Surface and aggregation properties of a plant-oil derived biosurfactant.

The plant-oil derived biosurfactant HeBra® shows a high surface activity combined with a versatile aggregation behavior. The hydrophilic protein head groups provide an excellent water solubility that still enables micelle formation due to the hydrophobic interactions of the fatty acid chains. The observed low CMC of 1 g L-1 allows an efficient utilization in different application fields already at very low concentrations. The mixture of low and high molecular weight components provides highly dynamic behavior during foam formation or dispersion processes combined with the formation of large and stable structures in solutions and at surfaces.

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo.

The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence on the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.

Interactions of silica nanoparticles with poly(ethylene oxide) and poly(acrylic acid): effect of the polymer molecular weight and of the surface charge.

The properties and the structure of polymer-modified silica nanoparticles were investigated by several characterization methods, with an emphasis on scattering techniques. Both bare and amino functionalized nanoparticles were used. To determine the effect of the charge, the polymer used was either nonionic poly(ethylene oxide) (PEO) or partially deprotonated poly(acrylic acid) (PAA). The particles coated with PEO were investigated by small-angle neutron scattering using the method of external contrast variation to observe the polymer coverage. The quantity adsorbed was found to be increasing with the molecular weight, and the surface type, bare or aminated, did not have a significant influence on the quantity adsorbed. The adsorption of PAA on positively charged aminated particles was investigated by dynamic light scattering and zeta potential measurements. A charge reversal, from positive to negative, was induced by the presence of PAA. Through the derivation of the structure factor, small-angle X-ray scattering provided significant information on the formation of aggregates at low PAA concentrations.

Structure and dynamics of nanoemulsions: insights from combining dynamic and static neutron scattering.

Despite their lack of thermodynamical stability, nanoemulsions can show a remarkable degree of kinetic stability. Among the various different preparation methods the phase-inversion concentration method is particularly interesting as it occurs spontaneously. Here we investigate such a system composed of a surfactant, cosurfactant, and oil that upon dilution with water forms long time metastable oil-in-water nanoemulsion droplets. The dynamics of the amphiphilic monolayers and its elastic properties is important for their stability and therefore the monolayer dynamics have been investigated by neutron spin echo (NSE). Despite the difficulties arising from the inherently polydisperse nature and the large number of different components necessarily contained in commercial nanoemulsion formulations, information concerning the membrane rigidity was extracted from the combination of small angle neutron scattering and NSE and several different formulations are compared. These results show that small amounts of different admixed ionic surfactants can modify the monolayer rigidity substantially and similarly effects of surface bound polyelectrolytes have been evaluated.

Solubilisation of different medium chain esters in zwitterionic surfactant solutions--effects on phase behaviour and structure.

We studied the effect of solubilisation of methyl esters with different chains of medium length into the binary surfactant system tetradecyldimethylamine oxide/water at constant surfactant concentration of 200 mM. As esters we employed valeric, capronic, enanthic, and pelargonic methyl ester, thereby decreasing the polarity. Always a phase sequence L(1)-L(α)-L(1) is observed with increasing ester concentration, where the L(α)-phase increases in extent and goes to much lower temperatures with increasing chain length of the ester. Viscosity measurements show a maximum at intermediate concentrations of additive that is independent of the type of ester. From SANS measurements detailed information about the structural changes occurring during the rod-to-sphere transition in the system of the shortest additive is deduced, which proceeds first through a pronounced rod growth. Interestingly, for the different esters an almost constant value of the volumic solubilisation capacity is observed, in agreement with the relatively constant interfacial tension. For the different esters no effect on the radius and the area requirement at the amphiphilic interface is observed at the solubilisation boundary. The microemulsions present here are spherical aggregates where the ester is partitioned between core and shell. From the SANS and interfacial tension data the effective bending constants of the surfactant monolayers were deduced and they show that the extension of the L(α)-phase is directly related to a corresponding increase in the bending constants of the surfactant/ester monolayers.

Effects of electrolyte concentration and counterion valence on the microstructural flow regimes in dilute cetyltrimethylammonium tosylate micellar solutions.

The shear thickening behavior and the transition to shear thinning are examined in dilute cetyltrimethylammonium tosylate (CTAT) micellar solutions as a function of surfactant concentration and ionic strength using electrolytes with different counterion valence. Newtonian behavior at low shear rates, followed by shear thickening and shear thinning at higher shear rates, are observed at low and intermediate surfactant and electrolyte concentrations. Shear thickening diminishes with increasing surfactant concentration and ionic strength. At higher surfactant or electrolyte concentration, only a Newtonian region followed by shear thinning is detected. A generalized flow diagram indicates two controlling regimes: one in which electrostatic screening dominates and induces micellar growth, and another, at higher electrolyte and surfactant concentrations, where chemical equilibrium among electrolyte and surfactant counterions controls the rheological behavior by modifying micellar breaking and reforming. Analysis of the shear thickening behavior reveals that not only a critical shear rate is required for shear thickening, but also a critical deformation, which appears to be unique for all systems examined, within experimental error. Moreover, a superposition of the critical shear rate for shear thickening with surfactant and electrolyte concentration is reported.

Aqueous laponite clay dispersions in the presence of poly(ethylene oxide) or poly(propylene oxide) oligomers and their triblock copolymers.

The effect of polyethylene oxide (PEO) or polypropylene oxide (PPO) oligomers of various molecular weight (Mw) as well as of triblock copolymers, based on PEO and PPO blocks, on aqueous laponite RD suspensions was studied with small-angle neutron scattering (SANS). The radius of gyration (RG) increases for low M w whereas the opposite occurs for larger Mw. This behavior is explained on the basis that an effective R G is given by two contributions: (1) the size of the particles coated with the polymer and (2) the interactions between the laponite RD particles which are attractive for small and repulsive for large polymers. The SANS curves in the whole Q-range are well described by a model of noninteracting polydisperse core+shell disks, where the thickness of the polymer layer increases with the Mw. The adsorbed polymer is in a more compact conformation compared to a random coil distribution while the fraction of the polymer in the shell formed around the laponite RD particles is nearly independent of Mw. For increasing laponite RD amounts, at a given polymer composition, the thickness of the polymer slightly changes. In some cases, where also gelation is sped up, a structure factor with attractive interaction was employed which allowed to evaluate the attractive forces between the laponite RD particles. The gelation time was determined for mixtures at fixed copolymer and laponite RD concentrations. Surprisingly, it is observed that gels are formed despite the fact that the binding sites of the laponite RD particles are almost covered but the polymer size is too small to prevent aggregation. The gelation rate is correlated to structure and thermodynamics of these systems. Namely, when the balance between the steric forces and the depletion attractive forces undergoes an abrupt change the gelation time also undergoes a sharp variation. For lower and comparable Mw, PPO speeds up the gelation more efficiently than PEO while for higher Mw the gelation kinetics is slowed down again. Interestingly, copolymers of PEO and PPO blocks do not induce gelation in the time-window where the homopolymers do.

Aqueous block copolymer-surfactant mixtures and their ability in solubilizing chlorinated organic compounds. A thermodynamic and SANS study.

Within the topic of surfactant enhanced solubilization of additives sparingly soluble in water, volumetric, solubility, conductivity, and small-angle neutron scattering (SANS) experiments on mixtures composed of alpha,omega-dichloroalkane, surfactant, copolymer, and water were carried out at 298 K. The triblock copolymers (ethylene oxide)132(propylene oxide)50(ethylene oxide)132 (F108) and (ethylene oxide)76(propylene oxide)29(ethylene oxide)76 (F68) were chosen to investigate the role of the molecular weight keeping constant the hydrophilic/hydrophobic ratio. The selected surfactants are sodium decanoate (NaDec) and decyltrimethylammonium bromide (DeTAB) with comparable hydrophobicity and different charged heads. The alpha,omega-dichloroalkanes were chosen as contaminant prototypes. For the water + surfactant + copolymer mixtures, both the volume and the SANS results straightforwardly evidenced that (1) monomers of NaDec and copolymer unimers generate small mixed aggregates, (2) monomers of DeTAB combined with copolymer unimers do not form aggregates, and (3) unimeric copolymer is solubilized into NaDec and DeTAB micelles. The alpha,omeaga-dichloroalkanes presence induces the F108 aggregation even at very low copolymer composition. The addition of surfactant disintegrates the F108 aggregates and, consequently, the additive is expelled into the aqueous phase. Once F108 is in the unimeric state, it forms copolymer-micelle aggregates which incorporate the oil. In the case of F68 both the volumetric and the SANS data reveal that the additive does not alter the copolymer unimeric state. Moreover, they show that for the aqueous DeTAB-F68 system the additive trapping in both the copolymer-micelle aggregate and the pure micelles takes place being enhanced in the former aggregate in agreement with solubility experiments. For the NaDec-F68 mixtures, an additional solubilization process in the premicellar copolymer-surfactant microstructures occurs. SANS and conductivity data show that the additive incorporation into the mixed and the pure micelles does not essentially influence the structural properties of the aggregates.

The solubilisation behaviour of some dichloroalkanes in aqueous solutions of PEO-PPO-PEO triblock copolymers: a dynamic light scattering, fluorescence spectroscopy, and SANS study.

The aggregation behaviour of PEO-PPO-PEO triblock copolymers in water and in water + chlorinated additive mixtures was studied by means of fluorescence spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). The copolymers were chosen such as to investigate the effects of molecular architecture (L35 and 10R5) and molecular weight by keeping constant the hydrophilic/hydrophobic balance (F88 and F108). 1,2-Dichloroethane was used as a prototype of water basins contaminants. The hydrodynamic radius of the block copolymer aggregates (R(h,M)) and the intensity ratio of pyrene of the first and the third vibrational band (I(1)/I(3)) were determined as a function of temperature (10-45 degrees C) and concentration. The copolymer architecture essentially does not affect R(h,M) in the entire range of temperature and concentration investigated. At a given temperature, increasing macromolecular size leads to a decrease of R(h,M). With rising temperature R(h,M) also decreases. According to the DLS results, the I(1)/I(3) change with temperature clearly detects the aggregation only for F88 and F108. The presence of 1,2-dichloroethane, at concentrations close to its solubility in water, does not lead to changes in the distribution of hydrodynamic radii for L35 and 10R5. Larger quantities of additive induce the formation of quite polydisperse mixed aggregates for L35 and of networks for 10R5. In the case of F88 and F108, low concentrations of additive lead to formation of mixed aggregates with smaller R(h,M). The SANS results corroborate the DLS and fluorescence findings proving enhancement of the copolymer aggregation through the presence of 1,2-dichloroethane. The DLS findings combined with those from the fluorescence spectroscopy provide some insight into the site of solubilisation of the additive in the aggregates.

A novel viscoelastic system from a cationic surfactant and a hydrophobic counterion.

The phase behavior of 2-hydroxy-1-naphthoic acid (2,1-HNC) mixed with cetyltrimethylammonium hydroxide (CTAOH) is reported. This novel system is compared with the published one of 3-hydroxy-2-naphthoic acid (3,2-HNC) mixed with CTAOH. We investigated the phase behavior and properties of the phases in aqueous solutions of 100 mM CTAOH with 2,1-HNC. In both systems a multilamellar vesicle phase is formed when the naphthoate/surfactant ratio (r) reaches unity. When an increasing amount of 2,1-HNC is mixed with a micellar solution of 100 mM CTAOH, an isotropic low-viscous micellar solution, a viscoelastic gel (consisting of rodlike micelles), a turbid region (two-phase region), and a viscoelastic liquid crystalline gel (consisting of multilamellar vesicles, MLV) were formed. The vesicular phase is highly viscoelastic and has a yield stress value. The transition from the micellar to the vesicle phase occurs for CTAOH/2,1-HNC over a two-phase region, where micelles and vesicles coexist. Also it was noticed that 2,1-HNC is dissolved in 100 mM CTAOH until the naphthoate/surfactant ratio reaches approximately 1.5, and the liquid crystalline phases were found to change their color systematically when they were viewed between two crossed polarizers. The vesicles have been characterized by differential interference contrast microscopy, freeze-fracture electron microscopy, and cryo-electron microscopy (cryo-TEM). The vesicles were polydisperse and their diameter ranged from 100 to 1000 nm. The interlamellar spacing between the bilayers was determined with small angle neutron scattering and agrees with the results from different microscopical methods. The complex viscosity rises by six orders of magnitude when rodlike micelles are formed. The complex viscosity decreases again in the turbid region, and then rises approximately six orders of magnitude above the water viscosity. This second rising is due to the formation of the liquid crystalline MLV phase.

Dynamics of the self-assembly of unilamellar vesicles.

We have studied the transient stages in the formation of unilamellar vesicles with millisecond time resolution. The self-assembly was initiated by rapid mixing of equimolar amounts of anionic and zwitterionic micelles and the transient micellar entities were probed by time-resolved small-angle x-ray scattering. Within the mixing time, original micelles transformed to disklike micelles which evolved further to a critical size and then closed to form monodisperse unilamellar vesicles within a second. Subsequent growth led to an unexpected broadening of the vesicle size distribution.

Millisecond-range time-resolved small-angle x-ray scattering studies of micellar transformations.

The transformation of mixtures of cationic and anionic micelles to vesicles has been studied by time-resolved small-angle x-ray scattering (SAXS). Equimolar amounts of ionic surfactant solutions, the anionic TexaponN70-H and the cationic TTAOH, were mixed by a stopped-flow device. Time-resolved SAXS patterns reveal that within the mixing time (<10 ms) mixed micelles are formed. These globular micelles dissolve within about 400-1000 ms and form monodisperse unilamellar vesicles in a much slower process of 5-100 s duration.

Structural Changes Induced in the Surfactant System C(12)E(4)/Benzyl Alcohol/Water by the Admixture of the Cationic Surfactant Cetylpyridinium Chloride.

The influence of the addition of the cationic surfactant cetylpyridinium chloride (CPyCl) on the structure of the different phases of the ternary surfactant system C(12)E(4)/benzyl alcohol/water in the dilute region has been studied by means of small angle neutron scattering (SANS) and freeze-fracture microscopy (FF-TEM). In the ternary system various different subregions of the L(alpha)-phase were identified as a function of the concentration of the cosurfactant, benzyl alcohol. Addition of small amounts of CPyCl suppresses these different L(alpha)-phases in favor of the one composed of multilamellar vesicles. Addition of somewhat larger amounts (up to 2 mol% relative to the total surfactant concentration) destabilizes the formation of bilayer structures completely and leads to the formation of micellar solutions. This demonstrates that in this surfactant system the incorporation of very small amounts of cationic surfactant has a pronounced and systematic fluence on its phase behavior and its structures. Copyright 2001 Academic Press.

Phase Behavior, Structure, and Physical Properties of the Quaternary System Tetradecyldimethylamine Oxide, HCl, 1-Hexanol, and Water.

The phase diagram of the ternary surfactant system tetradecyldimethylamine oxide (TDMAO)/HCl/1-hexanol/water shows with increasing cosurfactant concentration an L(1) phase, two L(alpha) phases (a vesicle phase L(alpha1) and a stacked bilayer phase L(alphah)), and an L(3) phase, which are separated by the corresponding two-phase regions L(1)/L(alpha) and L(alpha)/L(3). In this investigation, the system was studied where some of the TDMAO was substituted by the protonated TDMAO. Under these conditions, one finds for constant surfactant concentration of 100 mM TDMAO a micellar L(1) phase, an L(alpha1) phase (consisting of multilamellar vesicles), and an interesting isotropic L(1)(*) phase in the middle of the L(1)/L(alpha) two-phase region. The L(1)(*) phase exists at intermediate degrees of charging of 30-60% and for 40-120 mM TDMAO and 70-140 mM hexanol concentration. At surfactant concentrations less than 80 mM the L(1)(*)-phase borders directly on the L(1) phase. The phase transition between the L(1) phase and the L(1)(*) phase was detected by electric conductivity and rheological measurements. The conductivity values show a sharp drop at the L(1)/L(1)(*) transition, and the zero shear viscosity of the L(1)(*) phase is much lower than in L(1) phase. The form and size of the aggregates in L(1)(*) were detected with FF-TEM and SANS. This phase contains small unilamellar vesicles (SUV) of about 10 nm and some large multilamellar vesicles with diameters up to 500 nm. The system exhibits another peculiarity. For 100 mM surfactant, the clear L(alpha1)-phase exists only at chargings below 30%. With oscillating rheological measurements a parallel development of the storage modulus G' and the loss modulus G" was observed. Both moduli are frequency independent and the system possesses a yield stress. The storage modulus is a magnitude larger than the loss modulus. Copyright 2000 Academic Press.

Structural Changes in the Isotropic Phase of the Ternary Surfactant System: Tetradecyldimethylamine Oxide/Benzyl Alcohol/Water.

The surfactant system tetradecyldimethylamine oxide (TDMAO)/benzyl alcohol/water has been studied. In the phase diagram of this ternary system a large isotropic region is encountered that connects the water corner to the benzyl alcohol corner. This isotropic phase has been investigated in some detail by means of electric conductivity, viscosity, electric birefringence, and small-angle neutron scattering (SANS) measurements. From these experiments it can be concluded that for roughly equal amounts of alcohol and water a bicontinuous structure is present, similar to that typically observed for bicontinuous microemulsions. The structural units present become continuously smaller with increasing alcohol content, and at very high alcohol content only small reverse aggregates are present. The formation of this bicontinuous phase can be understood by the fact that the presence of the benzyl alcohol reduces the stiffness of the surfactant film, and therefore such a "sponge"-type structure is favored. With increasing surfactant concentration the amphiphilic film becomes stiffer again, which leads to the formation of a lamellar phase. The corresponding phase boundary is exactly related to the amphiphilicity factor as it can be deduced from the scattering experiments. Copyright 1998 Academic Press.