Commercial Wet-Spun Singlewall and Dry-Spun Multiwall Carbon Nanotube Fiber Surface O-Functionalization by Ozone Treatment.

In this work, we demonstrate controlled introduction of O-functional groups on commercial carbon nanotube fibers (CNTFs) with different nanotube morphologies obtained by dry- and wet-spinning by treatment with gaseous ozone (O₃(g)). Our test samples were (1) wet-spun fibers of smalldiameter (1-2 nm) singlewall (SW)-CNTs and (2) dry-spun fibers containing large-diameter (20 nm) multiwall (MW)-CNTs. Our results indicate that SW-CNTFs undergo oxygenation to a higher extent than MW-CNTFs due to the higher reactivity of SW-CNTs with a larger curvature strain. Oxygenation resulting from O₃ exposure was evidenced as increase in surface O atomic% (at% by X-ray photoelectron spectroscopy, XPS) and as reductions in G/D (by Raman spectroscopy) as well as electrical conductivities due to changes in nanotube graphitic structure. By XPS, we identified the emergence of various types of O-functionalities on the fiber surfaces. After long duration O3 exposure (>300 s for SW-CNTFs and >600 s for MW-CNTFs), both sp² C═O (carbonyl) and sp³ C-O moieties (ether/hydroxy) were observed on fiber surfaces. Whereas, only sp³ C-O (ether/hydroxy) components were observed after shorter exposure times. O₃ treatment led to only changes in surface chemistry, while the fiber morphology, microstructure and dimensions remained unaltered. We believe the surface chemistry controllability demonstrated here on commercial fibers spun by different methods containing nanotubes of different structures is of significance in aiding the practical application development of CNTFs.