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.

Thermotropic liquid crystalline copolyester fibers according to various heat treatment conditions

Thermotropic liquid crystal copolyester (TLCP) was synthesized using a melt polymerization method, with a molar ratio composition of 2,5-diethoxy terephthalic acid (ETA), hydroquinone (HQ), and p-hydroxybenzoic acid (HBA) of 1:1:3. TLCP exhibited nematic liquid crystalline mesophase and maintained nematic textures under all heat treatment conditions applied. The synthesized TLCP was processed into fibers using a capillary rheometer. The liquid crystalline mesophase, thermo-mechanical properties, and morphology of TLCP fibers obtained under various heat treatment conditions were investigated. The thermo-mechanical properties of the heat-treated fibers were improved compared to those of the as-spun fibers. The best results were obtained for TLCP fibers annealed at 230 °C for 9 h. The heat-treated fibers showed a well-developed microfiber morphology compared to the as-spun fibers. In the spun fibers, a skin–core morphology was observed regardless of the heat treatment conditions, and a well-developed fiber morphology better than the core area was observed in the skin area. The diameter of the fiber heat-treated at 230 °C for 9 h was approximately 60–110 nm.