Flocculation of Hematite with Polyacrylic Acid: Fractal Structures in the Reaction- and Diffusion-Limited Aggregation Regimes

Abstract

The structure of hematite aggregates in the presence of fairly monodisperse polyacrylic acid (PAA) with two different molecular weights (Mw= 1.36 × 106,Mw/Mn= 1.53;Mw= 3.69 × 104,Mw/Mn= 1.60) was studied using static light scattering (SLS). The fractal dimensions were calculated from the scattering exponents, after taking into account the finite size of aggregates, using exponential and Gaussian cutoff functions. Three flocculation regimes, namely, pre-DLA, DLA (diffusion-limited aggregation), and post-DLA, were defined based on the polymer concentration. In the DLA regime, fractal dimension values,Df= 1.84 ± 0.02 and 1.73 ± 0.02, were obtained using exponential and Gaussian cutoff functions, respectively. A fractal dimension of approximately 2.0 was found, as expected, in the pre-DLA regime (at PAA concentrations lower than the optimal dosage for a DLA regime) where the flocculation rate was reaction limited. In contrast, in the post-DLA regime, the flocculation was slow but the structure of aggregates was as tenuous as in the DLA regime with a fractal dimensionDf≈ 1.8. Moreover, for all three regimes, theDfvalues were independent of the molecular weights of PAA. The lower fractal dimension in post-DLA was probably due to the increased concentration of polymer chains between adjacent particles in aggregates. The steric hindrance favored tip-to-tip aggregation, leading to a more tenuous structure.