In this article,
we revisit the colloidal stability of clay imogolite nanotubes by
studying the effect of electrostatic interactions on geo-inspired
synthetic nanotubes in aqueous dispersions. The nanotubes in question
are double-walled aluminogermanate imogolite nanotubes (Ge-DWINTs)
with a well-defined diameter (4.3 nm) and with an aspect ratio around
4. Surface charge properties are assessed by electrophoretic measurements,
revealing that the outer surfaces of Ge-DWINT are positively charged
up to high pH values. A series of Ge-DWINT dispersions have been prepared
by osmotic stress to control both the ionic strength of the dispersion
and the volume fraction in nanotubes. Optical observations coupled
to small and wide-angle X-ray scattering (SAXS/WAXS) experiments allow
us to unravel different nanotube organizations. At low ionic strength
(IS < 10–2 mol L–1), Ge-DWINTs
are fully dispersed in water while they form an arrested gel phase
above a given concentration threshold, which shifts toward higher
volume fraction with increasing ionic strength. The swelling law,
derived from the evolution of the mean intertube distance as a function
of the nanotube concentration, evidences a transition from isotropic
swelling at low volume fractions to one-dimensional swelling at higher
volume fractions. These results show that the colloidal stability
of Ge-DWINT is driven by repulsive interactions for ionic strengths
lower than 10–2 mol L–1. By contrast,
higher salt concentrations lead to attractive interactions that destabilize
the colloid suspension, inducing nanotube coagulation into larger
structures that settle over time or form opaque gels. Detailed simulations
of the WAXS diagram reveal that aggregates are mainly formed by an
isotropic distribution of small bundles (less than four nanotubes)
in which the nanotubes organized themselves in parallel orientation.
Altogether, these measurements allow us to give the first overview
of the phase diagram of colloidal dispersions based on geo-inspired
imogolite-like nanotubes.