Abstract P-38: Tunable Soft Networks of Wormlike Micelles and Clay Particles

Background: Over the past few decades, there has been a great deal of interest in the aqueous self-assembly of surfactant molecules into giant wormlike micelles (WLMs). These cylindrical aggregates undergo reversible breakdown processes and in favorable cases can grow up to few tens of micrometers that is comparable with the length of high molecular weight polymer. The viscoelastic properties of WLMs can be easily modified by different additives like salts or polymers. A new emerging research area consists of tuning the WLM solution properties by inorganic nanoparticles. It suggests, in particular, the use of networks of entangled WLMs as a matrix for producing soft nanocomposites with different kinds of embedded nanoparticles that are promising for controlled release, template synthesis, and oilfield applications. These materials can combine adaptive rheological properties of the WLM matrix and the functionality of nanofiller. Methods: Rheometry and cryo-transmission electron microscopy were combined to investigate the structure and properties of mixed WLMs of zwitterionic oleylamidopropyl dimethyl betaine and anionic sodium dodecyl sulfate surfactants and platelike particles of bentonite clay. Results: This system demonstrates the formation of giant linear long-lived WLMs, which even at extremely low surfactant concentrations reach a sufficient length to entangle with each other and form a temporally persistent network. The stability of these micelles can be due to electrostatic attraction between the headgroups of the anionic and zwitterionic surfactants and favorable volume/length hydrophobic ratio in the surfactant mixture. At increasing surfactant concentration, the long-lived linear micelles transform into fast-breaking branched micelles. Stable viscoelastic suspensions of clay particles in semi-dilute solutions of WLM were elaborated. They represent a novel type of soft nanocomposite with the tunable matrix. Structural studies revealed that the clay is dispersed in a dense network of entangled WLM in the form of 100-nm tactoids. Rheological investigations demonstrated that clay particles can induce an increase of viscosity and relaxation time by up to one order of magnitude. The effect of the clay becomes more pronounced with increasing content of anionic surfactant, when the micelles become branched. This behavior was explained by the stabilization of micelle-nanoclay junction points due to the screening of the repulsion between positively charged fragments of zwitterionic head groups by added anionic surfactant. Conclusion: The pronounced effect of nanoparticles on the viscoelasticity of the network formed by branched WLMs was observed for the first time. The nanoparticles-WLM junctions were confirmed by cryo-TEM data. The elaborated systems are of interest for many industrial applications

Strong Viscosity Increase in Aqueous Solutions of Cationic C22-Tailed Surfactant Wormlike Micelles

The viscoelastic properties and structure parameters have been investigated for aqueous solutions of wormlike micelles of cationic surfactant erucyl bis(hydroxyethyl) methylammonium chloride with long C22 tail in the presence inorganic salt KCl. The salt content has been varied to estimate linear to branched transition conditions due to screening of the electrostatic interaction in the networks. The local cylindrical structure and low electrostatic repulsion was obtained by SANS data. The drastic power law dependencies of rheological properties on surfactant concentrations were obtained at intermediate salt content. Two power law regions of viscosity dependence were detected in semi-dilute solutions related to “unbreakable” and “living” micellar chains. The fast contour length growth with surfactant concentration demonstrated that is in good agreement with theoretical predictions

Ga-In Alloy Segregation within a Porous Glass as Studied by SANS

Nanolattices can play the role of templates for metals and metallic alloys to produce functional nanocomposites with particular properties affected by nanoconfinement. To imitate the impact of nanoconfinement on the structure of solid eutectic alloys, we filled porous silica glasses with the Ga-In alloy, which is widely used in applications. Small-angle neutron scattering was observed for two nanocomposites, which comprised alloys of close compositions. The results obtained were treated using different approaches: the common Guinier and extended Guinier models, the recently suggested computer simulation method based on the initial formulae for neutron scattering, and ordinary estimates of the scattering hump positions. All of the approaches predicted a similar structure of the confined eutectic alloy. The formation of ellipsoid-like indium-rich segregates was demonstrated

SANS Studies of the Gallium–Indium Alloy Structure within Regular Nanopores

Potential applications of nanolattices often require filling their empty space with eutectic metallic alloys. Due to confinement to nanolattices, the structure of phase segregates in eutectic alloys can differ from that in bulk. These problems are poorly understood now. We have used small angle neutron scattering (SANS) to study the segregation in the Ga-In alloy confined to an opal template with the regular pore network, created by a strict regularity of opal constituents in close similarity with nanolattices. We showed that SANS is a powerful tool to reveal the configuration of segregated phases within nanotemplates. The In-rich segregates were found to have specific structural features as small sizes and ordered arrangement