The influence of oxygen-containing functional groups on the dispersion of single-walled carbon nanotubes in amide solvents.

Surface composition plays an important role in carbon nanotube dispersibility in different environments. Indeed, it determines the choice of dispersion medium. In this paper the effect of oxidation on the dispersion of HiPCO single-walled carbon nanotubes (SWNTs) in N-methyl-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-dodecyl-pyrrolidinone (N12P) and cyclohexyl-pyrrolidinone (CHP) was systematically studied. During the oxidation process, similar amounts of carboxylic acid and phenolic groups were introduced to mostly already existing defects. For each solvent the dispersion limits and the absorption coefficients were estimated by optical absorption analysis over a range of SWNT concentrations. The presence of acid oxygenated groups increased SWNT dispersibility in NMP, DMF and DMA, but decreased in N12P and CHP. The absorption coefficients, however, decreased for all solvents after oxidation, reflecting the weakening of the effective transition dipole of the π-π transition with even limited extension functionalization and solvent interaction. The analysis of the results in terms of Hansen and Flory-Huggins solubility parameters evidenced the influence of dipolar interactions and hydrogen bonding on the dispersibility of oxidized SWNTs.

Multicomponent solubility parameters for single-walled carbon nanotube-solvent mixtures.

We have measured the dispersibility of single-walled carbon nanotubes in a range of solvents, observing values as high as 3.5 mg/mL. By plotting the nanotube dispersibility as a function of the Hansen solubility parameters of the solvents, we have confirmed that successful solvents occupy a well-defined range of Hansen parameter space. The level of dispersibility is more sensitive to the dispersive Hansen parameter than the polar or H-bonding Hansen parameter. We estimate the dispersion, polar, and hydrogen bonding Hansen parameter for the nanotubes to be = 17.8 MPa(1/2), = 7.5 MPa(1/2), and = 7.6 MPa(1/2). We find that the nanotube dispersibility in good solvents decays smoothly with the distance in Hansen space from solvent to nanotube solubility parameters. Finally, we propose that neither Hildebrand nor Hansen solubility parameters are fundamental quantities when it comes to nanotube-solvent interactions. We show that the previously calculated dependence of nanotube Hildebrand parameter on nanotube diameter can be reproduced by deriving a simple expression based on the nanotube surface energy. We show that solubility parameters based on surface energy give equivalent results to Hansen solubility parameters. However, we note that, contrary to solubility theory, a number of nonsolvents for nanotubes have both Hansen and surface energy solubility parameters similar to those calculated for nanotubes. The nature of the distinction between solvents and nonsolvents remains to be fully understood.