Bentonite is to be used as a sealing material for long-term storage of radioactive waste. During permafrost periods the buffer may freeze, causing the following: montmorillonite dehydration, ice formation, and pressure build-up that may fracture the surrounding rock. No previous study has been done on freezing of bentonite in saline water. Using small and wide angle X-ray scattering, the present study aimed to increase understanding of the combined impact of salt and temperature on the hydration (swelling) of Wyoming montmorillonite. The basal spacing of the Na-montmorillonite was very dependent on the water content, while this was not the case for the Ca-montmorillonite (after reaching 19 Å). The basal spacing of the free-swelling Na-montmorillonite (34–280 Å) was estimated successfully using simple calculations. During freezing of Na-montmorillonite in NaCl solution, both ice and hydrohalite formed (at -50 and -100ºC). At starting concentrations ≥ 1.5 M the basal spacing was not affected by freezing. During freezing of Ca-montmorillonite in CaCl2 solution, ice formed; antarcticite formed only sporadically. The basal spacing of the Ca-montmorillonite at high NaCl concentrations (>1 M) was greater at -50 and -100ºC (18 Å) than at 20ºC (16 Å). The opposite was observed at low concentrations. This change was attributed to small amounts of salts introduced into the montmorillonite interlayer, hence changing the interlayer water properties. The montmorillonite hydration was also temperature dependent; decreasing temperature increased the hydration (as long as no ice was formed) and increasing the temperature decreased the hydration. This was attributed to the temperature impact on the entropy of the hydration reaction. This observation was also reproduced in an experiment up to 90ºC. A small amount of salt in the groundwater was noted to reduce significantly the potential problem of ice formation in bentonite sealings.

The planned final disposal repositories of spent nuclear fuel in several countries, including Finland, pose significant scientific challenges due to their extremely long lifespan. One of the key materials proposed for use in Posiva Oy's repository in Finland is MX-80 bentonite in a compacted, water-saturated state. Border cases of calcium and sodium forms of purified bentonite were included in this study. The MX-80 in the repository is expected to undergo cation exchange due to the composition of the groundwater. The clays were studied at different dry densities between 0.7 and 1.6 g cm–3. The microstructure of the water-saturated, compacted clays was investigated using small-angle X-ray scattering, nuclear magnetic resonance and transmission electron microscopy. Additionally, atomic force microscopy was used to characterize the shape and size of the fine-fraction clay platelets. As expected, the average shape of the fine fractions was smaller than the bulk material, but a more elongated shape was present in the purified material. Mainly due to sample density, the pore structure was noticeably different for the Na form of purified bentonite at 0.7 g cm–3 density, but at higher degrees of compaction, no significant differences were noted between the samples. The laboratory results obtained in this study could be useful for safety and performance analysis of this high-level waste repository where sodium bentonite is used and is expected to change its charge-compensating cation composition during the repository's lifetime. Microstructural data may be used in modelling of diffusion and sorption by surface complexation modelling, for example, or as a basis for mechanical and water transport models.

The evolution of textural properties of Na/Ca-bentonite from Wyoming (MX-80) was studied by adsorption of nitrogen, water vapour, and ethylene glycol monoethyl ether. Clay suspensions were heated at 80 and 300ºC for up to 9 months in the absence of or in the presence of Fe and/or Fe oxides. The treatment without Fe did not change the textural properties of the samples significantly. The treatment at 80ºC in the presence of Fe resulted in a considerable increase in the external surface areas of the samples. The total and external surface areas and swelling capacities of the samples decreased following the treatment at 300ºC in the presence of Fe and Fe oxides. In the case of larger additions of Fe, the treatment at 300ºC resulted in a considerable decrease in the total and external surface areas and swelling capacity of the sample and in the formation of a network of large-size pores, in which all the pores were connected.

Compacted bentonite is to be used as a buffer material between waste canisters and the bedrock in the deep geological disposal of high-level nuclear waste in several countries. In spite of the fact that such large bentonite systems have long equilibration times, estimation of the material properties and performance in repository conditions is often based on short-term, laboratory-scale experiments. Sample-preparation procedures in these experiments may differ from the natural evolution of the bentonite in the repository, however, affecting the bentonite properties. The present study reports the influence on the structure of clay tactoids of four different preparation procedures of water-saturated, compacted MX-80 bentonite samples using four target dry bulk densities. Small-angle X-ray scattering was used to illustrate the differences between the samples. The different treatments of the bentonite samples may lead to different structural features. Clear differences between low-density samples prepared using different procedures were observed. The influence of the preparation methods was less, but still noticeable, for the high-density samples.