Silica-surfactant-polyelectrolyte film formation: evolution in the subphase

We have previously reported that robust mesostructured films will grow at the surface of alkaline solutions containing cetyltrimethylammonium bromide (CTAB), polyethylenimine (PEI), and silica precursors. Here we have used time-resolved small-angle X-ray scattering to investigate the structural evolution of the micellar solution from which the films form, at several different CTAB-PEI concentrations. Simple models have been employed to quantify the size and shape of the micelles in the solution. There are no mesostructured particles occurring in the CTAB-PEI solution prior to silica addition; however, after the addition of silicate species the hydrolysis and condensation of these species causes the formation of mesophase particles in a very short time, much faster than ordering observed in the film at the interface. The mesophase within the CTAB-PEI-silica particles finally rearranges into a 2D hexagonal ordered structure. With the aid of the previous neutron reflectivity data on films formed at the air/water interface from similar solutions, a formation mechanism for CTAB-PEI-silica films at the air/water interface has been developed. We suggest that although the route of mesostructure evolution of the film is the same as that of the particles in the solution, the liquid crystalline phase at the interface is not directly formed by the particles that developed below the interface.