Enhanced ordering in length-polydisperse carbon nanotube solutions at high concentrations as revealed by small angle X-ray scattering.

Carbon nanotubes (CNTs) are stiff, all-carbon macromolecules with diameters as small as one nanometer and few microns long. Solutions of CNTs in chlorosulfonic acid (CSA) follow the phase behavior of rigid rod polymers interacting via a repulsive potential and display a liquid crystalline phase at sufficiently high concentration. Here, we show that small-angle X-ray scattering and polarized light microscopy data can be combined to characterize quantitatively the morphology of liquid crystalline phases formed in CNT solutions at concentrations from 3 to 6.5% by volume. We find that upon increasing their concentration, CNTs self-assemble into a liquid crystalline phase with a pleated texture and with a large inter-particle spacing that could be indicative of a transition to higher-order liquid crystalline phases. We explain how thermal undulations of CNTs can enhance their electrostatic repulsion and increase their effective diameter by an order of magnitude. By calculating the critical concentration, where the mean amplitude of undulation of an unconstrained rod becomes comparable to the rod spacing, we find that thermal undulations start to affect steric forces at concentrations as low as the isotropic cloud point in CNT solutions.

Line Tension of Twist-Free Carbon Nanotube Lyotropic Liquid Crystal Microdroplets on Solid Surfaces.

Line tension, i.e., the force on a three-phase contact line, has been a subject of extensive research due to its impact on technological applications including nanolithography and nanofluidics. However, there is no consensus on the sign and magnitude of the line tension, mainly because it only affects the shape of small droplets, below the length scale dictated by the ratio of line tension to surface tension σ/τ. This ratio is related to the size of constitutive molecules in the system, which translates to a nanometer for conventional fluids. Here, we show that this ratio is orders of magnitude larger in lyotropic liquid crystal systems comprising micrometer-long colloidal particles. Such systems are known to form spindle-shaped elongated liquid crystal droplets in coexistence with the isotropic phase, with the droplets flattening when in contact with flat solid surfaces. We propose a method to characterize the line tension by fitting measured droplet shape to a macroscopic theoretical model that incorporates interfacial forces and elastic deformation of the nematic phase. By applying this method to hundreds of droplets of carbon nanotubes dissolved in chlorosulfonic acid, we find that σ/τ ∼ -0.84 ± 0.06 µm. This ratio is 2 orders of magnitude larger than what has been reported for conventional fluids, in agreement with theoretical scaling arguments.