Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

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El Rifaii, Karin ; Wensink, Henricus H. ; Dozov, Ivan ; Bizien, Thomas ; Michot, Laurent J. ; Gabriel, Jean-Christophe P. ; Breu, Josef ; Davidson, Patrick:
Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?
In: Langmuir. Bd. 38 (2022) Heft 48 . - S. 14563-14573.
ISSN 1520-5827
DOI: https://doi.org/10.1021/acs.langmuir.2c01821

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Abstract

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (approximate to 20 mu m) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (approximate to 100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.