Mechanical and Bonding Behaviors Behind the Bending Mechanism of Kaolinite Clay Layers

[Image: see text] The density functional theory-based calculations were performed on stripe models of the single kaolinite layer. The calculations helped to explain why halloysite mineral, a member of the kaolinite group existing in a tubular form, has rolled tubes only in one way. In that form, aluminol octahedral sheet, terminated by surface hydroxyl groups, represents the inner surface of the nanotubes. The bending models with the inner surface formed by the SiO tetrahedral sheet showed significant structural instability with monotonically increasing strain energy as a function of the curvature. In contrast, for the bending models with the octahedral sheet as the inner surface, stabilization energetic minima were found at curvatures of about 10 nm. The calculations were also performed on the individual sheets (tetrahedral and octahedral) of the kaolinite layer to show their contribution to the bending strain. We found that the decrease of the bending energy and the layer stabilization with respect to the planar configuration for curvatures with radii R(C) > ∼5 nm can be attributed mainly to three factors—(i) better match between octahedral and tetrahedral sheets, (ii) local structural changes of the SiO and AlOH polyhedral units, and (iii) increasing effectivity of hydrogen bonding of the outer surface OH groups.