Multiple thin film formation from dilute mixtures of polyethyleneimine (PEI) and cetyltrimethylammonium bromide (CTAB)

Dilute mixtures of the water soluble polymer polyethyleneimine (PEI) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) form mesostructured thin films at the air/solution interface. In this paper we show that these films form spontaneously, reaching an equilibrium composition. When the film is removed, a new solid film rapidly reforms, with a similar morphology when inspected by Brewster angle microscopy (BAM). Successive removal of films lead to a series of structurally similar films, until the amount of surfactant in solution approaches the lower limit of film forming concentration. The results obtained using surfactant-selective potentiometry suggest that the incipient polymer:surfactant aggregates are in a position to migrate to the surface rapidly after film removal, prior to mesostructure formation. X-ray reflectivity indicates that films formed at different PEI:CTAB compositions retain mesophase regular structures with the same d-spacing feature, equal to 52.2A. Grazing incidence diffraction measurements indicate that films are composed of small crystallites arranged in a random powder fashion, developing a rough surface morphology evidenced by BAM. The central finding is that PEI:CTAB films form when the amount of CTAB in solution is higher than a critical film formation concentration, very close to the critical aggregation concentration (CAC), allowing the formation of several equilibrated films from the same growing solution.