A model for the limiting surface tension of surfactant solutions (surface tension at and above the critical micelle concentration, cmc) was developed. This model takes advantage of the equilibrium between the surfactant molecules on the liquid/vacuum surface and in micelles in the bulk at the cmc. An approximate analytical equation for the surface tension at the cmc was obtained. The derived equation contains two parameters, which characterize the intermolecular interactions in the micelles, and the third parameter, which is the surface area per surfactant molecule at the interface. These parameters were calculated using a new atomistic modeling approach. The performed calculations of the limiting surface tension for four simple surfactants show good agreement with experimental data (~30% accuracy). The developed model provides the guidance for design of surfactants with low surface tension values.
Micelle formation in binary mixtures of surfactants is studied using a coarse-grained molecular simulation. When a vesicle composed of lipid and detergent types of molecules is ruptured, a disk-shaped micelle, the bicelle, is typically formed. It is found that cup-shaped vesicles and bicelles connected with worm-like micelles are also formed depending on the surfactant ratio and critical micelle concentration. The obtained octopus shape of micelles agree with those observed in the cryo-TEM images reported in [S. Jain and F. S. Bates, Macromol. 37, 1511 (2004).]. Two types of connection structu…
We investigate the morphology and energetics of a self-associating model cationic surfactant in water using coarse-grained molecular dynamics simulations. We develop an algorithm to track micelles contours and quantify various microstructural features, such as contour length, persistence length, mesh size, and entanglement-length. We demonstrate that branched and multiconnected structures govern the anomalous dependence of zero-shear viscosity on salt concentration. We predict reliably the end-cap energy of micelles, for the first time, from simulations.
Following up a recent paper on grafted sliding polymer layers (Macromolecules 2005, 38, 1434-1441), we investigated the influence of the sliding degree of freedom on the self-assembly of sliding polymeric surfactants that can be obtained by complexation of polymers with cyclodextrins. In contrast to the micelles of quenched block copolymer surfactants, the free energy of micelles of sliding surfactants can have two minima: the first corresponding to small micelles with symmetric arm lengths, and the second corresponding to large micelles with asymmetric arm lengths. The relative sizes and conc…
Flow-induced configuration dynamics and scission of rodlike micelles are studied for the first time using molecular dynamics simulations in presence of explicit solvent and salt. Predicted dependence of tumbling frequency and orientation distribution on shear rate S agrees with mesoscopic theories. However, micelle stretching increases the distance between the cationic head groups and adsorbed counter ions, which reduces electrostatic screening and increases the overall energy Phi linearly with micelle length. Micelle scission occurs when Phi exceeds a threshold value, independent of S.
Hypotheses: The aggregation number and length of spherocylindrical (rodlike, wormlike) micelles in solutions of an ionic surfactant and salt can be predicted knowing the molecular parameters and the input concentrations of the species. This can be achieved by upgrading the quantitative molecular thermodynamic model from the previous parts of this series with an expression for the electrostatic component of micelle scission energy that is the excess free energy of the spherical endcaps with respect to the cylindrical part of the micelle. Theory: The thermodynamics of micellization is extended t…
We present the first molecular dynamics study to probe the mechanisms of anomalous diffusion in cationic surfactant micelles in the presence of explicit salt and solvent-mediated interactions. Simulations show that when the counter ion density increases, saddle-shaped interfaces manifest leading to the formation of branched structures. In experiments, branched structures exhibit lower viscosity as compared to linear and wormlike micelles, presumably due to stress relaxation arising from the sliding motion of branches along the main chain. Our simulations provide conclusive evidence and a mecha…
Surfactants are amphiphilic molecules that spontaneously self-assemble in aqueous solution into various ordered and disordered phases. Under certain conditions, one-dimensional structures in the form of long, flexible wormlike micelles can develop. Cetyltrimethylammonium bromide (CTAB) is one of the most widely studied surfactants, and in the presence of sodium salicylate (NaSal), wormlike micelles can form at very dilute concentrations of surfactant. We carry out a systematic study of the microscopic structures of CTAB/NaSal over a surfactant concentration range of 2.5 - 15 mM and at salt-to-…
In this review, we report recent developments on the shear-induced transitions and instabilities found in surfactant wormlike micelles. The survey focuses on the non-linear shear rheology and covers a broad range of surfactant concentrations, from the dilute to the liquid-crystalline states and including the semi-dilute and concentrated regimes. Based on a systematic analysis of many surfactant systems, the present approach aims to identify the essential features of the transitions. It is suggested that these features define classes of behaviors. The review describes three types of transitions…
Normal micelle aggregates of amphiphilic surfactant in aqueous solvent are formed by a process of entropically driven self-assembly. The self-assembly of reverse micelles from amphiphilic surfactant in non-polar solvent in the presence of water is considered to be an enthalpically driven process. While the formation of normal and reverse surfactant micelles has been well characterized in theory and experiment, the nature of dry micelle formation, from amphiphilic surfactant in non-polar solvent in the absence of water, is poorly understood. In this study, a theory of dry reverse micelle format…
The self assembly of linear surfactants into reverse micelles (RMs) in nonpolar solvents and their efficiency in reducing the interfacial tension is studied using dissipative particle dynamics simulations. Given the importance of RMs as thickeners, among many other applications, their properties are studied here when formed in oil and in supercritical carbon dioxide (scCO2). Our simulations are found to be in agreement with experimental results of surfactant self assembly in scCO2 that found viscosity increments of up to 90 percent with 10 wt percent of surfactants. The role played by a small …
The eigenvalues and eigenvectors of the matrix of coefficients of the linearized kinetic equations applied to aggregation in surfactant solution determine the full spectrum of characteristic times and specific modes of micellar relaxation. The dependence of these relaxation times and modes on the total surfactant concentration has been analyzed for concentrations in the vicinity and well above the second critical micelle concentration (cmc2) for systems with coexisting spherical and cylindrical micelles. The analysis has been done on the basis of a discrete form of the Becker-Doering kinetic e…
Hypothesis: New dynamic phenomena can be observed in evaporating free liquid films from colloidal solutions with bimodal particle size distribution. Such distributions are formed in a natural way in mixed (slightly turbid) solutions of cationic and anionic surfactants, where nanosized micelles coexist with micronsized precipitated particles. Experiment: Without evaporation of water, the films thin down to thickness < 100 nm. Upon water evaporation from the film, one observes spontaneous film thickening (above 300 nm) and appearance of a dynamic vortex with a spot of thinner film in the center.…
We investigate the effects of gemini surfactants, telechelic chain and lipids on the nature of micelles formed by conventional single-tail surfactants in water by carrying out Monte Carlo simulations. In a mixture of gemini and single-tail surfactants in water we find direct evidence of micelles of predominantly single-tail surfactants some of which are dynamically cross-linked by gemini surfactants when the concentrations of the geminis is only a few mole percent and their spacers are {\it hydrophilic}. In contrast, mixtures of lipids and single-tail surfactants in water form only isolated mi…
Hypotheses: To correctly predict the aggregation number and size of wormlike micelles from ionic surfactants, the molecular-thermodynamic theory has to calculate the free energy per molecule in the micelle with accuracy better than 0.01 kT, which is a serious challenge. The problem could be solved if the effects of mutual confinement of micelle counterion atmospheres, as well as the effects of counterion binding, surface curvature and ionic interactions in the electric double layer (EDL), are accurately described. Theory: The electric field is calculated using an appropriate cell model, which …
The kinetics of non-ionic surfactant adsorption at a fluid-fluid interface from a micellar solution is considered theoretically. Our model takes into account the effect of micelle relaxation on the diffusion of the free surfactant molecules. It is shown that non-ionic surfactants undergo either a diffusion or a kinetically limited adsorption according to the characteristic relaxation time of the micelles. This gives a new interpretation for the observed dynamical surface tension of micellar solutions.
The tendency of amphiphilic molecules to form micelles in aqueous solution is a consequence of the hydrophobic effect. The fundamental difference between micelle assembly and macroscopic phase separation is the stoichiometric constraint that frustrates the demixing of polar and hydrophobic groups. We present a theory for micelle assembly that combines the account of this constraint with a description of the hydrophobic driving force. The latter arises from the length scale dependence of aqueous solvation. The theoretical predictions for temperature dependence and surfactant chain length depend…
Diffusion studies using nuclear magnetic resonance (NMR) spectroscopy were conducted on two model surfactant solutions of cetyltrimethylammonium bromide/sodium salicylate (CTAB/NaSal) and cetylpyridinium chloride/sodium salicylate (CPCl/NaSal). By increasing the salt-to-surfactant concentration ratio, these systems display two peaks in the zero-shear viscosity and relaxation time, which are indicative of transitions from linear to branched micellar networks. The goal of this work is to assess the sensitivity of NMR diffusometry to different types of micellar microstructures and identify the me…
Complex fluids such as emulsions, colloidal gels, polymer or surfactant solutions are all characterized by the existence of a "microstructure" which may couple to an external flow on timescales that are easily probed in experiments. Such a coupling between flow and microstructure usually leads to instabilities under relatively weak shear flows that correspond to vanishingly small Reynolds numbers. Wormlike micellar surfactant solutions appear as model systems to study two examples of such instabilities, namely shear banding and elastic instabilities. Focusing on a semidilute sample we show tha…
Metallic ion adsorption on surfactant aggregates were studied with Molecular dynamics simulations. Using ionic salts, such as lead sulfate (PbSO$_4$) and aluminum sulfate [Al$_2$(SO$_4$)$_3$], adsorption of lead and aluminum were investigated at different salt concentrations and different surfactant aggregates (micelles) sizes. The micelles were constructed with spherical shapes composed of sodium dodecyl sulfate (SDS) anionic surfactants. The electrostatic interactions between the positive ions and the negative SDS headgroups promote capture of the metal particles on the aggregate surface. Me…
Amphiphilic block copolymer solutions form various micellar structures including micelles and vesicles. We applied the density functional theory for block copolymers which we have proposed to amphiphilic block copolymer systems. The 3 dimensional simulation for AB diblock copolymer solutions and AB diblock copolymer / A homopolymer blends has been done and it is shown that the spherical micelles, cylindrical micelles and spherical vesicles are formed. It is also shown that the phase diagram for AB diblock copolymer / A homopolymer blends qualitatively agrees with the phase diagram obtained by …
The behavior of confined cylindrical micelle-forming surfactants under the influence of shear has been investigated using Monte Carlo simulations. The surfactants are modeled as coarse-grained lattice polymers, while the Monte Carlo shear flow is implemented with an externally imposed potential energy field which induces a linear drag velocity on the surfactants. It is shown that in the absence of shear, cylindrical micelles confined within a monolayer coarsen gradually with Monte Carlo "time" t, the persistence length of the micelles scaling as t^{0.24}, in agreement with the scaling obtained…
The relative importance of micelle solubilization and Krafft temperature on the appraisal of the flocculation rate is studied using a dodecane-in-water nanoemulsion as a model system. In 0.5 mM solutions of sodium dodecylsulfate (SDS), neither the critical micelle concentration (CMC) nor the Krafft point of the surfactant are attained between 300 and 700 mM NaCl and 20 < T < 25 °C. Hence, the addition of salt to a SDS-stabilized nanoemulsion only induces aggregation. Conversely, a surfactant concentration of 7.5 mM SDS promotes micelle solubilization or crystal precipitation depending on the p…
Hypotheses: A quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles of nonionic surfactants can be developed on the basis of a generalized model, which includes the classical 'phase separation' and 'mass action' models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: By analytical minimization of the free-energy functional we derived explicit expressions for the chain-extension and chain-end distribution functions in the hydrocarbon core of mixed micelles from t…
Hypotheses: Quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles in mixed nonionic surfactant solutions can be developed on the basis of a generalized model, which includes the classical phase separation and mass action models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: The model is based on explicit analytical expressions for the four components of the free energy of mixed nonionic micelles: interfacial-tension, headgroup-steric, chain-conformation compon…
We develop a theoretical model for the solubilization of phospholipid bilayers by micelle-forming surfactants. Cylindrical micelles, disc-like micelles and spherical micelles are considered as alternative resultant structures. The main question addressed is what kind of micelles can be expected under various thermodynamical conditions. Our analysis is based on a theoretical model that accounts for Helfrich energy of curvature of amphiphile monolayers and for the entropy of mixing of lipids and surfactants in mixed aggregates. We conclude that for usual values of the elastic parameters of amphi…
The surface aggregates structure of dimethyldodecylamine-N-oxide (C12DAO) in three silica dispersions of different particle sizes (16 - 42 nm) was studied by small-angle neutron scattering (SANS) in a H2O/D2O solvent mixture matching the silica. At the experimental conditions (pH 9) the surfactant exists in its nonionic form and the structure of the adsorbed layer is not affected by added electrolyte. It is found that C12DAO forms spherical surface micelles of 2 nm diameter on the 16 nm silica particles, but oblate ellipsoidal surface micelles are formed on the 27 and 42 nm particles. The dime…
The industrial implementation of biofuel production from lignocellulosic biomass faces a number of economic obstacles. One of these is the cost of enzymes, typically used for cellulose hydrolysis. Nature provides some hints towards the efficiency of this process, exampled in natural enzyme complexes - cellulosomes, produced by some microorganisms. Therefore, many research groups target synthetic routes to mimic such cellulosomes with synthetic structures when many questions remain to be addressed: the optimal chemical structure and size of such synthetic scaffolds, their adsorption on the cell…
Using the notion of aggregation work, we construct a system of differential equations for the aggregation number of micelles which is a function of the parameters of micellization (parametric equations). There are explicit solutions for two important models of spherical micelles. Based on these solutions, we obtain an analytical expression for the equilibrium concentration of surfactant monomers and consequently for the whole spectrum of equilibrium concentrations of molecular aggregates in this framework. Accuracy of these expressions is discussed, and they are applied on an example of micell…
We present a new theoretical approach to the kinetics of micelle formation in surfactant solutions, in which the various stages of aggregation are treated as constrained paths on a single free-energy landscape. Three stages of well-separated time scales are distinguished. The first and longest stage involves homogeneous nucleation of micelles, for which we derive the size of the critical nuclei, their concentration, and the nucleation rate. Subsequently, a much faster growth stage takes place, which is found to be diffusion-limited for surfactant concentrations slightly above the critical mice…
The formation of self assembled structures such as micelles has been intensively studied and is well understood. The ability of a solution of amphiphilic molecules to develop micelles is depending on the concentration and characterized by the critical micelle concentration (cmc), above which micelle formation does occur. Recent studies use a lattice approach in order to determine cmc and show that the correct modelling and analysis of cluster formations is highly non-trivial. We developed a minimalistic coarse grained model for amphiphilic molecules in the continuum and simulated the time evol…
The complexation between charged-neutral block copolymers and oppositely charged surfactants was investigated by light scattering experiments and by isothermal titration calorimetry (ITC). The copolymer was poly(sodium acrylate)-b-poly(acrylamide) and the surfactant dodecyltrimethylammonium bromide (DTAB). In a previous report, we had shown that the copolymers and the surfactants co-assembled spontaneously into colloidal complexes. Depending of the charge ratio Z = [DTA+]/[COO-], the complexes were either single surfactant micelles decorated by copolymers, or core-shell hierarchical structures…
Many ionic surfactants with wide applications in personal-care and house-hold detergency show limited water solubility at lower temperatures (Krafft point). This drawback can be overcome by using mixed solutions, where the ionic surfactant is incorporated in mixed micelles with another surfactant, which is soluble at lower temperatures. The solubility and electrolytic conductivity for a binary surfactant mixture of anionic methyl ester sulfonates (MES) with nonionic alkyl polyglucoside and alkyl polyoxyethylene ether at 5 deg C during long-term storage were measured. Phase diagrams were establ…
Molecular dynamics simulations to study the behaviour of anionic (Sodium Dodecylsulfate, SDS) and nonionic (Monooleate of Sorbitan, SPAN80) surfactants close to a SiO$_{2}$ (silicon dioxide) surface were carried out. Simulations showed that a water layer was first adsorbed on the surface and then the surfactants were attached on that layer. Moreover, it was observed that water behaviour close to the surface influenced the surfactant adsorption since a semi-spherical micelle was formed on the SiO$_{2}$ surface with SDS molecules whereas a cylindrical micelle was formed with SPAN80 molecules. Ad…
The self-assembly of two nonionic surfactants, pentaethylene glycol monododecyl ether (C12E5) and n-dodecyl-ß-maltoside (ß-C12G2), in the presence of a purpose-synthesized silica sol of uniform particle size (diameter 16 nm) has been studied by adsorption measurements, dynamic light scattering and small-angle neutron scattering (SANS) using a H2O/D2O mixture matching the silica, in order to highlight the structure of the surfactant aggregates. For C12E5 strong aggregative adsorption onto the silica beads, with a high plateau value of the adsorption isotherm above the CMC was found. SANS measur…
Several surfactant molecules self-assemble in solution to form long, cylindrical, flexible wormlike micelles. These micelles can be entangled with each other leading to viscoelastic phases. The rheological properties of such phases are very interesting and have been the subject of a large number of experimental and theoretical studies in recent years. We shall report on our recent work on the macrorheology, microrheology and nonlinear flow behaviour of dilute aqueous solutions of a surfactant CTAT (Cetyltrimethylammonium Tosilate). This system forms elongated micelles and exhibits strong visco…
We investigate the effect of surface waves generated by the Faraday instability on a shear-thickening surfactant solution under vertical vibrations. We show that a prolonged oscillation of the surface above the instability onset leads to an increase of the fluid viscosity. This phenomenon is evidenced by comparing the time needed for the instability to develop in the fluid at rest and once the fluid has been shaken above onset: pre-shaking may delay the instability by two orders of magnitude. A simple model based on a time-dependent viscosity is proposed which accounts quantitatively for the e…
We use the Random Phase Approximation (RPA) to compute the structure factor, S(q), of a solution of chains interacting through a soft and short range repulsive potential V. Above a threshold polymer concentration, whose magnitude is essentially controlled by the range of the potential, S(q) exhibits a peak whose position depends on the concentration. We take advantage of the close analogy between polymers and wormlike micelles and apply our model, using a Gaussian function for V, to quantitatively analyze experimental small angle neutron scattering profiles of semi-dilute solutions of hairy wo…
The rate of micelle solubilization (SR) can be appraised following the decrease of the radius of a macroscopic drop of oil in contact with a surfactant solution [Todorov, 2002]. Alternatively, the time required for the dissolution of a liquid dispersion can be used for this purpose. Here, the decrease of the turbidity of a dodecane-in-water (d/w) nanoemulsion in 7.5 mM sodium dodecylsulfate (SDS) is studied at sodium chloride concentrations of 100, 300, 500, 700, 900, and 1000 mM NaCl. These salinities correspond to non-aggregating (< 300), aggregation-promoted (500) and surfactant precipitati…
Experiments indicate that microdroplets undergoing micellar solubilization in the bulk of surfactant solution may excite Marangoni flows and self-propel spontaneously. Surprisingly, self-propulsion emerges even when the critical micelle concentration is exceeded and the Marangoni effect should be saturated. To explain this, we propose a novel model of a dissolving active droplet that is based on two fundamental assumptions: (a) products of the solubilization may inhibit surfactant adsorption; (b) solubilization prevents the formation of a monolayer of surfactant molecules at the droplet interf…
If many micelles adsorb onto the same polymer molecule then they are said to form a necklace. A minimal model of such a necklace is proposed and shown to be almost equivalent to a 1-dimensional fluid with nearest-neighbour interactions. The thermodynamic functions of this fluid are obtained and then used to predict the change in the critical micellar concentration of the surfactant in the presence of the polymer. If the amount of polymer is not too large there are two critical micellar concentrations, one for micelles in necklaces and one for free micelles.
The interfacial tension between immiscible liquids is studied as a function of a model linear surfactant length and concentration using coarse grained, dissipative particle dynamics numerical simulations. The adsorption isotherms obtained from the simulations are found to be in agreement with Langmuir model. The reduction of the interfacial tension with increasing surfactant concentration is found to display some common characteristics for all the values of chain length modeled, with our predictions being in agreement with Szyszkowski equation. Lastly, the critical micelle concentration is pre…
The role of ionic interactions between sodium dodecyl sulfate, SDS, and sapphire surfaces have been studied using specular neutron reflection to determine the structure and composition of adsorbed surfactant layers. Increasing the pH of the solution from 3 to 9 reduces the adsorption by reversing the charge of the alumina. This occurs at lower pH for the R-plane (1 -1 0 2) than the C-plane (0 0 0 1), corresponding to the different points of zero charge. The largest surface excess is about 6.5 micromol m-2, the thickness of the adsorbed layer is about 24 Angstrom and it contains roughly 20% wat…
The interactions among neutral polymer polyacrylamide (PAM) and the biosurfactant Surfactin and four betaines, N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SDDAB), N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (STDAB), N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SHDAB), and N-dodecyl-N,N-dimethyl-2-ammonio-acetate (C12BE), in phosphate buffer solution (PBS) have been studied by surface tension measurements, small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), and rheological experiments. It has been confirmed that the length of alkyl chain is …
A phase-field model is used to capture the surfactant-driven formation of fracture patterns in particulate monolayers. The model is intended for the regime of closely-packed systems in which the mechanical response of the monolayer can be approximated as a linearly elastic solid. The model approximates the loss in tensile strength of the monolayer as the surfactant concentration increases through the evolution of a damage field. Initial-boundary value problems are constructed and spatially discretized with finite element approximations to the displacement and surfactant damage fields. A compar…
We report the observation of dynamical behaviour in dilute, aqueous solutions of a surfactant CTAT (cetyl trimethylammonium p-toluenesulphonate), below the overlap concentration c$^{\star}$. At these concentrations, CTAT forms cylindrical micelles and shows a pronounced shear thickening transition above a concentration-dependent critical shear rate $\dotγ_{c}$. An analysis of the time-series of the stress relaxations at controlled shear rates in the shear-thickening regime shows the existence of correlation dimensions greater than two and positive Lyapunov exponents. This indicates the existen…
The dynamics of wetting and dewetting is largely determined by the velocity field near the contact lines. For water drops it has been observed that adding surfactant decreases the dynamic receding contact angle even at a concentration much lower than the critical micelle concentration (CMC). To better understand why surfactants have such a drastic effect on drop dynamics, we constructed a dedicated a setup on an inverted microscope, in which an aqueous drop is held stationary while the transparent substrate is moved horizontally. Using astigmatism particle tracking velocimetry, we track the 3D…
Surfactants play an important role in various physiological and biomechanical applications. An example is the respiratory system, where pulmonary surfactants facilitate the breathing and reduce the possibility of airway blocking by lowering the surface tension when the lung volume decreases during exhalation. This function is due to the dynamic surface tension of pulmonary surfactants, which depends on the concentration of surfactants spread on the liquid layer lining the interior surface of the airways and alveoli. Here, a finite membrane element formulation for liquids is introduced that all…
We report the formation of colloidal complexes resulting from the electrostatic co-assembly between anionic surfactants and cationic polyelectrolytes or block copolymers. Combining light and x-ray scattering experiments with cryogenic transmission and optical microscopy, we emphasize a feature rarely addressed in the formation of the electrostatic complexes, namely the role of the mixing concentration on the microstructure. At low mixing concentration, electrostatic complexes made from cationic-neutral copolymers and alkyl sulfate surfactants exhibit spherical core-shell microstructures. With …
The effects of the addition of sub-micrometer sized colloidal silica spheres on the linear and nonlinear rheology of semi-dilute solutions of a viscoelastic gel are studied. For a 1.4 wt.% solution of the surfactant CTAT, a peak in the zero shear rate viscosity $η_{\circ}$ is observed at approximately equal weight percents of silica and CTAT. This peak shifts to lower silica concentrations on increasing either the CTAT concentration or the surface charge on silica and disappears when the CTAT concentration is increased to 2.6wt%. The increases in $η_{\circ}$ and the high frequency plateau modu…
When the theoretical values of the interfacial tension -resulting from the homogeneous distribution of ionic surfactant molecules amongst the interface of emulsion drops- are plotted against the total surfactant concentration, they produce a curve comparable to the Gibbs adsorption isotherm. However, the actual isotherm takes into account the solubility of the surfactant in the aqueous bulk phase. Hence, assuming that the total surfactant population is only distributed among the available oil/water interfaces, one can calculate what surface concentration is necessary to reproduce the experimen…
We studied a system formed by a mixture of a thermoresponsive negatively charged graft copolymer (Alg-g-PNIPAAm) with a brush-type structure, and an oppositely charged surfactant (DTAB), in bulk and at the air-solution interface. We performed experiments of surface tension, electrophoretic mobility, dynamic and static light scattering and atomic force microscopy in order to characterize the complexes formed as a function of DTAB concentration and temperature. We found that these polymer-surfactant complexes are able to respond by changing their sizes, both in bulk and at the air-solution inter…