Chemical Force Microscopy Study on the Interactions of COOH Functional Groups with Kaolinite Surfaces: Implications for Enhanced Oil Recovery

Clay-oil interactions play a critical role in determining the wettability of sandstone oil reservoirs, which, in turn, governs the effectiveness of enhanced oil recovery methods. In this study, we have measured the adhesion between -COOH functional groups and the siloxane and aluminol faces of kaolinite clay minerals by means of chemical force microscopy as a function of pH, salinity (from 0.001 M to 1 M) and cation identity (Na+ vs. Ca2+). Results from measurements on the siloxane face show that Ca2+ displays a reverse low-salinity effect (adhesion decreasing at higher concentrations) at pH 5.5, and a low salinity effect at pH 8. At a constant Ca2+ concentration of 0.001 M, however, an increase in pH leads to larger adhesion. In contrast, a variation in the Na+ concentration showed less effect in varying the adhesion of -COOH groups to the siloxane face. Measurements on the aluminol face showed a reverse low-salinity effect at pH 5.5 in the presence of Ca2+, whereas an increase in pH with constant ion concentration resulted in a decrease in adhesion for both Ca2+ and Na+. Results are explained by looking at the kaolinite's surface complexation and the protonation state of the functional group, and highlight a more important role of the multicomponent ion exchange mechanism in controlling adhesion than the double layer expansion mechanism.