Use of complementary neutron techniques in studying the effect of a solid/liquid interface on bulk solution structures

By appropriate combination of neutron scattering techniques, it is possible to obtain structural information at various distances from a solid/liquid interface and thus probe in some detail how the surface structures evolve into bulk structures. We have used neutron reflectometry (NR) with a newly developed shear cell, near surface small angle neutron scattering (NSSANS) again in combination with the new shear cell, and regular small angle neutron scattering (SANS) with a standard Couette shear cell to probe the structures formed in our aqueous surfactant systems and how they react to a flow field, particularly in the near surface region of a solid/liquid interface. We present data for a 20mM aqueous solutions of 70% cetyltrimethylammonium 3,5-dichlorobenzoate (abbreviated CTA3,5ClBz) and 30% CTAB. This system forms a very viscoelastic solution containing long threadlike micelles. NR only probes to a depth of about 0.5 {mu}m from the surface in these systems and clearly indicates that adsorbed onto the surface is, surfactant layer which is insensitive to shear. The depth probed by the NSSANS is on the order of 20-30 {mu}m and is determined by the transmission of the sample, the angle of incidence, and the wavelength. In this region, the rods align under shear into a remarkably well ordered hexagonal crystal. The SANS from the Couette cell averages over the entire sample, so that the signal is dominated by scattering from the bulk. While the near surface hexagonal structure is clearly visible, these data are not consistent with the crystal structure persisting throughout the bulk, leading to the postulate that the bulk structure is a two dimensional (2D) liquid where the rods align with the flow, but do not order in the other two dimensions

Structure factor of polymers interacting via a short range repulsive potential: application to hairy wormlike micelles

We use the Random Phase Approximation (RPA) to compute the structure factor, S(q), of a solution of chains interacting through a soft and short range repulsive potential V. Above a threshold polymer concentration, whose magnitude is essentially controlled by the range of the potential, S(q) exhibits a peak whose position depends on the concentration. We take advantage of the close analogy between polymers and wormlike micelles and apply our model, using a Gaussian function for V, to quantitatively analyze experimental small angle neutron scattering profiles of semi-dilute solutions of hairy wormlike micelles. These samples, which consist in surfactant self-assembled flexible cylinders decorated by amphiphilic copolymer, provide indeed an appropriate experimental model system to study the structure of sterically interacting polymer solutions