Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties

TLDR

X‑ray diffraction patterns of <1 µm montmorillonite were modeled under controlled RH on Li‑, Na‑, K‑, Mg‑, Ca‑, and Sr‑saturated specimens, and heterogeneity was quantified by the standard deviation of the 00l reflection series (ξ), showing that hydration states are organized into two interstratified contributions rather than random distribution. Quantitative X‑ray diffraction analysis confirmed prior smectite hydration reports yet revealed systematic coexistence of contrasting layer types, demonstrating that smectite hydration is heterogeneous with partially segregated, interstratified contributions rather than a single homogeneous population.

Abstract

Hydration of the <1 μm size fraction of SWy-1 source clay (low-charge montmorillonite) was studied by modeling of X-ray diffraction (XRD) patterns recorded under controlled relative humidity (RH) conditions on Li-, Na-, K-, Mg-, Ca-, and Sr-saturated specimens. The quantitative description of smectite hydration, based on the relative proportions of different layer types derived from the fitting of experimental XRD patterns, was consistent with previous reports of smectite hydration. However, the coexistence of smectite layer types exhibiting contrasting hydration states was systematically observed, and heterogeneity rather than homogeneity seems to be the rule for smectite hydration. This heterogeneity can be characterized qualitatively using the standard deviation of the departure from rationality of the 00l reflection series (ξ), which is systematically larger than 0.4 Å when the prevailing layer type accounts for ~70% or less of the total layers (~25% of XRD patterns examined). In addition, hydration heterogeneities are not distributed randomly within smectite crystallites, and models describing these complex structures involve two distinct contributions, each containing different layer types that are interstratifed randomly. As a result, the different layer types are partially segregated in the sample. However, these two contributions do not imply the actual presence of two populations of particles in the sample.