Molecular Atomistic Simulations of Clay Swelling in Water Dispersions

Abstract

An atomistic model has been constructed for a dimeric montmorillonite type clay aggregate. The solid was supposed to be dispersed in water. The surrounding aqueous phase was modified from pure water to either salt or polymer solution, and finally represented by a mixed solution containing electrolytes and polyols. A combined energy minimisation procedure followed by a 100 ps real time molecular dynamic simulation was performed on each amorphous cell modelling the solid dispersion. 3D periodic boundary conditions were established to ensure fluid spatial continuity and the calculations proceeded at room temperature. Sodium, potassium and calcium chlorides were tested as shale swelling inhibition additives. The lower hydration energy cation K⁺ was the most effective swelling inhibitor. The adsorption of poly(propylene glyco)s to the ideal smectite surface was also studied. Their tendency to remain adsorbed was associated with the irreversibility of the polymer adsorption process. The conformational changes obtained for organic molecules were responsible for the final orientation of the clay sheets. So it was possible to conclude from qualitative observations that intramolecular interactions may determine a clay dispersion–agglomeration transition by modifying the system entropy. Finally, it was also concluded that specific combinations of additives could enhance their individual capabilities by synergistic effects, determining the effectiveness for some water-based mud formulations.