Atomic force microscopy study of montmorillonite dissolution under highly alkaline conditions

Montmorillonite dissolution under highly alkaline conditions (pH = 3.3; I= 0.3 M) was investigated by bulk dissolution methods and in situ atomic force microscopy (AFM). In bulk dissolution experiments, initial SiO2 concentrations were high, and a steady state was reached after 136 h. The dissolution rates derived from the edge surface area (ESA) at the steady-state condition at 30, 50 and 70 degrees C were 3.39 x 10(-12), 1.75 x 10(-11) and 5.81 x 10(-1)1 mol/m(2) s, respectively. The AFM observations were conducted under three conditions: (Run 1) short-term in situ batch dissolution at RT; (Run 11) long-term in situ flow-through dissolution at RT; and (Run III) long-term batch dissolution at 50 degrees C. The observed reductions in montmorillonite particle volume for Runs I and 11 were due primarily to edge-surface dissolution. The ESA-based dissolution rate for Run I (10(-9) mol/m(2) s) was three orders of magnitude faster than that for Run 11 (10(-12) mol/m(2) s). The rate obtained for Run II corresponded to the rate at the steady-state conditions in the bulk dissolution experiments. A small number of etch pits developed in Run III slightly increased the ESA of montmorillonite since most of the montmorillonite particles were separated into monolayers lacking three-dimensional periodicity. The ESA-based dissolution rate for Run III was 2.26 x 10(-11) mol/m(2) s. Dissolution rates based on long-term AFM observations could be directly compared with steady-state rates obtained from bulk dissolution experiments. The AFM observations indicated that dissolution occurred at edge surfaces; therefore, the ESA should be used to calculate the dissolution rate for montmorillonite under alkaline conditions. Dissolution rates of individual particles with different morphologies estimated by AFM were similar to rates estimated from bulk dissolution experiments.