Macromolecules, Vol.45, No.12, 5157-5166, 2012
Effect of Adsorbed Amphiphilic Copolymers on the Interfacial Activity of Superparamagnetic Nanoclusters and the Emulsification of Oil in Water
A series of sub-100 nm superparamagnetic iron oxide nanoparticles with amphiphilic poly(acrylic acid-b-butylacrylate); PAA-b-PBA) copolymer shells were synthesized and characterized by NMR spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and a superconducting quantum interference device (SQUID) to investigate the effect of the polymer structure on the interfacial tension for nanoparticles adsorbed at the dodecane-water interface. Large reductions in interfacial tension of up to 27.6 mN/m were measured at nanoparticle concentrations of 0.27 wt %, indicating significant nanoparticle adsorption and interaction between the oil and water molecules at the interface. The adsorption energy of the polymer-coated nanoparticles at the dodecane/water interface was determined from the interfacial tension and nanoparticle radius, and analyzed in terms of the structure of the polymer stabilizer. Furthermore, the equilibrium adsorption of amphiphilic copolymer-functionalized iron oxide nanoclusters at the oil water interface was determined by material balance from the concentration in the excess water phase and the known overall oil/water interfacial area. The formation and stabilization of oil droplets were on the order of 10 mu m in water with unusually low nanoparticle concentrations was explained in terms of the high interfacial activity of the particles.