Heteroaggregation of Multiwalled Carbon Nanotubes and Hematite Nanoparticles: Rates and Mechanisms

The heteroaggregation rates of negatively charged multiwalled carbon nanotubes (CNTs) and positively charged hematite nanoparticles (HemNPs) were obtained over a broad range of nanoparticle distributions using time-resolved dynamic light scattering (DLS). Binary systems comprising CNTs and HemNPs were prepared using low ionic strength solutions to minimize the concurrent occurrence of homoaggregation. To elucidate the mechanisms of heteroaggregation, the structures of CNT-HemNP aggregates were observed using cryogenic transmission electron microscopy (cryo-TEM). An initial increase in the CNT concentration, while keeping the HemNP concentration constant, resulted in a corresponding increase in the rate of heteroaggregation, which occurred through the bridging of HemNPs by CNT strands. At the optimal CNT/HemNP mass concentration ratio (CNT/HemNP ratio) of 0.0316, the heteroaggregation rate reached 3.3 times of the HemNP homoaggregation rate in the diffusion-limited regime. Increasing the CNT/HemNP ratio above the optimal value, however, led to a dramatic decrease in the growth rate of heteroaggregates, likely through a blocking mechanism. In the presence of humic acid, the trends in the variation of the heteroaggregation rate with CNT/HemNP ratio were similar to that in the absence of humic acid. However, as the humic acid concentration was increased, the maximum aggregate growth rate decreased due to the lessening in the available surface of the HemNPs that CNTs can attach to through favorable electrostatic interaction.