We have systematically investigated the phase diagram of clay particles in water to understand the relation between the local and macroscopic properties and the structures of clay suspensions. We focused, in particular, on sodium Cloisite (CNa) particles at concentrations typically used in nanocomposites (concentrations from 1 to 4 wt %) and at an extended range of ionic strengths (10 -5 to 10 -2 M NaCl). The suspensions have been characterized using rheology and a combination of scattering techniques (neutrons, X-rays, and light). We demonstrate the existence of a liquid cluster phase at low clay and intermediate salt concentrations and provide new insight into the nature of the solidlike dispersions at low and high ionic strengths.

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We explored the behavior and the characteristics of xyloglucan polysaccharide chains extracted from tamarind seeds in aqueous media. The initial solubilization is achieved by using a 0.01 M NaOH solution. The absence of compact aggregates in the solution and the average molecular mass of the individual chains were unambiguously demonstrated by size exclusion chromatography with multi-angle light scattering detection. The composition and the stability of the solution were quantitatively checked over weeks by using liquid state nuclear magnetic resonance with DMSO as internal standard. The conformational characteristics of the chains were measured using nondestructive small-angle neutron scattering (SANS). The unambiguous determination of the Flory exponent (ν = 0.588) by SANS enabled us to directly prove that xyloglucan chains in water behave like semiflexible worm-like chains with excluded volume statistics (good solvent), contrary to most of the neutral water-soluble polymer chains that rather exhibit Gaussian statistics (θ-solvent). In addition to the Flory exponent, the persistence length l(p) and the cross section of the chains were also determined by SANS with utmost precision, with values of 80 and of 7 Å, respectively, which provides a complete description of the conformational characteristics of XG chains at all relevant length scales.

The present paper reports on dispersions of internally liquid crystalline particles, formed from monoglyceride and oil mixtures, stabilized with discrete disklike particles of Laponite clay. Small-angle X-ray scattering (SAXS) was used to probe the presence of dispersed particles as well as their internal liquid crystalline structure. The data were compared to scattering results of reference systems, namely, from the bulk as well as from well-defined particles formed with a polymer as the emulsifier. The submicrometer sizes of the various particles could be derived using dynamic light scattering (DLS). The possible mechanisms involved in the stabilization of each of the different phases by the Laponite platelets, including the role of the residual salt, are discussed. Time-resolved experiments were performed over 60 days in order to follow the evolution of both the internal structure and size of the particles. In particular, we discuss the peculiar behavior of the sample without added oil, where the cubosomes transform into hexosomes over time. The effect of the high pH induced by the Laponite platelets in water, which could result in a hydrolysis of the monoglycerides, was shown to be responsible for the observed cubosome-to-hexasome transition, as well as for the decrease in the lattice parameters.

Abstract. The concentration profiles of monomers and counterions in star-branched polyelectrolyte micelles are calculated through Monte-Carlo simulations, using the simplest freely-jointed chain model. We have investigated the onset of different regimes corresponding to the spherical and Manning condensation of counterions as a function of the strength of the Coulomb coupling. The Monte-Carlo results are in fair agreement with the predictions of Self-Consistent-Field analytical models. We have simulated a real system of diblock copolymer micelles of (sodium-polystyrene-sulfonate)(NaPSS)-(polyethylene-propylene)(PEP) with f=54 hydrophilic branches of N = 251 monomers at room temperature in salt-free solution and compared the calculated form factor with our neutron-scattering data.

We report the results of small-angle neutron scattering (SANS) studies on aqueous solutions of spherical polyelectrolyte micelles formed by association of charged-neutral diblock copolymers. The neutral moieties are found to self-assemble into small dense spheres (cores of the micelles) whose sizes are independent of the polymer concentration c. In the dilute regime, c < c * , where c * is the overlap concentration of the micelles, the conformation of the charged groups, which form the corona of the micelles, is found to be extended. A liquid-like order is observed over a wide concentration range spanning from the dilute regime to the concentrated regime. For c > c * , polyelectrolyte correlations appear at smaller spatial scales and coexist with the liquid-like order. These results suggest that for dense brushes, above c * , the rod-like statistics of the charged chains begin to disappear due to contraction of corona arms or by interpenetration of coronae. For less dense brushes, the charged chains are found to be extended up to concentrations far above c * , before the progressive development of polyelectrolyte correlations.

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We present an experimental study dedicated to understanding the behaviour of polyelectrolyte chains when salt goes into a polyelectrolyte brush. We use the ability of asymmetric neutral-charged diblock copolymers to anchor to a selective interface or to self-assemble in water, to examine polyelectrolyte brushes both in planar and in spherical geometries. Using neutron reflectivity, the monomer profile of planar brushes has been found to switch from a Gaussian profile to a parabolic profile, showing that at large spatial scale a salted planar brush behaves like a neutral one in good solvent. Using small angle neutron scattering, it is found that spherical brushes exhibit the same behaviour at a large spatial scale although polyelectrolyte chains remain rod-like at a small spatial scale whatever the salinity is. The charged chains inside a polyelectrolyte brush could be viewed as ‘surveyor’s chains’, which fold their rod-like segments of persistence length lp. In the last part, spherical polyelectrolyte brushes in contact have been examined. Their behaviour is discussed in terms of interdigitation or contraction of the brushes.