Wedekind, Y. Viisanen, M. Kulmala, V. Zdímal, J. Smolík, and H. Lihavainen, J. Chem. Phys. 128, 134312 (2008)] and might be less intensive for substances in the homologous series with higher equilibrium vapor pressure. A comparison with the theoretical approach by Wedekind et al. [Phys. Rev. Lett. 101, 12 (2008)] shows that the effect goes in the same direction but that the intensity is much stronger in experiments than in theory.

Co-condensation of nonane and D2O in a supersonic nozzle.

We study the unary and binary nucleation and growth of nonane-D2O nanodroplets in a supersonic nozzle. Fourier Transform Infrared spectroscopy measurements provide the overall composition of the droplets and Small Angle X-ray Scattering experiments measure the size and number density of the droplets. The unary nucleation rates Jmax of nonane, 9.4 × 10(15) < Jmax /cm(-3) s(-1) < 2.0 × 10(16), and those of D2O, 2.4 × 10(17) < Jmax /cm(-3) s(-1) < 4.1 × 10(17), measured here agree well with previous results. In most of the binary condensation experiments new particle formation is dominated by D2O, but the observed nucleation rates are decreased by up to a factor of 6 relative to the rates measured for pure D2O, an effect that can be partly explained by non-isothermal nucleation theory. The subsequent condensation of D2O is inhibited both by the increased temperature of the binary droplets relative to the pure D2O droplets, and because the binary droplet surface is expected to be comprised largely of nonane. For the one case where nonane appears to initiate condensation, we find that the nucleation rate is about 50% higher than that observed for pure nonane at comparable pv0, consistent with significant particle formation driven by D2O.

Singlet oxygen photo-oxygenation in water/pluronic F-127 hydrogels: increased reaction efficiency coupled with a switch in regioselectivity.

Pluronic F-127 hydrogels are highly efficient microenvironments for photochemical reactions, as demonstrated for singlet oxygen reactions of monoalkenes. Nonpolar substrates are localized in the nanosized polymer compartment, which can be visualized by neutron scattering. The efficiency of (1)O(2) reactions is strongly increased for tiglate derivatives and the regioselectivity of the ene reaction of trisubstituted alkenes is completely switched in comparison with solution phase and inverted in comparison with intrazeolite photo-oxygenations.

Nucleation of ethanol, propanol, butanol, and pentanol: a systematic experimental study along the homologous series.

We present homogeneous vapor-liquid nucleation rates of the 1-alcohols (C(n)H(2n+1)OH, n = 2-4) measured in the well-established two-valve nucleation pulse chamber as well as in a novel one-piston nucleation pulse chamber at temperatures between 235 and 265 K. The nucleation rates and critical cluster sizes show a very systematic behavior with respect to the hydrocarbon chain length of the alcohol, just as their thermo-physical parameters such as surface tension, vapor pressure, and density would suggest. For all alcohols, except ethanol, predictions of classical nucleation theory lie several orders of magnitude below the experimental results and show a strong temperature-dependence typically found in nucleation experiments. The more recent Reguera-Reiss theory [J. Phys. Chem. B 108(51), 19831 (2004)] achieves reasonably good predictions for 1-propanol, 1-butanol, and 1-pentanol, and independent of the temperature. Ethanol, however, clearly shows the influence of strong association between molecules even in the vapor phase. We also scaled all experimental results with classic nucleation theory to compare our data with other data from the literature. We find the same overall temperature trend for all measurement series together but inverted and inconsistent temperature trends for individual 1-propanol and 1-butanol measurements in other devices. Overall, our data establishe a comprehensive and reliable data set that forms an ideal basis for comparison with nucleation theory.

Freezing water in no-man's land.

We report homogeneous ice nucleation rates between 202 K and 215 K, thereby reducing the measurement gap that previously existed between 203 K and 228 K. These temperatures are significantly below the homogenous freezing limit, T(H)≈ 235 K for bulk water, and well within no-man's land. The ice nucleation rates are determined by characterizing nanodroplets with radii between 3.2 and 5.8 nm produced in a supersonic nozzle using three techniques: (1) pressure trace measurements to determine the properties of the flow as well as the temperature and velocity of the droplets, (2) small angle X-ray scattering (SAXS) to measure the size and number density of the droplets, and (3) Fourier Transform Infrared (FTIR) spectroscopy to follow the liquid to solid phase transition. Assuming that nucleation occurs throughout the droplet volume, the measured ice nucleation rates J(ice,V) are on the order of 10(23) cm(-3) s(-1), and agree well with published values near 203 K.

Microstructure of supercritical CO2-in-water microemulsions: a systematic contrast variation study.

Microemulsions of the type H(2)O-scCO(2)-surfactant are potential candidates for novel solvent mixtures in the field of green chemistry. Furthermore, scCO(2)-microemulsions are highly interesting from a fundamental point of view since their properties such as the bending elastic constants can be strongly influenced solely by varying the pressure without changing the components. With this motivation we studied the phase behavior and the microstructure of water-rich scCO(2)-microemulsions. Such microemulsions were formulated using the technical grade non-ionic surfactants Zonyl FSO 100 and Zonyl FSN 100. At elevated pressures the temperature dependent phase behavior of these systems follows the general patterns of non-ionic microemulsions. Small angle neutron scattering experiments were conducted to determine the length scales and the topology of the microstructure of these systems. Having determined the exact scattering length densities and the composition of the respective sub-phases by a systematic contrast variation we could show that these systems consist of CO(2)-swollen microemulsion droplets that are dispersed in a continuous aqueous-phase. The scattering data were analyzed using a newly derived form factor for polydisperse, spherical core/shell particles with diffuse interfaces. The underlying analytical density profiles could be confirmed applying the model-free Generalized Indirect Fourier Transformation (GIFT) to the scattering data. Following the general patterns of non-ionic microemulsions the radius of the microemulsion droplets is found to increase almost linearly upon the addition of CO(2).

Soft fluctuating surfactant membranes in supercritical CO2-microemulsions.

The bending rigidity of surfactant membranes in novel bicontinuous CO(2)-microemulsions of the type H(2)O/NaCl-scCO(2)-Zonyl FSH/Zonyl FSN 100 was determined using both high pressure small angle neutron scattering and neutron-spin echo spectroscopy. As an important result it was found, that the stiffness of the membrane increases solely by an increase of the pressure.

Homogeneous water nucleation in a laminar flow diffusion chamber.

Homogeneous nucleation rates of water at temperatures between 240 and 270 K were measured in a laminar flow diffusion chamber at ambient pressure and helium as carrier gas. Being in the range of 10(2)-10(6) cm(-3) s(-1), the experimental results extend the nucleation rate data from literature consistently and fill a pre-existing gap. Using the macroscopic vapor pressure, density, and surface tension for water we calculate the nucleation rates predicted by classic nucleation theory (CNT) and by the empirical correction function of CNT by Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)]. As in the case of other systems (e.g., alcohols), CNT predicts a stronger temperature dependence than experimentally observed, whereas the agreement with the empirical correction function is good for all data sets. Furthermore, the isothermal nucleation rate curves allow us to determine the experimental critical cluster sizes by use of the nucleation theorem. A comparison with the critical cluster sizes calculated by use of the Gibbs-Thomson equation is remarkably good for small cluster sizes, for bigger ones the Gibbs-Thomson equation overestimates the cluster sizes.

Phase behaviour of propane- and scCO(2)-microemulsions and their prominent role for the recently proposed foaming procedure POSME (Principle of Supercritical Microemulsion Expansion).

In this study we present a systematic investigation of the phase behaviour of microemulsions containing near- or supercritical solvents. The starting point of this study are microemulsions of the type water/NaCl-propane-polyethyleneglycol mono-n-alkyl ether at a pressure of p = 220 bar. Replacing propane stepwise by supercritical carbon dioxide the typical phase behavior of microemulsions systems can still be observed using scCO(2) as the only nonpolar solvent. Thus, increasing the temperature a phase inversion from a CO(2)-in-water to a water-in-CO(2) microemulsion via a balanced CO(2) microemulsion is found for the first time. Such mixtures of water and scCO(2) are expected to be versatile solvents in green chemistry. In addition, the formulation of supercritical microemulsions is the initial step in the Principle Of Supercritical Microemulsion Expansion (POSME) (DE Pat., 102 60 815 B4, 2008), which is a promising new approach for the production of low-cost nanocellular foams. In contrast to conventional foaming procedures, this approach suggests the formation of nanofoams by expanding micelles swollen with a supercritical blowing agent, thereby ensuring the unhindered formation and growth of bubbles without mass transport.

Argon nucleation in a cryogenic supersonic nozzle.

We have measured pressures p and temperatures T corresponding to the maximum nucleation rate of argon in a cryogenic supersonic nozzle apparatus where the estimated nucleation rates are J=10(17+/-1) cm(-3) s(-1). As T increases from 34 to 53 K, p increases from 0.47 to 8 kPa. Under these conditions, classical nucleation theory predicts nucleation rates of 11-13 orders of magnitude lower than the observed rates while mean field kinetic nucleation theory predicts the observed rates within 1 order of magnitude. The current data set appears consistent with the measurements of Iland et al. [J. Chem. Phys. 127, 154506 (2007)] in the cryogenic nucleation pulse chamber. Combining the two data sets suggests that classical nucleation theory fails because it overestimates both the critical cluster size and the excess internal energy of the critical clusters.

Homogeneous nucleation of a homologous series of n-alkanes (C(i)H(2i+2), i=7-10) in a supersonic nozzle.

Homogeneous nucleation rates of the n-alkanes (C(i)H(2i+2); i=7-10) were determined by combining information from pressure trace measurements and small angle x-ray scattering (SAXS) experiments in a supersonic Laval nozzle. The condensible vapor pressure p(J max), the temperature T(J max), the characteristic time Deltat(J max), and supersaturation S(J max) corresponding to the peak nucleation rate J(max) were determined during the pressure trace measurements. These measurements also served as the basis for the subsequent SAXS experiments. Fitting the radially averaged SAXS spectrum yielded the mean droplet radius r, 5

Crossover from nucleation to spinodal decomposition in a condensing vapor.

The mechanism controlling the initial step of a phase transition has a tremendous influence on the emerging phase. We study the crossover from a purely nucleation-controlled transition toward spinodal decomposition in a condensing Lennard-Jones vapor using molecular dynamics simulations. We analyze both the kinetics and at the same time the thermodynamics by directly reconstructing the free energy of cluster formation. We estimate the location of the spinodal, which lies at much deeper supersaturations than expected. Moreover, the nucleation barriers we find differ only by a constant from the classical nucleation theory predictions and are in very good agreement with semiempirical scaling relations. In the regime from very small barriers to the spinodal, growth controls the rate of the transition but not its nature because the activation barrier has not yet vanished. Finally, we discuss in detail the influence of the chosen reaction coordinate on the interpretation of such simulation results.

Homogeneous nucleation of nitrogen.

We investigated the homogeneous nucleation of nitrogen in a cryogenic expansion chamber [A. Fladerer and R. Strey, J. Chem. Phys. 124, 164710 (2006)]. Gas mixtures of nitrogen and helium as carrier gas were adiabatically expanded and cooled down from an initial temperature of 83 K until nucleation occurred. This onset was detected by constant angle light scattering at nitrogen vapor pressures of 1.3-14.2 kPa and temperatures of 42-54 K. An analytical fit function well describes the experimental onset pressures with an error of +/-15%. We estimate the size of the critical nucleus with the Gibbs-Thomson equation yielding critical sizes of about 50 molecules at the lowest and 70 molecules at the highest temperature. In addition, we estimate the nucleation rate and compare it with nucleation theories. The predictions of classical nucleation theory (CNT) are 9 to 19 orders of magnitude below the experimental results and show a stronger temperature dependence. The Reguera-Reiss theory [Phys. Rev. Lett. 93, 165701 (2004)] predicts the correct temperature dependence at low temperatures and decreases the absolute deviation to 7-13 orders of magnitude. We present an empirical correction function to CNT describing our experimental results. These correction parameters are remarkably close to the ones of argon [Iland et al., J. Chem. Phys. 127, 154506 (2007)] and even those of water [J. Wolk and R. Strey, J. Phys. Chem. B 105, 11683 (2001)].