Molecular Dynamics Simulation of Hydration and Swelling of Mixed-Layer Clays in the Presence of Carbon Dioxide

Abstract

Swelling of clay minerals is an important phenomenon that is relevant to many problems in geoscience, oil and gas reservoirs, geophysics, and engineering. The phenomenon is even more complex when carbon dioxide is also present. Since sequestration of CO2 in sedimentary rock has been under active consideration as a way of alleviating the increasing concerns over climate change for which CO2 is a prime culprit, studying swelling of clays minerals in the presence of CO2 has taken on added urgency. The swelling changes the permeability and porosity of porous formations, which in turn may lead to a reactivation of dormant fractures, triggering seismic activities, and opening up new pathways for CO2 to return to the porous formations’ surface. Although the large majority of sedimentary rocks contain various types of mixed-layer clays (MLCs) with intermixed stacking sequences of several types of distinct layers within a single crystal, the vast majority of the past experimental and computational studies of the swelling was focused on pure clays. We present the results of extensive molecular dynamics simulation of hydration and swelling of illite-montmorillonite (I-MMT) MLCs, the most common type of mixed clays, in the presence of both water and CO2 and various combinations of interlayer cations, Na+ and K+. To understand the differences with pure clays, we also report on the same phenomenon in the MMT only. At low CO2 concentrations in Na-MMT, which has its layers’ charge concentrated in its octahedral sheet, weak ion–surface interactions result in fully hydrated ions and, therefore, more extensive swelling than in I-MMT. Without CO2, adsorption of the cations at the illite surface increases the hydrophobicity of its surface. Thus, in the asymmetric interlayer of I-MMT, illite with stronger surface–ion interactions causes accumulation of cations near its surface, which limits their hydration and, therefore, controls swelling of the MLCs. Further inhibition of swelling of Na-MLC can be achieved by increasing the concentration of K+ in the interlayer. At higher CO2 concentrations, however, intercalation of water and CO2 results in a completely different behavior, since in the 2W and 3W hydration states, the hydrophobicity of the MMT surface is stronger than that of illite. Therefore, the density distributions of the intercalated molecules are considerably different from that with water only, which together with disruption of the water network by CO2 reduces the difference between the extent of swelling of the MLC and pure MMT.

Study of soil expansion characteristics in rainfall-induced red-bed shallow landslides: Microscopic and macroscopic perspectives

“…They found that ionic hydration was the main reason for the expansion of the flagstone crystal layer [ 18 ]. Gimmi and Churakov’s findings are consistent with those of Rahromostaqim and Sahimi, who experimentally investigated the hydration energies of various alkali metal ions and the surface hydration energies of montmorillonite [ 18 , 19 ]. However, these studies are still at the level of experimental or numerical calculation and do not involve the red-bed field; thus, the corresponding theoretical model of expansion of red-bed weathered soil needs to be studied.…”

“…For example, Kamal et al (2019) found through experiments that water and hydrochloric acid cause expansion of clay minerals such as kaolinite, illite and chlorite, causing damage to the formation [ 17 ]. Rahromostaqim et al (2019) found through numerical calculations that ion type has a great influence on the expansion of clay minerals [ 19 ]. This paper fills the gap in theoretical research and establishes a relationship between theory and practice.…”

Effect of Layer Charge Density on Hydration Properties of Montmorillonite: Molecular Dynamics Simulation and Experimental Study

“…Marry and Mignon studied the behavioral characteristics of different cations (Li + , Na + , and K + ) in the hydration process of montmorillonite by methods of MC and MD simulation, and found that as the water content between the smectite layers increased, Li + and Na + were easily separated from the montmorillonite interlayer, while K + moved to the surface of the siloxane tetrahedron and was bound to the surface [17,18,19]. Rahromostaqim compared the hydration and expansion properties of illite-montmorillonite (I-MMT) and Na-montmorillonite using molecular dynamics simulation, and found that at low CO 2 concentrations in Na-MMT, which has its layers’ charge concentrated in its octahedral sheet, weak ion-surface interactions result in fully hydrated ions and, therefore, more extensive swelling than in I-MMT [20]. Most researchers believe that montmorillonite with stronger hydration ability layer cations (such as Na + , Li + ) has higher expansion and hydrophilicity [21,22,23,24].…”

Molecular dynamics simulation and experimental study of micro‐structure and gel properties of single chain alkyl ammonium intercalated Na‐montmorillonite

“…25 According to the semi-cell structural formula described in section 2.1, 8a  4b  1c super-cell models were established. 13 The isomorphic substitution mainly occurs in octahedron (Mg 2+ substitutes Al 3+ ) and tetrahedron (Al 3+ substitutes Si 4+ ), 22,26 and always obeys Loewenstein's rule.…”