Phase behavior and shear alignment in SWNT-surfactant dispersions

The effect of single-walled carbon nanotubes (SWNT) on the phase behavior of the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous solutions is investigated at room temperature. Small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM) are used for characterization of bulk dispersions and nanometrically thin films. Additional carbonaceous additives (fullerenes, multi-walled carbon nanotubes, and carbon black) serve as reference systems. It is found that dispersions of carbonaceous additive (excluding fullerenes) at intermediate surfactant concentrations (below the liquid-crystalline region of the native surfactant) induce demixing and macroscopic phase separation in otherwise homogeneous solutions of CTAB. Two coexisting liquid phases of similar CTAB concentrations are observed, with the carbonaceous species residing within the lower phase. At high CTAB concentrations (liquid-crystal region) the SWNTs are found to incorporate into the ordered lyotropic liquid-crystalline phase while preserving the native d-spacing. Investigation of nanometrically thin films at intermediate surfactant concentrations under external shear reveals shear-induced structure (SIS) in the presence of minute amounts of SWNTs. The effect is found to be exclusive to SWNT and does not occur in dispersions of other carbonaceous additives.