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Flexibility of nanolayers and stacks: implications in the nanostructuration of clays

Abstract : The basic structural units of adsorbing microporous materials such as clays and cementitious materials are flexible nanolayers. The flexibility of these layers is reported to play a crucial role in the structuration of these materials, potentially affecting therefore the thermo-mechanical behavior of such materials. Adsorbed fluids are structured in a discrete number of layers within the space between the nanolayers in these materials. This discrete nature of adsorption states may lead to micro-instabilities due to non-convex energy profiles. The transition between adsorption states may involve the bending of layers. Bending contributes to metastability, which is reported to be a potential source of the irreversibilities notably in clay behavior. In this paper, we determine the bending modulus of clay nanolayers by the combination of plate theory with molecular simulations of sodium montmorillonite. The case of clays is illustrative of the behavior of phyllosilicates (i.e. sheet-silicates) which are ubiquitous minerals in the Earth's crust. We discuss the conditions in which clay particles, i.e. a stack of nanolayers, can be viewed as thin plates. Estimations of the bending modulus according to the hydration state and dimensions of clay particles are provided. We analyze the implications of the flexibility of the layers in the behavior of a stack of layers as well as in the transitions between adsorption states. The energy barrier associated with bending of clay layers and the characteristic length of bending in such transitions are provided. Our results contribute to a better understanding of the nanostructure of layered adsorbing materials.
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Tulio Honorio, Laurent Brochard, Matthieu Vandamme, Arthur Lebée. Flexibility of nanolayers and stacks: implications in the nanostructuration of clays. Soft Matter, Royal Society of Chemistry, 2018, 14 (36), pp.7354 - 7367. ⟨10.1039/C8SM01359D⟩. ⟨hal-01896675⟩



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