While the concept of interfacial tension synergism in surfactant mixtures is well established, little attention has been paid to the possibility of synergistic effects on the interfacial rheology of mixed surfactant systems. Furthermore, interfacial tension synergism is most often investigated for mixtures of surfactants residing in a single phase. Here, we define dilatational modulus synergism and report a study of interfacial tension isotherms and complex dilatational moduli for a binary surfactant system with the two surfactants accessing the oil/water interface from opposite sides. Using an oil-soluble fatty acid surfactant (palmitic acid, PA) that may be ionized at the oil/water interface and a quaternary ammonium water-soluble cationic surfactant (tetradecyltrimethylammonium bromide, TTAB), the binary interfacial interaction was tuned by the aqueous phase pH. Interfacial tensions and dilatational moduli were measured by the pendant drop method for the binary surfactant system as well as the corresponding single-surfactant systems to identify synergistic effects. The possible occurrence of dilatational modulus synergism was probed from two perspectives: one for a fixed total surfactant concentration and the other for a fixed interfacial tension. The aqueous pH was found to have a controlling effect on both interfacial tension synergism and the dilatational modulus synergism. The conditions for interfacial tension synergism coincided with those for the storage modulus synergism: both tension and storage modulus synergisms were observed under all conditions tested at pH 7 where PA was mostly deprotonated, for both perspectives examined, but not for any conditions tested at pH 3 where PA is mostly protonated. The loss modulus synergism exhibited more complex behaviors, such as frequency and interfacial tension dependences, but again was only observed at pH 7. The tension and modulus synergism at pH 7 were attributed to the increased attraction between ionized PA and cationic TTAB and the formation of catanionic complexes at the oil/water interface.
Surfactant-driven Marangoni spreading generates a fluid flow characterized by an outwardly moving "Marangoni ridge". Spreading on thin and/or high viscosity subphases, as most of the prior literature emphasizes, does not allow the formation of capillary waves. On deep, low viscosity subphases, Marangoni stresses may launch capillary waves coupled with the Marangoni ridge, and new dependencies emerge for key spreading characteristics on surfactant thermodynamic and kinetic properties.Computational and physical experiments were performed using a broad range of surfactants to report the post-deposition motion of the surfactant front and the deformation of the subphase surface. Modeling coupled the Navier-Stokes and advective diffusion equations with an adsorption model. Separate experiments employed tracer particles or an optical density method to track surfactant front motion or surface deformation, respectively.Marangoni stresses on thick subphases induce capillary waves, the slowest of which is co-mingled with the Marangoni ridge. Changing Marangoni stresses by varying the surfactant system alters the surfactant front velocity and the amplitude - but not the velocity - of the slowest capillary wave. As spreading progresses, the surfactant front and its associated surface deformation separate from the slowest moving capillary wave.
Molecular architecture and composition of amphiphilic bottlebrush copolymers will dictate the dominant interfacial relaxation modes and the corresponding dilatational rheology for adsorbed layers at oil/water interfaces in a way that will correlate with the emulsifying efficiency of different bottlebrush copolymers.Amphiphilic, xylene-soluble poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PBA) heterografted bottlebrush copolymers with controlled differences in backbone length, hydrophilicity and arm length were synthesized by atom transfer radical polymerization. Dilatational rheology of adsorbed layers at the xylene/water interface was probed via pendant drop tensiometry by measuring the interfacial stress response to either large-amplitude strain cycling or small-amplitude strain oscillation. The rheological response was recorded as a function of interfacial pressure for adsorbed layers under different compression states. Emulsifying efficiency was determined as the lowest copolymer concentration that yielded water-in-xylene emulsions with at least one-month stability against coalescence.The more hydrophilic copolymers with longer PEO arms exhibited non-hysteretic stress-strain response curves in large-amplitude strain cycling and a tendency for the modulus to increase with increasing interfacial pressure. These were more efficient emulsifiers than less hydrophilic copolymers that exhibited hysteretic interfacial rheology. Mere existence of significant moduli did not correlate with high emulsifying efficiency, while an increase in modulus with increasing interfacial pressure did so.
In this paper, an effective approach is demonstrated for the fabrication of IrO2-decorated polystyrene@functionalized polypyrrole (core@shell; PS@PPyNH2) microspheres. The synthesis begins with the preparation of monodispersive PS microspheres with a diameter of 490 nm, by a process of emulsifier-free emulsion polymerization, followed by a copolymerization process involving pyrrole and PyNH2 monomers in a PS microsphere aqueous suspension, to produce uniform PS@PPyNH2 microspheres with a diameter of 536 nm. The loading of 2 nm IrO2 nanoparticles onto the PS@PPyNH2 microspheres can be easily adjusted by tuning the pH value of the IrO2 colloidal solution and the PS@PPyNH2 suspension. At pH 4, we successfully obtain IrO2-decorated PS@PPyNH2 microspheres via electrostatic attraction and hydrogen bonding simultaneously between the negatively-charged IrO2 nanoparticles and the positively-charged PS@PPyNH2 microspheres. These IrO2-decorated PS@PPyNH2 microspheres exhibit a characteristic cyclic voltammetric profile, similar to that of an IrO2 thin film. The charge storage capacity is 5.19 mA cm-2, a value almost five times greater than that of PS@PPyNH2 microspheres. In addition, these IrO2-decorated PS@PPyNH2 microspheres exhibit excellent cell viability and biocompatibility.
Marangoni spreading driven by localized surfactant solution deposition previously has been studied only for single surfactant systems. For binary surfactant mixtures, interactions that generate surface tension synergism, a thermodynamic effect, may also synergistically enhance Marangoni spreading dynamics, introducing the concept of Marangoni synergism. Spreading dynamics and possible Marangoni synergism should depend not only on thermodynamic properties but also kinetic properties of the binary system.Tracer experiments that capture post-deposition surfactant front motion were performed in parallel with computational modeling, using binary surfactant pairs with varying interaction strengths. The model coupled the Navier-Stokes and advective diffusion equations with a Frumkin-type binary adsorption model.We confirm the existence of Marangoni synergism. Stronger binary surfactant attraction favors synergism in both surface tension reduction and Marangoni spreading. Binary composition ranges over which surface tension synergism occurs differ from those for Marangoni synergism, indicating that the origins of the two synergistic effects are not identical. Analysis of model spreading velocities show that the thermodynamic spreading parameter is the controlling factor at early times for both single and binary surfactant systems, while the intrinsic adsorption and desorption kinetics influence spreading velocities and thus the occurrence of Marangoni synergism at later times.
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