In this article, we describe the rheology of Na montmorillonite suspensions as a function of pH, at constant ionic strength. The observed behavior is discussed quantitatively in terms of the potential energy of interaction between particles, keeping in mind the anisotropic nature of clay particles. The extended DLVO model that includes electrostatic, van der Waals, and polar acid-base contributions to the total energy is used. It is found that face-to-face interactions are virtually independent of pH, whereas edge-to-edge interactions are most attractive at the isoelectric point of edges (pH approximately 7). The most significant variations occur in face-to-edge potential energy, with strong attractions at pHG", the difference being larger at acid pH values. These results, in addition to potential energy calculations, suggest the existence of an elastic, coagulated structure up to pH 7, whereas as the pH is increased such structure is more relaxed because of electrostatic repulsions. Similar conclusions are reached when creep-recovery data are analyzed. Copyright 2000 Academic Press.