—Atomic force microscopy (AFM) is a novel method for measuring changes in clay swelling in situ at the tactoid level in an aqueous environment. While the swelling process has been directly observed at the mesoscale level for multi-tactoid aggregates and the associated pores, no method to date has allowed the direct observation of swelling dynamics at the nanoscale. In initial proof-of-concept studies, individual tactoids of a Na-exchanged nontronite (NAu-1) were imaged in a solution of 5 mM NaCl. When multiple line profiles were examined on the same tactoid, the changes in height varied and depended on which layers of the profile were transected, and demonstrated that AFM analyses can be used to directly probe intratactoid heterogeneity in the swelling process. To better visualize this heterogeneity, a method was developed to restrict AFM images to include only the portions of a tactoid above a threshold height. A comparison of the changes in these images for multiple threshold values revealed that swelling in one part of a tactoid may occur simultaneously with compression in another portion, which suggests that the encroachment of layers into intra-tactoid micropores can partially compensate for the overall volume change. Finally, to demonstrate the ability of this technique to monitor in situ swelling changes as the surrounding aqueous environment is modified, a tactoid of K-montmorillonite (SWy-2) was monitored during cation exchange as a KCl solution was replaced with NaCl. After exchange, a transition from the crystalline swelling regime to the osmotic regime was observed. Subsequent height profiles were unchanged for a period of several hours and indicated that the AFM measurements were stable in the absence of changes to the aqueous phase composition. Because this technique is the first method that allows the swelling of a single tactoid to be monitored in an aqueous solution, it complements the ensemble-averaged data obtained from diffraction and scattering techniques.

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