Freezing and thawing of montmorillonite — A time-resolved synchrotron X-ray diffraction study

The evolution of phases over time during freezing and thawing of unconfined Na- and Ca-montmorillonites (Wyoming, MX-80) was studied with time-resolved synchrotron X-ray diffraction. The clay samples were: (i) powder equilibrated to ambient atmosphere and (ii) pastes of 30 mass% montmorillonite in pure water. The phases were characterised in-situ using a stream of nitrogen gas for temperature control.The behaviour of montmorillonite during freezing and thawing is important in final repositories for spent nuclear fuel that are using bentonite as a buffer material.The Na-montmorillonite equilibrated to ambient atmosphere (one-layer hydrate) was unaffected by freezing down to − 50 °C. The Ca-montmorillonite equilibrated to ambient atmosphere (two-layer hydrate) showed a minor decrease in basal spacing (0.11 Å) by freezing down to − 50 °C. The magnitude of the decrease in basal spacing was high compared to the thermal contraction of the similar minerals muscovite and pyrophyllite and some dehydration of the clay was likely to be involved. Wet Na-montmorillonite in pure water was highly affected by freezing causing the osmotic phase to collapse during ice formation to 19 Å (three-layer hydrate) and later to a mixture of two and three-layer hydrates (− 15 °C) and at lower temperatures to two-layer hydrate (16 Å, − 50 °C).The Ca-montmorillonite in pure water was present as a 19 Å three-layer hydrate at + 20 °C and expanded upon cooling, producing two partly overlapping 001 reflections corresponding to three and four-layer hydrates prior to the ice formation. A mean d-value of the 002 peaks of the four-layer hydrate was determined to be 10.8 Å, which corresponded to a basal spacing of 21.6 Å. To our knowledge this is the first time a distinct four-layer-water hydrate is reported for Ca-montmorillonite in pure water. After the ice formation started, the montmorillonite was dehydrated to three-layer hydrate and at − 15 °C to a mixture of two and three-layer hydrates. At − 50 °C only two-layer hydrate was present.The ice formation and the dehydration of the montmorillonite occurred simultaneously. The effects of freezing on the montmorillonite were shown to be reversible during the thawing.The two dimensional diffraction rings gave information on the ice texture. The highly dispersed Na-montmorillonite (high surface area) in pure water facilitated the nucleation of the ice crystals and gave rise to uniformly sized crystals, while the Ca-montmorillonite (not dispersed, lower surface area) gave rise to non-uniformly sized ice crystals.