54f Isotropic-Nematic Phase Transition of Single-Walled Carbon Nanotubes in Strong Acids

Pradeep Rai1, Robert A. Pinnick1, Nicholas Parra-Vasquez1, Virginia A. Davis2, Howard K. Schmidt3, Robert H. Hauge3, Richard E. Smalley3, and Matteo Pasquali1. (1) Department of Chemical and Biomolecular Engineering, MS-362, Rice University, 6100 Main Street, Houston, TX 77005, (2) Department of Chemical Engineering, Auburn University, 230 Ross Hall, Auburn, AL 36849-5127, (3) Department of Chemistry, MS-60, Rice University, 6100 Main Street, Houston, TX 77005

We present the first quantitative assessment of the maximum amount of nanotubes that can exist in the isotropic phase (φiso,max) of single-walled carbon nanotubes (SWNTs) in Brønsted-Lowry acids. We employ a centrifugation technique in conjunction with UV-Vis-nIR spectroscopy to quantify φiso,max, which is also the critical concentration of the isotropic-nematic transition of SWNTs in strong acids. Centrifugation of biphasic dispersions of SWNTs, i.e., acid dispersions consisting of an isotropic phase in equilibrium with an ordered nematic liquid crystalline phase, results in a clear phase separation where the isotropic phase is supernatant. UV-Vis-nIR absorbance measurements yields φiso,max, i.e, the maximum concentration of SWNTs that can exist in the isotropic phase in a given acid for a given SWNTs length distribution. At low SWNT concentration (below 200 ppm) in superacids, light absorbance in the range from 400 to 1400 nm scales linearly with concentration. This Beer's Law behavior yields calibration curves for measuring SWNTs concentration in acids. We find that the critical concentration of the isotropic-nematic transition increases with acid strength in accordance with the previously proposed sidewall protonation mechanism for dispersing SWNTs in acids.