RESUMEN
The formation of imogolite nanotubes is reported to be a kinetic process involving intermediate roof-tile nanostructures. Here, the structural evolution occurring during the synthesis of aluminogermanate double-walled imogolite nanotubes is in situ monitored, thanks to an instrumented autoclave allowing the control of the temperature, the continuous measurement of pH and pressure, and the regular sampling of gas and solution. Chemical analyses confirm the completion of the precursor's conversion with the release of CO2, ethanol, and dioxane as main side products. The combination of microscopic observations, infrared, and absorption spectroscopies with small and wide-angle X-ray scattering experiments unravel a unique growth mechanism implying transient single-walled nanotubes instead of the self-assembly of stacked proto-imogolite tiles. The growth formation of these transient nanotubes is followed at the molecular level by Quick-X-ray absoprtion specotrscopy experiments. Multivariate data analysis evidences that the near neighboring atomic environment of Ge evolves from monotonous to a more complex one as the reaction progresses. The following transformation into a double-walled nanotube takes place at a nearly constant mean radius, as demonstrated by the simulation of X-ray scattering diagrams. Overall, transient nanotubes appear to serve for the anchoring of a new wall, corresponding to a mechanism radically different from that proposed in the literature.
RESUMEN
Many ionic surfactants, such as sodium dodecyl sulfate (SDS) crystallize out of solution if the temperature falls below the crystallization boundary. The crystallization temperature is impacted by solution properties and can be decreased with the addition of salt. We studied SDS crystallization at liquid/vapor interfaces from solutions at high ionic strength (sodium chloride). We show that the surfactant crystals at the surface grow from adsorbed SDS molecules, as evidenced by the preferential orientation of the crystals identified by using grazing incidence X-ray diffraction. We find a unique time scale for the crystal growth from the evolution of structure, surface tension, and visual inspection, which can be controlled through varying the SDS or NaCl concentrations.
RESUMEN
HYPOTHESIS: Imogolite nanotubes (INTs) are unique anisometric particles with monodisperse nanometric diameters. Aluminogermanate double-walled INTs (Ge-DWINTs) are obtained with variable aspect ratios by controlling the synthesis conditions. It thus appears as an interesting model system to investigate how aspect ratio and ionic valence influence the colloidal behavior of highly anisometric rods. EXPERIMENTS: The nanotubes were synthesized by hydrothermal treatment for 5 or 20 days to modify the aspect ratio while the electrostatic interactions were investigated by comparing the colloidal stability in symmetric and asymmetric electrolytes. The phase behavior and their related microstructure were determined by optical observations and small-angle X-ray scattering measurements, coupled with interparticle distance modelling. FINDINGS: We revealed that colloidal suspensions of Ge-DWINTs prepared in NaCl are guided by repulsive double layer forces, undergoing different liquid crystal phase transitions before stiffen into a glass-like state. We found that the microstructure can be rationalized by taking into account the anisometric nature of the particles. By contrast, dispersions prepared with asymmetric electrolytes are governed by strong attractive forces and thus form space-filling gels containing large nanotubes aggregates.