Surface charging, polyanionic coating and colloid stability of magnetite nanoparticles

Abstract

The formation of small and large molecular polyanionic coating on the surface of magnetite (Fe 3O 4) nanoparticles and their role in the stability enhancement of aqueous magnetic fluids are compared. Magnetite was synthesized and stabilized with citric (CA) and humic (HA) acids. The macromolecular HA, a notable fraction of the natural organic matter (NOM), contains mainly carboxylic groups similarly to the CA, and both acids are able to form surface complexes on the ≡Fe–OH sites of iron oxides. The pH-dependent charge state of particles and their aggregation were quantified, and the enhanced salt tolerance of stabilized systems was studied. The dynamic light scattering (DLS) method was used to characterize colloidal stability under different conditions. The average particle size and electrophoretic mobility were measured, and the electrolyte tolerance was tested in coagulation kinetic measurements. The colloidal stability of magnetite dispersions depends sensitively on the pH and the concentration of organic acids present. The trace amount of HA neutralizes the positive charges on magnetite surface under acidic condition only in part, and so it promotes the aggregation between the particles having both positive sites and negative humate patches on the surface. Above the adsorption saturation, the surface becomes completely covered causing the reversal of charge sign and overcharging of nanoparticles. The magnetite nanoparticles become stabilized in a way of combined steric and electrostatic effects. The thicker layer of macromolecular HA provides better electrosteric stability than that of CA coating. However, in the presence of either CA or HA, the dissolution of magnetite is enhanced due to the complexation of iron ions in the aqueous medium.