Lyotropic structures in a thermotropic liquid crystal.

We have investigated the nature of didodecyldimethylammonium bromide (DDAB)/water aggregates dispersed in 4-n-pentyl-4'-cyanobiphenyl thermotropic liquid crystal (5CB). The structure of this microemulsion has been probed by small-angle neutron and X-ray scattering experiments far above the nematic-to-isotropic phase transition temperature of the solvent. Our data show that the stability of this system is controlled by strong attractive van der Waals interactions between spherical inverted micelles. These interactions also explain why other swollen mesophases in related cosurfactant/DDAB/water/5CB phase diagrams are not observed. When approaching the isotropic-to-nematic phase transition, scattering experiments additionally confirm the predominance of an increasing attractive interaction due to the 5CB paranematic fluctuations.

Self-diffusion and collective diffusion of charged colloids studied by dynamic light scattering.

A microemulsion of decane droplets stabilized by a nonionic surfactant film is progressively charged by substitution of a nonionic surfactant molecule by a cationic surfactant. We check that the microemulsion droplets remain identical within the explored range of volume fraction (0.02-0.18) and of the number of charges per droplet (0-40). We probe the dynamics of these microemulsions by dynamic light scattering. Despite the similar structures of the uncharged and charged microemulsions, the dynamics are very different. In the neutral microemulsion, the fluctuations of polarization relax, as is well-known, via the collective diffusion of the droplets. In the charged microemulsions, two modes of relaxation are observed. The fast one is ascribed classically to the collective diffusion of the charged droplets coupled to the diffusion of the counterions. The slow one has, to our knowledge, not been observed previously neither in similar microemulsions nor in charged spherical colloids. We show that the slow mode is also diffusive and suggest that its possible origin is the relaxation of local charge fluctuations via the local exchange of droplets bearing different numbers of charges. The diffusion coefficient associated with this mode is then the self-diffusion coefficient of the droplets.

Analysis by the two-fluids model of the dynamical behavior of a viscoelastic fluid probed by dynamic light scattering.

The dynamic properties of a model transient network have been studied by dynamic light scattering. The network is formed by microemulsion droplets linked by telechelic polymers (modified hydrophilic polymers with two grafted hydrophobic stickers). We compare the properties of two networks that are similar but for the residence time of the hydrophobic stickers in the droplets. The results are interpreted according to the so-called two-fluids model, which was initially developed for semidilute polymer solutions and which we extend here to any Maxwellian viscoelastic medium characterized by its elastic modulus and terminal time as measured by rheology. This model is found to describe consistently and quantitatively the experimental observations.

Self-diffusion and collective diffusion in a model viscoelastic system.

We use dynamic light scattering (DLS) and fluorescence recovery after pattern photobleaching (FRAPP) to investigate the dynamics of a model transient network made of an oil-in-water droplet microemulsion to which small amounts of a telechelic polymer are added. The DLS correlation functions exhibit three relaxation modes. The two first modes can be interpreted quantitatively in the frame of the classical De Gennes-Brochard theory of DLS in viscoelastic system. The third, slower mode is diffusive and arises from the ternary character (droplets, polymers, and water) of the system. By contrast, the pattern relaxation in FRAPP exhibits a single-, slow-exponential decay with a characteristic time proportional to the squared inverse scattering vector: the corresponding self-diffusion coefficient of the droplets is found to be close to the diffusion coefficient characterizing the third mode in DLS. We interpret these results in terms of the coupled relaxation of the concentration fluctuations of the polymers and the droplets.