Ordered phases containing single-walled carbon nanotubes (SWNTs) are essential to exploit the highly anisotropic properties of such nanoparticles. Knowledge of the phase behavior for the above dispersions is therefore needed. Unfortunately, the processing of nanotubes at high concentration remains experimentally challenging. To date, solvent evaporation and ultracentrifugation procedures have been used to increase the volume fraction of carbon nanotubes and obtain (pseudo)-binary phase diagrams. We present here a novel phase separation strategy, allowing investigations of the phase behavior of concentrated dispersions of DNA-stabilized carbon nanotubes. This strategy is based on the osmotic compression due to added polymers such as sodium dextransulfate (SDxS) or polyethylene glycol (PEG) and on the control of the ionic strength. The phase behavior of the compressed DNA/SWNTs complexes is analyzed and discussed. It is observed that added polymers induce the separation of a SWNT-rich anisotropic phase in equilibrium with an isotropic polymer-rich one. The volume fraction of the ordered phase can be controlled by the concentration of added polymer, making this strategy efficient for investigations of concentrated nanotube dispersions and developments of novel materials based on the anisotropic phases containing such nanoparticles
Drying graphene oxide (GO) films are subject to extensive wrinkling, which largely affects their final properties. Wrinkles were shown to be suitable in biotechnological applications; however, they negatively affect the electronic properties of the films. Here, we report on wrinkle tuning and patterning of GO films under stress-controlled conditions during drying. GO flakes assemble at an air-solvent interface; the assembly forms a skin at the surface and may bend due to volume shrinkage while drying. We applied a modification of evaporative lithography to spatially define the evaporative stress field. Wrinkle alignment is achieved over cm areas. The wavelength (i.e., wrinkle spacing) is controlled in the μm range by the film thickness and GO concentration. Furthermore, we propose the use of nanoparticles to control capillary forces to suppress wrinkling. An example of a controlled pattern is given to elucidate the potential of the technique. The results are discussed in terms of classical elasticity theory. Wrinkling is the result of bending of the wet solid skin layer assembled on a highly elastic GO dispersion. Wavelength selection is the result of energy minimization between the bending of the skin and the elastic deformation of the GO supporting dispersion. The results strongly suggest the possibility to tune wrinkles and patterns by simple physicochemical routes.
Carbon nanotubes were dispersed in a sodium dodecylsulfate/decanol/water nematic fluid. The long-term stability of the dispersions is ensured by the small density gradients existing between nanotubes and the nematic fluid, and by its viscosity, as well. Presumably, surfactant or nematic micelles adsorb onto nanotubes and concur to stabilize them. A Rheo 2 H NMR characterization was performed. It was supported by classical 2 H quadrupole splitting and pulsed field gradient spin−echo NMR, allowing to ascertain the diffusive trends therein. The nematic fluid shows uniaxial spectral profiles and marked diffusion anisotropy. No such effects were observed in nanotube-containing nematic dispersions. In addition, the measured water self-diffusion values are substantially lower than the pure nematic fluid. In the absence of shear, dispersed nanotubes do not modify the quadrupole splitting amplitude, but affect the spectral profiles. The reasons for the observed behavior are briefly outlined. In the presence of shear, the spectral modifications are substantial and lead to the onset of isotropic dispersions, after long-time shearing.
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