Polymer/surfactant mixtures as dispersants and non-covalent functionalization agents of multiwalled carbon nanotubes: Synergism, morphological characterization and molecular picture

While surfactants and polymers have been independently investigated as agents to separate, disperse and stabilize carbon nanotubes (CNTs) in water, mixed polymer/surfactant (P/S) systems have been far less studied for those ends. In this work, we investigated the ability of various types of P/S mixtures to effectively separate multiwalled carbon nanotubes (MWNTs) in water, using rigorously controlled processing conditions. Two types of mixtures were explored: i) nonionic polymer (PVP, polyvinylpyrrolidone) and ionic surfactant (sodium dodecylbenzene sulfonate, SDBS, or cetyltrimethylammonium bromide, CTAB); and ii) ionic polymer (poly(diallyl dimethyl ammonium chloride), PDDA, and sodium polyacrylate, PAS) and nonionic surfactant (TX-100). Detailed, high precision dispersibility curves (concentration of dispersed nanotubes vs. total P/S concentration, at fixed S concentration) are presented for four P/S mixtures (PVP/SDBS, PVP/CTAB, PDDA/TX-100 and PAS/TX-100) and their respective individual components. Quantitative metrics extracted from the dispersibility curves allow for reliable comparisons between the systems. In all P/S mixtures, beneficial (synergistic) effects in nanotube dispersibility are observed compared to the individual components, with the exception of the PDDA/TX-100 one for which a detrimental (antagonistic) effect occurs. Morphological characterization of the as-obtained dispersions by scanning electron microscopy (SEM) shows a significant degree of nanotube separation by the P/S systems. Surface tension and zeta potential measurements provide further information on the interactions at play between the MWNTs and the P/S mixtures, allowing to conceive plausible mechanisms for the synergistic effects observed. P/S association may not only offer conditions for an enhanced dispersibility of CNTs but also expand the types of noncovalent, reversible functionalization required in many applications, such as the development of nanocomposite particles, films and coatings.