Small-angle light scattering studies of dense AOT-water-decane microemulsions

Summary We have performed extensive studies of a three-component microemulsion system composed of AOT-water-decane (AOT=sodium-bis-ethylhexyl-sulfosuccinate is an ionic surfactant) using small-angle light scattering (SALS). The small-angle scattering intensities are measured in the angular interval 0.001–0.1 radians, corresponding to a Bragg wave number range of 0.14 μm⁻¹<Q<<1.4 μm⁻¹. The measurements were made by changing temperature and volume fraction ϕ of the dispersed phase (water + AOT) in the range 0.05<ϕ<0.75. All samples have a fixed water-to-AOT molar ratio,w=[water]/[AOT]=40.8, in order to keep the same average droplet size in the stable one-phase region. With the SALS technique, we have been able to observe all the phase boundaries of a very complex phase diagram with a percolation line and many structural organizations within it. We observe at the percolation transition threshold, a scaling behavior of the intensity data. This behavior is a consequence of a clustering among microemulsion droplets near the percolation threshold. In addition, we describe in detail a structural transition from a droplet microemulsion to a bicontinuous one as suggested by a recent small-angle neutron scattering experiment. The loci of this transition are located several degrees above the percolation temperatures and are coincident with the maxima previously observed in shear viscosity. From the data analysis, we show that both the percolation phenomenon and this novel structural transition are derived from a large-scale aggregation between microemulsion droplets.     

Cluster description of water-in-oil microemulsions near the critical and percolation points

The three-component ionic microemulsion system consisting of AOT/water/decane shows an unusual phase behavior in the vicinity of room temperature. The phase diagram in the temperature-volume fraction (of the dispersed phase) plane exhibits a lower consolute critical point at about 40 degrees centigrades and 10% volume fraction. A percolation line, starting from the vicinity of the critical point, cuts across the plane, extending to high volume fraction side at progressively lower temperatures. In this paper we review the evidence that allows to interpret the phase behavior of our system in terms of interacting spherical droplets. We also investigate the dynamics of droplets, below and approaching the critical point by dynamic light scattering. The first cumulant and time evolution of the droplet density correlation function can be quantitatively calculated by assuming the existence of polydispersed fractal clusters formed by the microemulsion droplets due to attraction. The relaxation phenomena observed in an extensive set of measurements of electrical conductivity and permittivity close to percolation is also reviewed and interpreted through the same cluster-forming mechanism, which reproduces the most relevant features of the frequency-dependent complex dielectric constant of this system. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

A study of the properties of mixed nonionic surfactants microemulsions by NMR, SAXS, viscosity and conductivity

The pseudoternary phase behavior of the water/sucrose laurate/ethoxylated mono-di-glyceride/R (+)-limonene systems was investigated for different surfactants mixing ratios (w/w) at 25 °C. The microemulsion boundaries were determined and the surfactants content at the interface of water- R (+)-limonene was estimated. For surfactants mixing ratio (w/w) equals unity, the area of the one phase microemulsion region reaches its maximum. The system with the maximum microemulsion area was investigated using electrical conductivity, dynamic viscosity, small angle X-ray scattering, and nuclear magnetic resonance. Electrical conductivity increases as the water volume fraction increases and a percolation threshold was observed. Dynamic Viscosity varies as function of the water volume fraction in a non-monotonic way giving two-peaked plot. The characteristics of the domain size of the microemulsions called periodicity measured by small angle X-ray scattering increases with the increase in the water volume fraction. The correlation length of the domain size reaches a maximum when plotted against the water volume fraction in the microemulsions. Relative diffusion coefficients of water increase and those of oil decrease with increasing the water volume fractions in the microemulsions indicating structural transitions.     

On PbS nanoparticles formed in the compartments of water/AOT/n-heptane microemulsion

Colloidal nanodispersion of lead sulfide has been prepared in the aqueous compartments of water/AOT/n-heptane. Compartmentalization has prevented growth and coagulation of particles in the dispersion. The uv–vis and fluorescence spectral measurements of the colloidal PbS dispersion were taken. Particle size has been determined by laser light scattering, transmission electron microscopy and absorption spectroscopy. The effects of temperature, ω (water/AOT mole ratio), [AOT], and [PbS] on the particle size have been examined. The nanodispersed particles in microemulsion capped with thiophenol and dodecanethiol were isolated and characterized by the TEM and FTIR methods.     

Percolation phenomenon of calcium bis(2-ethylhexyl) sulfosuccinate water-in-oil microemulsions by conductivity and dielectric spectroscopy measurements

The sodium counterion (Na+) of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) surfactant was exchanged with calcium Ca2+ to investigate the counterion charge effect on the structure of water in normal decane microemulsions. Ohmic conductivity and dielectric permittivity measurements were performed on samples at constant water to surfactant mole ratio [water]/[Ca(AOT)(2)]=26.6. Increasing the volume fraction of the dispersed phase phi, a percolation phenomenon was observed at the constant temperature of 25 degrees C. The percolation threshold was found at phi approximately 15% by Ohmic conductivity and static dielectric permittivity studied as a function of phi, and by the frequency dependence of the complex permittivity. Critical exponents typical of the static percolation mechanism (formation of bicontinuous microemulsions) were found below and above threshold. The comparison of these results obtained for the two different counterions, Ca2+ and Na+, in AOT surfactant water in normal decane microemulsions allows detection of an important difference. The percolation below threshold is dynamic for the sodium-based microemulsions, accounting for the formation of clusters of droplets, whereas calcium-based microemulsions show a static percolation. For this system, the coalescence of droplets begins to occur below threshold at phi approximately 12%.     

On PbS nanoparticles formed in the compartments of water/AOT/n-heptane microemulsion

Colloidal nanodispersion of lead sulfide has been prepared in the aqueous compartments of water/AOT/n-heptane. Compartmentalization has prevented growth and coagulation of particles in the dispersion. The uv–vis and fluorescence spectral measurements of the colloidal PbS dispersion were taken. Particle size has been determined by laser light scattering, transmission electron microscopy and absorption spectroscopy. The effects of temperature, ω (water/AOT mole ratio), [AOT], and [PbS] on the particle size have been examined. The nanodispersed particles in microemulsion capped with thiophenol and dodecanethiol were isolated and characterized by the TEM and FTIR methods.This revised version was published online in August 2005 with a corrected issue number.     

AOT微乳体系中纳米银的可控合成及其紫外-可见光谱研究

在以琥珀酸二异辛酯磺酸钠(AOT)为表面活性剂、环己烷为连续相形成的W/O型微乳体系中,用增溶于微乳液水核中的AgNO₃为银源、水合肼为还原剂制备了纳米银溶胶,利用UV-Vis光谱分析了AgNO₃的浓度、AOT的浓度、还原剂的种类和水与表面活性剂的物质的量比(W)等参数对形成粒子数量及平均粒径的影响,为纳米银粒子的可控合成和纳米银的UV-Vis光谱解析提供了新的依据。研究表明,适当增大AgNO₃的浓度,有利于形成粒径较小的纳米银粒子;W值增大,形成粒子的平均粒径和粒子数量明显增加。和NaBH₄相比,水合肼在反胶束中的溶解性能较好,有利于微乳液反胶束中Ag+的还原。增大AOT的浓度,在一定范围内胶束对反应物的增溶能力增强,胶束的半径也相应减小,有利于形成数量较多、平均粒径较小的纳米银粒子。     

Complex patterns in reactive microemulsions: self-organized nanostructures?

In a reverse microemulsion consisting of water, oil (octane), an anionic surfactant [aerosol OT (AOT)], and the reactants of the oscillating Belousov-Zhabotinsky (BZ) reaction, a variety of complex spatiotemporal patterns appear. These include traveling and standing waves, spirals that move either toward or away from their centers, spatiotemporal chaos, Turing patterns, segmented waves, and localized structures, both stationary and oscillatory. The system consists of nanometer-sized droplets of water containing the BZ reactants surrounded by a monolayer of AOT, swimming in a sea of oil, through which nonpolar BZ intermediates can diffuse rapidly. We present experimental and computational results on this fascinating system and comment on possible future directions for research.     

Synthesis and characterization of dispersions of ZnCrO4 prepared in AOT stabilized water/heptane microemulsion

Dispersions of zinc chromate (ZnCrO₄) were prepared in H₂O/AOT (sodium bis(2-ethylhexyl sulfosuccinate))/n-heptane water-in-oil (W/O) microemulsion medium with various water pool sizes and precursor concentration both without and with sonication. The formation of ZnCrO₄ in the microemulsion was verified by XRD and FTIR measurements. The absorbance of the dispersions formed in different water pool sizes was studied. Their dimension in the microemulsion medium was determined by the dynamic light scattering method. Enthalpy of formation of ZnCrO₄ in W/O microemulsion medium was measured by isothermal titration calorimetry (ITC). The dimension and morphology of the formed ZnCrO₄ colloidal particles examined by transmission electron microscopy (TEM) were strongly dependent on the water pool size, precursor concentration and sonication.     

Infrared absorption and water structure in aerosol OT reverse micelles

Summary The structure of water in bis(2-ethylhexyl)sodium sulfosuccinate (AOT) micelles has been studied as a function of the [H₂O]/[AOT] ratio (W) by using the absorption IR due to O−H stretching modes in the 3800–3000 cm⁻¹ range. Three systems have been studied: water/AOT/carbon tetrachloride, water/AOT/n-heptane and water/AOT iso-octane. Experimental spectra are presented and discussed for the O−H stretching region both of H₂O and isotopically diluted HDO molecules in D₂O. We have restricted ourselves to the region of small amounts of water (0<W<20) where the properties of the systems change strongly with the water content. The results show that IR spectra can be expressed as sum of contributions from interfacial and bulk-like water. The fraction of water in the two “regions” within the water pool was evaluated as a function ofW. From the data a continuous variation appears in the water properties inside micellar cores rather than a two-steps hydration mechanism. The solubilization of water is described in terms of hydration of the AOT head group and Na⁺ counterions. The maximum hydration number of AOT was found to be 3.5. The same behaviour has been observed in the three solvents studied.     

Combinatorial Models of Rigidity and Renormalization

We first introduce the percolation problems associated with the graph theoretical concepts of (k,l)-sparsity, and make contact with the physical concepts of ordinary and rigidity percolation. We then devise a renormalization transformation for (k,l)-percolation problems, and investigate its domain of validity. In particular, we show that it allows an exact solution of (k,l)-percolation problems on hierarchical graphs, for k≤l<2k. We introduce and solve by renormalization such a model, which has the interesting feature of showing both ordinary percolation and rigidity percolation phase transitions, depending on the values of the parameters.     

Synthesis and photoluminescence properties of Nd2O3 nanoparticles modified by sodium bis 2-ethylhexyl sulfosuccinate

This paper reports that Nd₂O₃ nanoparticles modified by AOT(sodium bis(2-ethylhexyl) sulfosuccinate) were prepared using microemulsion method in the system of water and propanol/AOT/toluene. Transmission electron microscopy shows that the Nd₂O₃ nanoparticles take the shape of sphere with 18\,nm and 31nm with different preparation. The organic sol of Nd₂O₃ nanoparticles is very stable at room temperature. X-ray diffraction results show that the product has hexagonal phase structure. Two ultraviolet emission band at 344\,nm and 361\,nm corresponding to the transition of ⁴D_3/2→4I_9/2 and 2P_3/2→⁴I₁₁₂ or ⁴D_3/2 →⁴I_13/2 were observed.     

Temperature and pressure effects on the bending modulus of monolayers in a ternary microemulsion

We performed small-angle neutron scattering and neutron spin echo experiments on a ternary microemulsion composed of ionic surfactant AOT, water, and decane. Thermal fluctuations of monolayers have been investigated as a function of temperature and pressure. The amphiphilic monolayers become more flexible with increasing temperature and more rigid with increasing pressure. These results are consistent with the microscopic picture that the head-head repulsion of the AOT molecules is enhanced at high temperature while an attractive interaction between the hydrophobic tails of the AOT molecules increases at high pressure.     

Enhanced Hydrodynamic Radius of AOT/n-heptane/Water Reverse Micellar System Through Altered Electrostatic Interactions and Molecular Self-Assemblies

We have demonstrated a unique approach to alter the aqueous pool size of an AOT/n-heptane/water reverse micellar system. A positively charged dye Rhodamine B (RhB) and negatively charged Rose Bengal (RB) were incorporated in the reverse micellar pool to investigate the effect of electrostatic interactions and stacking effects among the dye molecules on the AOT/n-heptane/water interface. Dynamic light scattering revealed increase in reverse micellar pool size in presence of positively charged dye aggregates at the oil–water interface. However, less expansion was observed in presence of negatively charged dye aggregates (RB). This confirms the role of electrostatic interaction in modulating the hydrodynamic radius. A head-to-tail type of stacking of RhB molecules at the interface favors this expansion. The differences in stacking of the two dyes inside the reverse micelles and their torsional mobility indicated the role of the reverse micellar interface and H-bonding ability of the microenvironment on dye aggregation. Conductivity measurements demonstrated a significant drop in percolation temperature of the reverse micellar system in presence of dye aggregates. This confirms the effect of dye aggregation and electrostatic interaction on such expansion. This strategy can be exploited for solubilizing greater amounts and a wider variety of drug molecules in microemulsions.

Graphical abstract

     

Diels‐Alder Reaction in microemulsions with ionic liquid

The Diels‐Alder Reaction (DAR) between N‐ethylmaleimide and 2,3‐dimethyl‐1,3‐butadiene was studied in microemulsions with ionic liquid (IL) for the first time. The apparent second‐order rate constants were determined by spectrophotometry in the microemulsion. The effect of solvent on the DAR rate was investigated and interpreted. The experimental results showed that the reaction rate in the microemulsion with IL was enhanced and it was faster than that in pure isooctane and in generic AOT microemulsion. The effect of the IL on the apparent second rate constant (k₂) was explained. The effect of temperature on the reaction rate was studied, and values of apparent activation energy were estimated in various microemulsion with IL. Copyright © 2012 John Wiley & Sons, Ltd.     

Percolation of polyatomic species on a square lattice

In this paper, the percolation of (a) linear segments of size k and(b) k-mers of different structures and forms deposited on a square lattice have been studied. In the latter case, site and bond percolation have been examined. The analysis of results obtained by using finite size scaling theory is performed in order to test the universality of the problem by determining the numerical values of the critical exponents of the phase transition occurring in the system. It is also determined that the percolation threshold exhibits a exponentially decreasing function when it is plotted as a function of the k-mer size. The characteristic parameters of that function are dependent not only on the form and structure of the k-mers but also on the properties of the lattice where they are deposited.Received: 3 September 2003, Published online: 23 December 2003PACS: 64.60.Ak Renormalization-group, fractal, and percolation studies of phase transitions - 68.35.Rh Phase transitions and critical phenomena - 68.35.Fx Diffusion; interface formation     

Investigation of W/O microemulsion droplets by contrast variation light scattering

Dynamic and static light scattering experiments have been performed at various molar ratios (γ) of water to AOT and temperatures on water-in-oil (W/O) microemulsions dispersed in n-heptane, n-octane, and n-nonane. Size and shape fluctuations of microemulsion droplets are determined with very high precision because polydispersity influences the characteristic features of scattering data as well as the hydrodynamic radius withγ. Self-consistent interpretation of dynamic and static light scattering data using optical properties and packing consideration on the basis of the layered sphere model are obtained. The estimated extent of polydispersity index of 17% is found, whereas the polydispersity is independent of the alkane types. The geometrical parameters, e.g., hydrodynamic radius, area per head group of the surfactant molecule and thickness of the surfactant layer of microemulsion droplets are also estimated and compared in three different n-alkane types. The best interpretation of the temperature dependence of data has shown a transition from spherical droplets to ellipsoid aggregates with increasing temperature. Axial ratio increases with increase of temperature and the longer the alkane the larger is the axial ratio. The parameters describing the polydispersity and shape change are in agreement with theoretical and experimental results found in the literature     

Wide-range cooling characteristics of a selected isotactic polypropylene

An increased knowledge of polymer crystallization kinetics and its effect on the crystalline structure is of particular importance at high cooling rates. The aims of this study were to explore the range of utility and complementarity of various methods (densitometry, microscopy, wide-angle x-ray diffraction [WAXD], and small-angle light scattering [SALS]) on the characterization of the crystalline structure of a high purity isotactic polypropylene (PP) in a wider cooling range than previously obtainable and to identify characteristic ranges of the structure as a function of cooling rate. High cooling rates, ranging to nearly 1000°C/sec, were obtained using a special quench device. The transition between truncated and isolated spherulites at 10°C/sec and the transition range between a pronounced α-monoclinic and a mainly mesomorphic phase were identified. The sizes of spherulites (ranging from partly truncated spherulites to a mesomorphic phase with no spherulites) were characterized by polarized optical microscopy and SALS. The influence of experimental conditions, such as beam diameter and sample thickness, on the SALS pattern was also investigated.     

A small angle neutron scattering study on the mixtures of pluronic L121 and anionic surfactant AOT

Small angle neutron scattering (SANS) experiments have been carried out on the micellar solutions containing mixtures of a hydrophobic triblock copolymer (L121, EO₅PO₆₈EO₅) and a hydrophobic anionic surfactant (AOT, sodium bis(2-ethylhexyl)sulphosuccinate) in water with varying ratio (R) of AOT to L121 for R = 0.15, 0.2, 0.3, 0.5 and 0.6. It is known that either L121 or AOT alone forms vesicles in water, but in the mixture with appropriate ratio of the two components a thermodynamically stable, isotropic solution of apparently small micelle-like aggregates is formed. We find that these micelles are prolate ellipsoidal.      

Percolation on Interdependent Networks with a Fraction of Antagonistic Interactions

Recently, the percolation transition has been characterized on interacting networks both in presence of interdependent interactions and in presence of antagonistic interactions. Here we characterize the phase diagram of the percolation transition in two Poisson interdependent networks with a percentage q of antagonistic nodes. We show that this system can present a bistability of the steady state solutions, and both discontinuous and continuous phase transitions. In particular, we observe a bistability of the solutions in some regions of the phase space also for a small fraction of antagonistic interactions 0<q<0.4. Moreover, we show that a fraction q>q _c =2/3 of antagonistic interactions is necessary to strongly reduce the region in phase-space in which both networks are percolating. This last result suggests that interdependent networks are robust to the presence of antagonistic interactions. Our approach can be extended to multiple networks, and to complex boolean rules for regulating the percolation phase transition.