X-ray studies of interlayer water absorption and mesoporous water transport in a weakly hydrated clay.

The swelling of layered smectite clay particles consists of a change in the interlayer repetition distance ( d -spacing) as a function of temperature and humidity. For the synthetic clay sodium fluorohectorite, hydrodynamically stable hydration states with zero, one and two intercalated monolayers of water have previously been reported, with discrete jumps in d -spacing at the transitions between the hydration states. Keeping the temperature fixed and varying the ambient relative humidity, we find small reproducible d -spacing changes also within the hydration states. These changes are monotonous as a function of relative humidity, and one order of magnitude smaller than the shift in d -spacing that is typical of the transition between two hydration states. The reproducibility and reliability of this relative humidity controlled d -shift enables us to use the interlayer repetition distance d as a measure of the local humidity surrounding the clay particles. We provide an example of application of this observation: imposing a humidity gradient over a quasi-one-dimensional temperature-controlled sample, and using x-ray diffraction to record the d -spacing, we are able to extract profiles of the relative humidity along the sample length. Their time evolution describes the transport of water through the mesoporous space inside the clay. An analysis of the measured humidity profiles based on the Boltzmann transformation, under certain simplifying assumptions, yields a diffusive behavior that is either normal or possibly weakly anomalous.