The Design and Control of Stability and Magnetic Properties of Imaging Nanoparticles

Yoon, Ki Youl
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There is significant interest in applying nanoparticle (NP) science to subsurface reservoirs to facilitate oil and gas recovery, image subsurface reservoirs, aid sequestration of CO2 and benefit environmental remediation. Imaging nanoparticles have been designed with long-term dispersion stability in brine and minimal retention in reservoir rock and with preferential adsorption at oil-water interfaces. Polymer-stabilized nanoparticles provide sufficient electrostatic repulsion for high colloidal stability, as characterized by the zeta potential. The small size of the clusters, superparamagnetic properties, and high salt tolerance are highly beneficial in various applications including magnetomotive and electromagnetic imaging and mapping of petroleum reservoirs. Superparamagnetic nanoclusters may be used in imaging in biomedicine and in mapping of petroleum reservoirs, by generating either ultrasonic or acoustic signals with oscillating magnetic motion. For a given magnetization per weight of iron oxide, nanoclusters with sub ~100 nm diameters experience a much larger magnetic force than that of the primary sub- 10 nm primary particles. Aqueous dispersions of 0.1-0.2 wt% superparamagnetic iron oxide nanoclusters were stabilized with citric acid, poly(acrylic acid) (PAA), or poly(styrene sulfonate-alt-maleic acid) (PSS-alt-MA) on the particle surface, with a high loading of ~90% iron oxide. For nanoclusters with only 12% (w/w) PSS-alt-MA electrosteric stabilization was sufficient even in 8 wt% NaCl. Both PAA and PSS-alt-MA were used to stabilize nanoclusters with controlled size during synthesis in aqueous media. To obtain a permanent coating on the surface of clusters cross-linking of the polymer for different cross-linking densities was applied. In this general and highly flexible approach, iron oxide nanoparticles may be formed with an adsorbed polymer stabilizer, which is then permanently bound to the surface via cross-linking. To investigate interfacial activity of nanoparticles, oil-in-water emulsions were stabilized with iron oxide nanoclusters or graphene oxide platelets. In each case, the stabilization was achieved by designing the hydrophilic/hydrophobic nature of surface coating. For oil/water emulsions, the droplet size was as low as ~1 micron diameter, and strongly shear-thinning rheology was observed. A series of sub-100 nm superparamagnetic iron oxide nanoparticles with amphiphilic poly(acrylic acid-b-butylacrylate), (PAA-b-PBA) copolymer shells was synthesized 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 obtained for a 0.27 wt% nanoparticle concentration indicating significant nanoparticle adsorption and interaction with 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, oil-in-water emulsions stabilized with graphene oxide nanoplatelets were found to remain stable for several months even at high salinity (up to 5 wt% NaCl, for pH = 2 to 10). The droplet sizes were as small as ~1 μm with a low nanoplatelet concentration of 0.2 wt%.