The self-assembly of two nonionic surfactants, pentaethylene glycol monododecyl ether (C12E5) and n-dodecyl-b-maltoside (b-C12G2), in the presence of a purpose-synthesized silica sol of uniform particle size (diameter 16 nm) has been studied by adsorption measurements, dynamic light scattering and small-angle neutron scattering (SANS) using a H2O/D2O mixture matching the silica, in order to highlight the structure of the surfactant aggregates. For C12E5, strong aggregative adsorption onto the silica beads, with a high plateau value of the adsorption isotherm above the CMC was found. SANS measurements were made at a series of loadings, from zero surfactant up to maximum surface coverage. It is found that the spherical core-shell model nicely reproduces the SANS data up to and including the local maximum at q = 0.42 nm-1 but not in the Porod region of high q, indicating that the surface area of the adsorbed surfactant is underestimated by the model of a uniform adsorbed layer. A satisfactory representation of the entire scattering profiles is obtained with the model of micelle-decorated silica beads, indicating that C12E5 is adsorbed as spherical micellar aggregates. This behaviour is attributed to the high surface curvature of the silica, which prevents an effective packing of the hydrophobic chains of the amphiphile in a bilayer configuration. For the maltoside surfactant b-C12G2 very weak adsorption on the silica beads was found. The SANS profile indicates that this surfactant forms oblate ellipsoidal micelles in the silica dispersion, as in the absence of the silica beads.

Reinforcement in nanocomposites with tunable structure: observation of chains in crowded environments

Lecture on scattering from self-assembled systems

Most metals and ceramics are aggregates of crystalline grains. Grain-boundaries (GBs) are two-dimensional lattice defects that separate the different grains and that control the bulk mechanical properties of polycrystalline materials. In particular, the sliding and the migration of GBs play important roles in the plastic deformation. Moreover the plastic behaviour depends crucially on the size of the crystallites. Colloidal polycrystals behave as most metals and ceramics at larger time and length scales, allowing to investigate their morphology and mechanical properties by direct 3-D visualization. In this talk I will show how the texture of a colloidal model polycrystalline system is tailored by adding controlled amounts of impurity and by changing the speed of crystallization. The morphology is analyzed quantitatively by confocal microscopy and for the first time the kinetics of growth of the crystallites, the distribution and the role of the impurities during solidification is observed proving theoretical predictions not detectable in molecular systems.

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.

The complexation of micelles or charged nanoparticles with neutral-charged block copolymers in aqueous solutions leads to the formation of colloidal superstructures also termed ‘colloidal complexes'. Their primary interest relies in their monodispersity in size, and in their increased domain of stability. In this review, the structural characterization by dynamic light scattering, cryo-TEM, and small angle neutron scattering is presented. Small angle neutron scattering results have been analyzed using numerical simulations – Monte Carlo or reverse Monte Carlo (RMC). Such simulations are useful to show the compatibility between different models of colloidal superstructures, and experiment. Our results have allowed us to propose a generic structure of complex colloids, made of a dense core of interacting colloids, bridged by polyelectrolyte blocks, and a hydrated corona. We have shown that such superstructures are formed systematically in these systems, with either micelles or nanoparticles, for different copolymers, and different charges. The text is in French.

A short introduction to soft condensed matter (polymers, colloids, surfactants) is presented, with particular emphasis to recent progres and applications of small angle scattering. The text is in French.