Low Molecular Mass Gelators of Organic Liquids and the Properties of Their Gels

Wormlike micelles are elongated flexible self-assembly structures formed by the aggregation of amphiphiles. Above a threshold concentration, they entangle into a dynamic network, reminiscent of polymer solutions, and display remarkable visco-elastic properties, which have been exploited in numerous industrial and technological fields. Relating the microstructure of these intricate structures with their bulk properties is still an ongoing quest. In this review, we present a classification of wormlike micelles, with a focus on novel systems and applications. We describe the current state of understanding of their linear rheology and give a detailed account of recent progress in small-angle neutron scattering, a particularly powerful technique to elucidate their microstructure on a wide range of length-scales.

Wormlike micelles: where do we stand? Recent developments, linear rheology and scattering techniques

Polymeric materials near the liquid-solid transition (LST) exhibit a very distinct relaxation pattern. The reference point for analyzing these patterns is the instant of LST at which relaxation becomes self-similar over wide ranges of the relaxation time. The universality of this transition and its consequences have been explored extensively during the past decade. This study will present an overview of rheological implications inherent in liquid-solid transitions of polymers. The LST can be most reliably detected in a dynamic mechanical experiment in which the frequency independence of the loss tangent marks the LST. A wide variety of rheological observations of materials in the vicinity of an LST are discussed with respect to their universality. It is shown that polymer chemistry, molecular weight, stoichiometry, temperature, inhomogeneities, etc. greatly influence the material behavior near the LST. However, the characteristic self-similar relaxation is shown by all investigated materials, independent of the nature of the LST (e.g., both, physically and chemically crosslinking polymers). Several theories predict chemical and rheological properties in the vicinity of an LST. They are briefly discussed and compared with experimental results. A variety of applications for polymers near LST are presented that either already exist or can be envisioned. The self-similar relaxation behavior which results in a power law relaxation spectrum and modulus is not restricted to materials near LST. Different classes of polymers are described that also show power law relaxation behavior. What makes the self-similar relaxation specific for materials at LST is its occurrence at long times with the longest relaxation time diverging to infinity.

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Rheology of Polymers Near Liquid-Solid Transitions

Large hydrophobic monomers stearyl methacrylate (C18) and dococyl acrylate (C22) could be copolymerized with the hydrophilic monomer acrylamide in a micellar solution of sodium dodecyl sulfate (SDS). This was achieved by the addition of salt (NaCl) into the reaction solution. Salt leads to micellar growth and, hence, solubilization of the hydrophobes within the SDS micelles. The hydrogels thus obtained without a chemical cross-linker exhibit unique properties due to the strong hydrophobic interactions. They can only be dissolved in SDS solutions demonstrating the physical nature of cross-links. Results of dynamic light scattering, rheological and mechanical measurements show that the hydrophobic associations between the blocks of C18 or C22 units prevent water solubility and flow, while the dynamic nature of the junction zones provides homogeneity and self-healing properties together with a high degree of toughness. When fractured, the hydrogels formed using C18 associations can be repaired by bringing to...

Tough and Self-Healing Hydrogels Formed via Hydrophobic Interactions

Hierarchical self-assembly offers elegant and energy-efficient bottom-up strategies for the structuring of complex materials. For block copolymers, the last decade witnessed great progress in diversifying the structural complexity of solution-based assemblies into multicompartment micelles. However, a general understanding of what governs multicompartment micelle morphologies and polydispersity, and how to manipulate their hierarchical superstructures using straightforward concepts and readily accessible polymers remains unreached. Here we demonstrate how to create homogeneous multicompartment micelles with unprecedented structural control via the intermediate pre-assembly of subunits. This directed self-assembly leads to a step-wise reduction of the degree of conformational freedom and dynamics and avoids undesirable kinetic obstacles during the structure build-up. It yields a general concept for homogeneous populations of well-defined multicompartment micelles with precisely tunable patchiness, while using simple linear ABC triblock terpolymers. We further demonstrate control over the hierarchical step-growth polymerization of multicompartment micelles into micron-scale segmented supracolloidal polymers as an example of programmable mesoscale colloidal hierarchies via well-defined patchy nanoobjects.

/pdf/precise-hierarchical-self-assembly-of-multicompartment-3uxise8op5.pdf

Precise hierarchical self-assembly of multicompartment micelles

In certain surfactant solutions, such as aqueous cetyltrimethylammonium bromide (CTAB) in 0.1 M KBr, the amphiphiles are found to assemble reversibly into long, flexible worm-like micelles. Above a few per cent surfactant, these form an entangled viscoelastic fluid, reminiscent of a polymer solution. The authors review some recent experimental and theoretical progress concerning the equilibrium statistics and dynamics of these systems, which differ from normal polymer solutions in that the chains can break and reform reversibly.

http://iopscience.iop.org/article/10.1088/0953-8984/2/33/001/pdf

Statics and dynamics of worm-like surfactant micelles

The shear-thickening behaviour of wormlike micelles, at concentrations just below "overlap", remains unexplained. In some cases, it has recently been confirmed that very slow relaxations must be present even in the quiescent state—for example, the shear-thickening properties can depend on earlier thermal cycling. We present a speculative scenario based on the presence, just below the (apparent) overlap threshold, of large rings whose linking and delinking kinetics control the shear-thickening process. Equilibration between rings and open chains in turn controls the slow relaxations.

S J Candau

Papers

Statics and dynamics of worm-like surfactant micelles

Ring-driven shear thickening in wormlike micelles?