Substantial improvement of nanotube processability by freeze-drying

As-produced carbon nanotubes often contain a fraction of impurities such as metal catalysts, inorganic supports, and carbon by-products. These impurities can be partially removed by using acidic dissolution. The resulting nanotube materials have to be dried to form a powder. The processability of nanotubes subjected to regular (thermal vaporisation) drying is particularly difficult because capillary forces pack and stick the nanotubes irreversibly, which limits their dispersability in polymeric matrices or solvents. We show that this dramatic limitation can be circumvented by using freeze-drying instead of regular-drying during nanotube purification process. In this case, the nanotubes are trapped in frozen water which is then sublimated. As a result the final powder is significantly less compact and, more important, the nanotubes can be easily dispersed with no apparent aggregates, thereby greatly enhancing their processability, e.g., they can be used to make homogeneous composites and fibers. Results from coagulation spinning from water-based dispersions of regularly-dried and freeze-dried nanotubes are compared. We also show that freeze-dried materials, in contrast to regularly-dried materials, can be dissolved in organic polar solvents using alkali-doped nanotubes. High resolution TEM and XRD analysis demonstrate that the nanotube structure and quality are not affected at the nanoscale by freeze-drying treatments.