The swelling properties of smectite-type clay particles (including montmorillonite) are of interest in various industries. A fundamental understanding of the surface properties of smectite particles at the sub-micron level would facilitate investigation of the effect of distributed properties such as charge and elemental composition. Swelling and delamination of SWy-2 Na-montmorillonite (Na-Mnt) nano-clay particles were studied here using size distributions obtained by sedimentation field-flow fractionation (SdFFF). Fractions were examined by electron microscopy and inductively-coupled optical emission spectroscopy (ICP-OES). Two distinct populations were observed in the size distribution of SWy-2 Na-Mnt particles (bimodal size distribution), with mean equivalent spherical diameters of ~60 nm and 250 nm, respectively. In contrast, the size distribution of STx-1 Ca-montmorillonite (Ca-Mnt) particles showed only one peak with a mean equivalent spherical diameter of ~410 nm, which changed to 440 nm after 4 days of hydration. Analyses of the fractions by ICP-OES obtained along the size distribution of Na-Mnt showed an abundance of Ca and Mg in the fractions below 250 nm, and confirmed the presence of Fe and Mg as isomorphous substituents. Electron micrographs of the fractions obtained from Na-Mnt size distributions were used to calculate the thickness of the clay particles. Bridging forces between pure or Mg-substituted montmorillonite and either Ca2+ or Na+ were calculated using semi-empirical methods. The results demonstrated that swelling and delamination of Na-Mnt clay particles are dictated by properties such as elemental composition and surface charge which are distributed along the size distribution.

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