Polymer/surfactant interactions at the air/water interface

The development of neutron reflectometry has transformed the study and understanding of polymer/surfactant mixtures at the air/water interface. A critical assessment of the results from this technique is made by comparing them with the information available from other techniques used to investigate adsorption at this interface. In the last few years, detailed information about the structure and composition of adsorbed layers has been obtained for a wide range of polymer/surfactant mixtures, including neutral polymers and synthetic and naturally occurring polyelectrolytes, with single surfactants or mixtures of surfactants. The use of neutron reflectometry together with surface tensiometry, has allowed the surface behaviour of these mixtures to be related directly to the bulk phase behaviour. We review the broad range of systems that have been studied, from neutral polymers with ionic surfactants to oppositely charged polyelectrolyte/ionic surfactant mixtures. A particular emphasis is placed upon the rich pattern of adsorption behaviour that is seen in oppositely charged polyelectrolyte/surfactant mixtures, much of which had not been reported previously. The strong surface interactions resulting from the electrostatic attractions in these systems have a very pronounced effect on both the surface tension behaviour and on adsorbed layers consisting of polymer/surfactant complexes, often giving rise to significant surface ordering.     

Correlation of surfactant/polymer phase behavior with adsorption on target surfaces

In this contribution, the phase behavior of a surfactant/polymer mixed system is related to the adsorption of a complex derived from the mixture onto a target surface. The phase map for the system sodium dodecyl sulfate (SDS, a model anionic surfactant)/pDMDAAC (poly(dimethyl diallyl ammonium chloride), a cationic polymer) shows behavior very typical of surfactant/oppositely charged polyelectrolyte mixtures. The predominant feature is a broad, two-phase region in the phase map which lies asymmetrically around the 1:1 stoichiometry of surfactant charge groups to polymer charge units. The overall controlling principle driving the phase separation is charge compensation. Excess of polymer yields an isotropic solution, as does a great excess of surfactant (termed resolubilization). The phase separating in the SDS/pDMDAAC system is characterized by a positive zeta-potential when the polymer is in excess and a negative zeta-potential when the surfactant is in excess. The surface charge properties of the precipitated phases are essentially identical to those of target particles (ground borosilicate glass) dispersed at the same approximate position in the phase map, suggesting that the surfactant/polymer complex at the precipitation boundary is the same as that adsorbing onto the pigment particle. This conclusion is confirmed by depletion studies which allow the polymer adsorption density to be determined. For polymer-rich systems, essentially all of the surfactant adsorbs along with the polymer via a high-affinity isotherm with a plateau coverage of about 0.8 mg polymer/m (2). Surfactant-rich systems adsorb with a similar affinity, despite the mismatch of the complex charge matching that of the particle surface. Once adsorbed, these complexes are not readily removed by rinsing, though complexes adsorbed from SDS-rich systems will lose excess surfactant upon extreme dilution. Over a wide range of surfactant-rich compositions, from 1:1 stoichiometry out toward the resolubilization zone, a chemical analysis reveals that the surfactant/polymer precipitate species consists of a 1:1 charge complex with the addition of about 0.25 mol of surfactant/mol of complex. Resolubilization of these sparingly soluble species is achieved simply by dilution to below their solubility limit.     

Phase behavior and molecular thermodynamics of coacervation in oppositely charged polyelectrolyte/surfactant systems: a cationic polymer JR 400 and anionic surfactant SDS mixture

Coacervation in mixtures of polyelectrolytes and surfactants with opposite charge is common in nature and is also technologically important to consumer health care products. To understand the complexation behavior of these systems better, we combine multiple experimental techniques to systematically study the polymer/surfactant binding interactions and the phase behavior of anionic sodium dodecyl sulfate (SDS) surfactant in cationic JR 400 polymer aqueous solutions. The phase-behavior study resolves a discrepancy in the literature by identifying a metastable phase between the differing redissolution phase boundaries reported in the literature for the surfactant-rich regime. Isothermal titration calorimetry analyzed within the framework of the simple Satake-Yang model identifies binding parameters for the surfactant-lean phase, whereas a calculation for polymer-bound micelles coexisting with free micelles is analyzed in the surfactant-rich redissolution regime. This analysis provides a preliminary understanding of the interactions governing the observed phase behavior. The resulting thermodynamic properties, including binding constants and the molar Gibbs free energies, enthalpies, and entropies, identify the relative importance of both hydrophobic and electrostatic interactions and provide a first approximation for the corresponding microstructures in the different phases. Our study also addresses the stability and metastability of oppositely charged polyelectrolytes and surfactant mixtures.     

Complexation behaviour of cellulose derivative/surfactant mixtures investigated by nonlinear enhanced Rayleigh scattering

Complexation behaviour of cellulose derivative/surfactant mixtures in aqueous solution was investigated by nonlinear enhanced Rayleigh scattering (NERS). The NERS spectra of polymer solutions, including second-order scattering, third-order scattering, frequency doubling scattering and triplet frequency scattering were created using by spectrofluorometer. The results indicated that NERS intensity of cellulose derivative/surfactant systems changes differently with continuing addition of surfactant due to the complexation between cellulose derivative and surfactant. The critical micelle concentration of cellulose derivatives/surfactants system is easy to obtain. The change of NERS intensity reveals the complexation behaviour of cellulose derivative/surfactant and the aggregation state of polymer chains in evidence. Therefore, NERS had been successfully developed to study complexation behaviour of cellulose derivative/surfactant mixtures in solution.     

Dynamic adsorption of weakly interacting polymer/surfactant mixtures at the air/water interface

The dynamic adsorption of polymer/surfactant mixtures containing poly(ethylene oxide) (PEO) with either tetradecyltrimethylammonium bromide (C(14)TAB) or sodium dodecyl sulfate (SDS) has been studied at the expanding air/water interface created by an overflowing cylinder, which has a surface age of 0.1-1 s. The composition of the adsorption layer is obtained by a new approach that co-models data obtained from ellipsometry and only one isotopic contrast from neutron reflectometry (NR) without the need for any deuterated polymer. The precision and accuracy of the polymer surface excess obtained matches the levels achieved from NR measurements of different isotopic contrasts involving deuterated polymer, and requires much less neutron beamtime. The PEO concentration was fixed at 100 ppm and the electrolyte concentration at 0.1 M while the surfactant concentration was varied over three orders of magnitude. For both systems, at low bulk surfactant concentrations, adsorption of the polymer is diffusion-controlled while surfactant adsorption is under mixed kinetic/diffusion control. Adsorption of PEO is inhibited once the surfactant coverage exceeds 2 μmol m(-2). For PEO/C(14)TAB, polymer adsorption drops abruptly to zero over a narrow range of surfactant concentration. For PEO/SDS, inhibition of polymer adsorption is much more gradual, and a small amount remains adsorbed even at bulk surfactant concentrations above the cmc. The difference in behavior of the two mixtures is ascribed to favorable interactions between the PEO and SDS in the bulk solution and at the surface.     

Polyelectrolyte/surfactant mixtures at the air–solution interface

This review presents some of the recent developments in our understanding of the behaviour of polyelectrolyte/surfactant mixtures at the air–solution interface. The existence of a strong surface polyelectrolyte/surfactant interaction results in a complex pattern of surface adsorption. Recent studies, using a range of surface sensitive techniques, which include ellipsometry, neutron and X-ray reflectivity, surface tension and interfacial rheology, have considerably enhanced the understanding of their surface behaviour, which can be rationalized in terms of the competition between the formation of surface active polymer/surfactant complexes and solution polymer/surfactant micelle complexes.     

Effect of polymer molecular weight on the polymer/surfactant interaction

A thermodynamic analysis of the interaction between fourteen different molar mass poly(ethylene oxide)s (PEO) and sodium dodecyl sulfate (SDS) based on the measured surfactant-binding isotherms is given. The surfactant-binding isotherms were determined by the potentiometric method in the presence of 0.1 M inert electrolyte (NaBr). It was found that there is no PEO/SDS complex formation if M(PEO) < 1000. In the molecular weight range 1000 < M(PEO) < 8000, the critical aggregation concentration (cac) and the surfactant aggregation number are decreasing as the polymer molecular weight increases. The saturated bound surfactant amount is proportional to the number concentration of the polymer in this molecular weight range. If M(PEO) exceeds approximately 8000, the cac does not depend on the polymer molar mass, and the saturated bound amount of the surfactant becomes proportional to the mass concentration of the polymer. It was also observed that independently of the polymer molecular weight the surfactant aggregation number increases as the equilibrium surfactant monomer concentration increases from the cac to the critical micellar concentration (cmc). Finally, it was demonstrated that only one polymer molecule is involved in the complex formation independently of the polymer molecular weight.     

Adsorption and desorption of polymer/surfactant mixtures at solid-liquid interfaces: substitution experiments

The adsorption of mixtures of aqueous solutions of cationic hydroxyethylcellulose polymer JR400 and anionic surfactant, sodium dodecyl sulfate, using atomic force microscopy (AFM) has been studied. Samples with various compositions from different regions of the ternary phase diagram presented in our previous work were imaged by atomic force microscopy on freshly cleaved mica, and hydrophobically modified mica and silica in soft-contact mode. A series of "washing" (subsequent injection of compositions with gradually decreasing polymer/surfactant ratio) and "scratching" (mechanical agitation of the surface material with an AFM tip) experiments were performed. It was revealed that the morphology of the adsorbed layer altered in a manner following the changes in morphology in the bulk solution. These changes were evidenced in cluster formation in the layer. The results suggest that the influence of the surface was limited to the formation of the adsorbed layer where the local concentrations of polymer and surfactant were higher than those in the bulk. All further modifications were driven by changes in the mixture composition in bulk. Force measurements upon retraction reveal the formation of network structures within the surface aggregates that will greatly slow structural reequilibration.     

Foaming and foam stability for mixed polymer-surfactant solutions: effects of surfactant type and polymer charge

Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.     

Studies of synergism/antagonism for lowering dynamic interfacial tensions in surfactant/alkali/acidic oil systems, part 2: synergism/antagonism in binary surfactant mixtures

Experimental studies are conducted in order to elucidate the mechanisms responsible for synergism/antagonism for lowering dynamic interfacial tension in hydrocarbons/binary surfactant mixtures/brine systems. The dynamic interfacial tensions between hydrocarbons of different alkane carbon numbers (from 6 to 14) and solutions of binary surfactant mixtures were measured. We found that the synergism/antagonism for interfacial tension reduction in binary surfactant mixtures having low interfacial tension values was influenced by the alkane carbon number of oil phase, hydrophilic-lipophilic ability of surfactant, and NaCl concentration. A new explanation in view of interactions among surfactant molecules, oil molecules, and water molecules is provided.     

Macroscopic, mesostructured cationic surfactant/neutral polymer films: structure and cross-linking

Mesostructured films of alkyltrimethylammonium bromides or cetylpyridinium bromide and polyethylenimines that spontaneously self-assemble at the air/water interface have been examined using a range of surface sensitive techniques. These films are unusual in that they can be micrometers thick and are relatively robust. Here we show that the films can be cross-linked and thus removed from the liquid surface where they form, as solid, mesostructured polymer-surfactant membranes. Cross-linking causes little change in the structure of the films but freezes in the metastable mesostructures, enhancing the potential of these films for future applications. Cross-linked films, dried after removal from the solution surface, retain the ordered nanoscale structure within the film. We also report grazing incidence X-ray diffraction (GID), which shows that most films display scattering consistent with 2D-hexagonal phase crystallites of rodlike surfactant micelles encased in polymer. Polymer branching makes little difference to the film structures; however, polymer molecular weight has a significant effect. Films with lower polymer MW are generally thinner and more ordered, while higher polymer MW films were thicker and less ordered. Increased pH causes formation of thicker films and improves the ordering in low MW films, while high MW films lose order. To rationalize these results, we propose a model for the film formation process that relates the kinetic and thermodynamic limits of phase separation and mesophase ordering to the structures observed.     

Stabilization of bioderived surfactant/polyelectrolyte complexes through surfactant conjugation to the biopolymer

Mixtures of oppositely charged surfactants and polyelectrolytes self-assemble into a variety of nanostructured complexes. With the view of developing simpler and cleaner alternatives to synthetic nanomaterials, self-assembled nanostructures can be prepared from bioderived surfactant/polyelectrolyte mixtures. These complexes can be designed to vary their phase behavior and structure in response to external stimuli, and are simpler and cleaner to prepare than conventional synthetic copolymers (e.g., block or graft). Yet, some potential applications of surfactant/polyelectrolyte complexes are limited by their lower stability. Here, we overcome this limitation by covalently coupling the surfactant head group to the polymer chain. Visual observations and small-angle X-ray scattering (SAXS) reveal that covalent coupling dramatically improves stability at both the macroscopic and mesoscopic lengthscales. This suggests that, through covalent conjugation, stability of nanostructured surfactant/biopolymer complexes can be made to rival that of synthetic copolymers, thereby extending their use to applications that require long-lasting nanostructured materials.     

Three-phase separation in nonionic surfactant/hydrophobically modified polymer aqueous mixtures

Three-phase separation for Triton X-114 or Triton X-100 solutions with addition of hydrophobically modified hydroxyethyl cellulose was investigated experimentally. When the surfactant concentration was high enough, the solution slightly above the cloud point could separate into three macroscopic phases: a cloudy phase in between a clear phase and a bluish, translucent phase. The rate of phase separation was very low with the formation of the clear and cloudy phases followed by the emergence of the bluish phase. The volume fraction of the cloudy phase increases linearly with the global polymer concentration, whereas the volume fraction of the bluish phase increases linearly with the global surfactant concentration. Composition analyses found that most of the polymer stayed in the cloudy phase, as opposed to most of the surfactant in the bluish phase. The interesting phase behavior can be explained by an initial associative phase separation followed by a segregative phase separation in the cloudy phase.     

三元复合驱碱/表面活性剂/聚合物模拟原油乳状液稳定动力学特性

基于两相分离的乳状液稳定模型,研究了三元复合驱模拟原油乳状液稳定动力学特性;通过液膜强度和油水界面张力探讨了碱/表面活性剂/聚合物对模拟原油乳状液稳定动力学特性的影响机理。 结果表明,乳状液稳定模型可以很好的评价乳状液的稳定性,并得到乳状液的稳定动力学特性;碱浓度小于900 mg/L有利于乳状液的稳定,碱浓度大于900 mg/L不利于乳状液的稳定;表面活性剂和聚合物浓度的增加使得形成的模拟原油乳状液更加稳定;模拟原油乳状液的稳定作用主要是通过碱、表面活性剂降低油水界面张力并增加油水界面膜强度,聚合物通过提高界面膜强度实现的,三者存在协同效应。     

Rheology of viscoelastic solutions of cationic surfactant. Effect of added associating polymer

Rheological studies were performed with aqueous salt solutions of viscoelastic cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride (EHAC) and its mixtures with hydrophobically modified polyacrylamide. The solutions of surfactant itself above the concentration of crossover of wormlike micelles exhibit two regions of rheological response. In the first region, they behave like polymer solutions in semidilute regime characterized by viscoelastic behavior with a spectrum of relaxation times. In the second region, unlike polymer solutions their relaxation after shear is dominated by a single relaxation time. Being composed of "living" micelles, the EHAC solutions easily lose their viscosity at the variation of the external conditions. For instance, heating from 20 to 60 degrees C reduces viscosity by up to 2 orders of magnitude, while added hydrocarbons induce a sudden drop of viscosity by 3-6 orders of magnitude. Polymer profoundly affects the rheological properties of EHAC solutions. The polymer/surfactant system demonstrates a 10,000-fold increase in viscosity as compared to pure-component solutions, the effect being more pronounced for polymer with less blocky distribution of hydrophobic units. A synergistic enhancement of viscosity was attributed to the formation of common network, in which some subchains are made up of elongated surfactant micelles, while others are composed of polymer. At cross-links the hydrophobic side groups of polymer anchor EHAC micelles. In contrast to surfactant itself, the polymer/surfactant system retains high viscosity at elevated temperature; at the same time it keeps a high responsiveness to hydrocarbon medium inherent to EHAC.     

Ordering in surfactant mixtures induced by polymers

We studied ternary mixtures of nonionic surfactant (C12E6, n-dodecyl hexaoxyethylene glycol monoether), polymer (PEG, polyethylene glycol), and water. A small amount of PEG induces demixing into the polymer-rich and surfactant-rich phases in the ternary PEG/C12E6/water mixture. Above a certain concentration and/or molecular weight of PEG, the surfactant-rich phase orders, even in a solution consisting of a few percent of surfactant. The phase boundary acts as a semipermeable membrane, and the equilibrium is determined by the chemical potential of water in two phases. The explicit expression for the amount of PEG needed to order C12E6 water solution is given and verified experimentally. The analysis of the coexistence conditions leads to the conjecture that only two oxygen atoms in the outward part of the hydrophilic surfactant head strongly affect the chemical potential of water. Our methodology is generic, i.e., on the same basis one can design a similar experiment for any surfactant/polymer/water system and find the right proportions of polymer that induce order in a surfactant-rich phase.     

The effect of polymer chain length on the thermodynamics of acrylate/cyanobiphenyl mixtures

The effect of polymer molecular mass on the phase behaviour and solubility limits of polymer/liquid crystal mixtures is studied for blends of poly(methyl methacrylate) (PMMA) and the small-molecule liquid crystal, 4'-octyl-4-biphenylcarbonitrile (8CB). The phase diagrams from optical microscopy show a limit to the effect of increasing polymer molecular mass. The Flory-Huggins theory (FH) for polymer solutions is used to extract the interaction parameter, χ, from the phase diagrams. The initial FH fits are performed with the assumption that χ is independent of polymer molecular mass, but result in poor correlation to the microscopy data. When χ is allowed to scale with M _w, however, the FH fits are consistent with the limiting molecular mass behaviour. This result represents, to our knowledge, the first time that this scaling behaviour has been observed in polymer/liquid crystal blends. The solubility limit, β, of 8CB in PMMA for each polymer molecular mass is also determined and, when compared with the results of previous studies, support the concept that β is independent of both polymer composition and molecular masses when the polymer molecular mass exceeds ca. 5×10⁵ g mol^-1.     

Self-consistent field modeling of adsorption from polymer/surfactant mixtures

We report on the development of a self-consistent field model that describes the competitive adsorption of nonionic alkyl-(ethylene oxide) surfactants and nonionic polymer poly(ethylene oxide) (PEO) from aqueous solutions onto silica. The model explicitly describes the response to the pH and the ionic strength. On an inorganic oxide surface such as silica, the dissociation of the surface depends on the pH. However, salt ions can screen charges on the surface, and hence, the number of dissociated groups also depends on the ionic strength. Furthermore, the solvent quality for the EO groups is a function of the ionic strength. Using our model, we can compute bulk parameters such as the average size of the polymer coil and the surfactant CMC. We can make predictions on the adsorption behavior of either polymers or surfactants, and we have made adsorption isotherms, i.e., calculated the relationship between the surface excess and its corresponding bulk concentration. When we add both polymer and surfactant to our mixture, we can find a surfactant concentration (or, more precisely, a surfactant chemical potential) below which only the polymer will adsorb and above which only the surfactant will adsorb. The corresponding surfactant concentration is called the CSAC. In a first-order approximation, the surfactant chemical potential has the CMC as its upper bound. We can find conditions for which CMC < CSAC . This implies that the chemical potential that the surfactant needs to adsorb is higher than its maximum chemical potential, and hence, the surfactant will not adsorb. One of the main goals of our model is to understand the experimental data from one of our previous articles. We managed to explain most, but unfortunately not all, of the experimental trends. At the end of the article we discuss the possibilities for improving the model.     

Coalescence-induced coalescence and dimensional crossover during the phase separation in ternary surfactant/polymer/water mixtures

We studied the separation process in the ternary mixtures of nonionic surfactant (C(12)E(6), hexaethylene glycol monododecyl ether), polymer (PEG = poly(ethylene glycol)), and water. The separation process of PEG/water rich domains from the surfactant rich matrix was observed by the optical microscopy. From the morphological analysis, we determined the size of the domains as a function of time. On this basis we identified a dominating mechanisms of domains growth, that is the coalescence-induced coalescence mechanism. The coalescence (collision) event of two droplets induces a flow or a change of concentration distribution around droplets which pushes other droplets together inducing further growth. We also observed the evaporation-condensation (Lifshitz-Slyozov) mechanism of growth, but it did not affect the growth of large domains appreciably. We determined two regimes of the coalescence-induced coalescence associated with the dimensionality of the system. When the domains were smaller or comparable in size to the sample thickness we observe a three-dimensional growth. When the domains became larger than the sample thickness, a two-dimensional growth was observed. In the first regime, the size of the domains, L(t), grew linearly with t, while in the second regime, L(t) approximately t(0.3). In the binary, surfactant/water system, water domains grew by the geometrical coalescence-induced coalescence as L(t) approximately t in three dimensions.     

Polymerization of polymer/ferroelectric liquid crystal composites formed with branched liquid crystalline bismethacrylates

Polymerization and phase behaviour of a branched liquid crystalline bismethacrylate in a ferroelectric liquid crystal (FLC) were characterized. Addition of the monomer increases the temperature range of the smectic A phase, and, at relatively low concentrations of monomer, the temperature range increases to more than 10 times that observed in the neat FLC. Other phases such as the smectic C* phase are no longer exhibited as the monomer interferes with the inherent tilt of the FLC molecules. After polymerization, the polymer network phase separates and the phase transition temperatures return to values close to those of the FLC. The monomer also shows a high degree of orientational order before polymerization, which is retained to a large extent after polymerization. The order in the polymer network results in considerable birefringence at temperatures well above the clearing point of the pure FLC. This behaviour is induced by the order of the polymer network and interactions of the FLC molecules with the network which prevent a fraction of the FLC molecules from exhibiting typical phase behaviour. In the formation of the branched liquid crystalline bismethacrylates/FLC composites, a steady increase is observed in the polymerization rate as the polymerization temperature increases and the order of the FLC phase decreases, a behaviour significantly different from that observed in other monomer/FLC mixtures for which the polymerization rate increases as the order of the FLC phase increases. Additionally, at appropriate polymerization temperatures around the clearing point, polymerization driven endothermic phase transitions may be observed.