Sedimentation Kinetics of Magnetic Nanoparticle Clusters: Iron Oxide Nanospheres vs Nanorods

A detailed study of the sedimentation kinetics of iron oxide nanoparticle (IONP) clusters composed of nanospheres and nanorods is presented. Measurements were performed to determine the absorbance of an IONP suspension undergoing sedimentation over time by using a UV-vis spectrophotometer with simultaneous monitoring of the hydrodynamic diameter of the clusters formed with dynamic light scattering (DLS). Mathematical analysis based on Happel's spherical and cylindrical models was conducted to reveal the relationship between the settling velocity of the IONP clusters and their packing density. For the case of IONP clusters composed of rodlike particles, two distinctive phases of sedimentation were recorded, with the occurrence of rapid sedimentation at the beginning of the process (phase I) followed by a slower settling rate (phase II). In sedimentation phase II, even though the nanorod clusters had a hydrodynamic size of >500 nm, which was much larger than that of the nanosphere clusters (∼200 nm), their settling velocity of 0.0038 mm/min was still slower than that of the nanosphere clusters. Such observations were mainly a result of the packing density differences between the formed clusters; due to the end-to-end particle interactions of nanorods, the nanorod clusters were less tightly packed and more permeable. In addition to the mathematical analysis, quartz crystal microbalance with dissipation (QCM-D) was employed to measure the "softness" of the IONP clusters formed, and this physical property can be further related to their packing density. This study illustrated that for a rapidly aggregating system, such as magnetic IONPs, not only do the particle shape and size uniformity contribute to the physical properties of the particle clusters formed but also the nature of the aggregation, either end-to-end and/or side-to-side, should be carefully considered when designing a colloidally stable IONP suspension.