We report experiments on aqueous foams made of solutions of oligomers of cationic surfactants. The degree of oligomerization is varied up to 4, and two spacer lengths are used. We have studied both the interfacial dilational and shear rheology, the single thin film properties, the foamability of the solutions, as well as the aging and the mechanical properties of the 3D foams. We have found clear differences between the oligomeric systems at all length scales. We then discuss the correlations between the properties at the different length scales and see how the macroscopic features depend on the molecular structure. This work first allows us to determine the relevance of each measurement; in that respect, it stresses the important role of the timescales, and the need to monitor the liquid fraction and bubble size in order to perform correct comparisons. Secondly, this work provides information on how one could optimize foaming properties with oligomers, and the balance between the degree of oligomerization and spacer length.

The successive transitions of morphology in aqueous solutions of interacting micelles are directly evidenced by the position q* of the correlation peak of the small angle neutron scattering profiles. As the volume fraction Phi increases, q* successively fits to the dilution laws expected for spheres and cylinders, and eventually gets close to the one expected for sheets when the micelles get branched. Data in between the swelling laws are quantitatively analyzed in terms of aggregation number and junction density. Varying the temperature in the dilute regime yields the end-cap energy which varies with molecular structure and scales as Phi(-1/2). In the semidilute regime, the junction density scales as nu(j) similar to Phi(1.8), close but slightly faster than theoretically expected. The boosting effect of intermicellar repulsion on growth and branching is pointed out by the present results which directly show that both condensation processes keep the micelles further apart.

Liquid crystal defects are used as probes to study the local reorientation dynamics of the nematic surface director on SiOx alignment layers. The tracking of the defect's motion reveals the presence of solid friction forces, unexpected in this complex viscous fluid. We identify the director pinning due to a surface quenched disorder as a possible mechanism that gives rise to the measured solid friction.

Aqueous dispersions of exfoliated, bile-salt stabilized single-wall carbon nanotubes exhibit a first order transition to a nematic liquid-crystalline phase. The nematic phase presents itself in the form of micron-sized nematic droplets also known as tactoids, freely floating in the isotropic host dispersion. The nematic droplets are spindle shaped and have an aspect ratio of about four, irrespective of their size. We attribute this to a director field that is uniform rather than bipolar, which is confirmed by polarization microscopy. It follows that the ratio of the anchoring strength and the surface tension must be about four, which is quite larger than predicted theoretically but in line with earlier observations of bipolar tactoids. From the scatter in the data we deduce that the surface tension of the coexisting isotropic and nematic phases must be extremely low, that is, of the order of nN/m.

The surface aggregates structure of dimethyldodecylamine-N-oxide (C12DAO) in three silica dispersions of different particle sizes (16 - 42 nm) was studied by small-angle neutron scattering (SANS) in a H2O/D2O solvent mixture matching the silica. At the experimental conditions (pH 9) the surfactant exists in its nonionic form and the structure of the adsorbed layer is not affected by added electrolyte. It is found that C12DAO forms spherical surface micelles of 2 nm diameter on the 16 nm silica particles, but oblate ellipsoidal surface micelles are formed on the 27 and 42 nm particles. The dimensions of these oblate surface aggregates (minor and major semi-axes Rn and Rlat) are similar to those of C12DAO micelles in the aqueous solutions. It is concluded that the morphological transition from spherical to ellipsoidal surface aggregates is induced by the surface curvature of the silica particles. A comparison of the shape and dimensions of the surface aggregates formed by C12DAO and C12E5 on the 16 nm silica particles demonstrates that the nature of the surfactant head group does not determine the morphology of the surface aggregates, but has a strong influence on the number of surface aggregates per particle, due to the different interactions of the head groups with the silica surface.

Brambilla et al. Reply:

We report on a new class of self-assembled transient networks made of surfactant micelles of tunable morphology (from spheres, to rodlike to wormlike) reversibly linked by telechelic polymers. Linear rheological measurements show that three distinct domains can be defined depending on the morphologies of the micelles: a domain where the micelles are isolated and not entangled, an intermediate domain where the micelles are partially entangled and a domain where the micelles are fully entangled. Flow curves of the transient networks of tunable morphology suggest that one can associate to the three domains distinct failures modes: a brittle mode, an intermediate mode and finally a ductile/shear banding mode, as the micelles grow. Thanks to this unique class of self-assembled networks, a continuous failure mode transition from brittle to ductile has been evidenced.