Reversible flocculation of nanoparticles by a carbamate surfactant

Fatty alkyldiamine readily reacts with CO₂ in aqueous solution at pH 12 to reversibly form surface active carbamate species. The carbamate can be reverted to the amine by exposure to N₂ and heat. In this work, a carbamate-based surfactant (Y12-carbamate) has been used to disperse and stabilize hydrophobic nanoparticles. This state could be regarded as the "on" state of a series of cycle. The nanoparticles were then flocculated when the carbamate groups were cleaved by exposure to N₂ and heating, corresponding to the "off" state. In a subsequent cycle, the nanoparticles were re-dispersed by exposure to CO₂, while the pH remained at 12. This cycle of re-dispersion and flocculation could be repeated two times without impairing the particle size. However, further cycles increased the particle size, indicating that all particles could not be completely re-dispersed. In addition, we also investigated the effect of pH on the colloidal stability with sodium Y12-carbamate, by measuring particle size and electrophoretic mobility. The results showed that pH strongly influenced the stability of the nanoparticles. Sodium Y12-carbamate stabilized the particles with a negative electrophoretic mobility at pH well above pKa whereas at pH close to pKa of Y12-amine (pKa = 9.0), the particles quickly flocculated, as a result of an ion-pair formation between Y12-ammonium and Y12-carbamate.