Structural Organization of Na- and K-Montmorillonite Suspensions in Response to Osmotic and Thermal Stresses

Abstract

In order to understand the influence of salt concentration and temperature on the behavior and properties of clays used in drilling muds, we studied montmorillonite supensions (4 g clay/100 g solution) in 0.1, 0.5 and 1 M NaCl and KCl solutions. A fraction of each sample was heated to 200 °C in a closed vessel for 7 d, then cooled at room temperature (RT, 25 °C). Small-angle X-ray scattering (SAXS) spectra were recorded, for all the samples, at RT. The structure of the clay particles was determined by comparing the experimental intensity with the theoretical intensity computed from a model that took into account the number of layers per particle, the hydration state of the layers (0, l, 2, 3 or 4 water layers) and the order in the succession of these states. With this set of parameters, we can compute the mean statistical parameters M¯ (mean number of layers per particle), d¯ (mean interlayer distance) and δ¯²/d¯² (parameter describing the disorder of the distribution of interlayer distances). The evolution of these parameters shows that:

• 1) At low concentration (0.1 M NaCl or KCl), the samples do not consist of particles but of isolated layers (M = 1). The suspensions form gel-like structures. The difference between Na and K suspensions, or between heated and nonheated samples, is unnoticeable at the studied scale (5–500 Å).

• 2) An increase in salt concentration (from 0.1 to 0.5 M) brings the sample in a granular state: we notice the appearance of particles at 0.5 M (M¯ ≥ 25). Differences appear between NaCl and KCl suspensions, and the temperature effect becomes visible. Thus, we noticed that in NaCl suspensions, particles are composed of hydrated layers (1, 2, 3 or 4 water layers) and internal porosity (d > 30 Å), whereas suspensions in KCl are characterized by the presence of interlayer distances of 10 Å, that is, of collapsed layers. Particles in the KCl suspensions are much thicker than in the NaCl corresponding ones, and also less hydrated at the interlayer level as well as at the internal porosity level. Further increase in salt concentration (0.5 to 1 M) amplifies this effect. As far as temperature is concerned, its effect is to promote the clay dispersion by breaking up the particles, dehydrating and disordering them. This effect is more important for low salt concentration, that is, when the system is less stressed.