Insights into Extended Structures and Their Driving Force: Influence of Salt on Polyelectrolyte/Surfactant Mixtures at the Air/Water Interface.

This paper addresses the effect of polyelectrolyte stiffness on the surface structure of polyelectrolyte (P)/surfactant (S) mixtures. Therefore, two different anionic Ps with different intrinsic persistence length lP are studied while varying the salt concentration (0-10-2 M). Either monosulfonated polyphenylene sulfone (sPSO2-220, lP ∼20 nm) or sodium poly(styrenesulfonate) (PSS, lP ∼1 nm) is mixed with the cationic surfactant tetradecyltrimethylammonium bromide (C14TAB) well below its critical micelle concentration and studied with tensiometry and neutron reflectivity experiments. We kept the S concentration (10-4 M) constant, while we varied the P concentration (10-5-10-3 M of the monomer, denoted as monoM). P and S adsorb at the air/water interface for all studied mixtures. Around the bulk stoichiometric mixing point (BSMP), PSS/C14TAB mixtures lose their surface activity, whereas sPSO2-220/C14TAB mixtures form extended structures perpendicular to the surface (meaning a layer of S with attached P and additional layers of P and S underneath instead of only a monolayer of S with P). Considering the different P monomer structures as well as the impact of salt, we identified the driving force for the formation of these extended structures: compensation of all interfacial charges (P/S ratio ∼1) to maximize the gain of entropy. By increasing the flexibility of P, we can tune the interfacial structures from extended structures to monolayers. These findings may help improve applications based on the adsorption of P/S mixtures in the fields of cosmetic or oil recovery.

New structural approach to rationalize the foam film stability of oppositely charged polyelectrolyte/surfactant mixtures.

A novel structural framework is presented to rationalize the foam film stability of polyelectrolyte/surfactant mixtures using neutron reflectivity data. Provision of electrostatic or steric stabilization in thin foam films is related to the spatial distributions of molecules interacting from opposing air/water interfaces. The advance is discussed in the context of many studies on mixed systems over two decades that focused on macroscopic properties such as the surface tension, elasticity, potential and composition, but for which no robust correlations have been established. This concept can now be broadened to other colloidal dispersions of high impact for technical, environmental and life science applications.

Polymers and surfactants at fluid interfaces studied with specular neutron reflectometry.

This review addresses the advances made with specular neutron reflectometry in studies of aqueous mixtures of polymers and surfactants at fluid interfaces during the last decade (or so). The increase in neutron flux due to improvements in instrumentation has led to routine measurements at the air/water interface that are faster and involve samples with lower isotopic contrast than in previous experiments. One can now resolve the surface excess of a single deuterated component on the second time scale and the composition of a mixture on the minute time scale, and information about adsorption processes and dynamic rheology can also be accessed. Research areas addressed include the types of formed equilibrium surface structures, the link to foam film stability and the range of non-equilibrium effects that dominate the behavior of oppositely charged polyelectrolyte/surfactant mixtures, macroscopic film formation in like-charged polymer/surfactant mixtures, and the properties of mixtures of bio-polymers with surfactants and lipids.

Surface adsorption of sulfonated poly(phenylene sulfone)/C14TAB mixtures and its correlation with foam film stability.

Polyelectrolyte/surfactant mixtures of rigid monosulfonated poly(phenylene sulfone) (sPSO2-220) and tetradecyl trimethylammonium bromide (C14TAB) were investigated by surface tension, surface elasticity and foam film stability measurements. The results were compared to former measurements of polyelectrolyte/surfactant mixtures containing more flexible polyelectrolytes (PAMPS or PSS and C14TAB). For all polyelectrolyte/surfactant mixtures an increased surface adsorption in comparison to the pure surfactant was detected. Moreover, sPSO2-220/C14TAB mixtures showed a much higher surface activity and foam film stability than mixtures with more flexible polyelectrolytes. The results presented give insight into the surface adsorption and foam film formation of rigid polyelectrolyte/surfactant mixtures. Therefore, this study helps to understand the role of polyelectrolyte backbone rigidity in the formation and stabilization of foam films made from polyelectrolyte/surfactant mixtures.

Two-Dimensional Aggregation and Semidilute Ordering in Cellulose Nanocrystals.

The structural properties and aggregation behavior of carboxymethylated cellulose nanocrystals (CNC-COOH) were analyzed with small angle neutron scattering (SANS), transmission electron microscopy (TEM), atomic force microscopy (AFM), and dynamic light scattering (DLS) and compared to sulfuric acid hydrolyzed cellulose nanocrystals (CNC-SO3H). The CNC-COOH system, prepared from single carboxymethylated cellulose nanofibrils, was shown to laterally aggregate into 2D-stacks that were stable both in bulk solution and when adsorbed to surfaces. CNC-SO3H also showed a 2D aggregate structure with similar cross sectional dimensions (a width to height ratio of 8) as CNC-COOH, but a factor of 2 shorter length. SANS and DLS revealed a reversible ordering of the 2D aggregates under semidilute conditions, and a structure peak was observed for both systems. This indicates an early stage of liquid crystalline arrangement of the crystal aggregates, at concentrations below those assessed using birefringence or polarized optical microscopy.

Surface Adsorption of Oppositely Charged SDS:C(12)TAB Mixtures and the Relation to Foam Film Formation and Stability.

The complexation, surface adsorption, and foam film stabiliztation of the oppositely charged surfactants, sodium dodecyl sulfate (SDS) and dodecyl trimethylammonium bromide (C12TAB), is analyzed. The SDS:C12TAB mixing ratio is systematically varied to investigate whether the adsorption of equimolar or irregular catanionic surfactant complexes, and thus a variation in surface charge (i.e., surface excess of either SDS or C12TAB), governs foam film properties. Surface tension measurements indicate that SDS and C12TAB interact electrostatically in order to form stoichometric catanionic surfactant complexes and enhance surface adsorption. On the other hand it can be demonstrated that the SDS:C12TAB mixing ratio and, thus, a change in surface charge and composition plays a decisive role in foam film stabilization. The present study demonstrates that varying the mixing ratio between SDS and C12TAB offers a tool for tailoring surface composition and foam film properties, which are therefore not exclusively mediated by the presence of equimolar catanionic surfactant complexes. The SDS:C12TAB net amount and mixing ratio determine the type, stability, and thinning behavior of the corresponding foam film. These observations indicate the formation of a mixed surface layer, composed of the catanionic surfactant species surrounded by either free SDS or C12TAB molecules in excess. Furthermore, a systematic variation in CBF-NBF transition kinetics is rationalized on the basis of a microscopic phase transition within the foam films. Fundamental knowlegde gained from this research gives insight into the surface adsorption and foam film formation of catanionic surfactant mixtures. The study helps researchers to understand basic mechanisms of foam film stabilization and to use resources more efficiently.