Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: Electrospun composite nanofiber sheets

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Ge, Jason J. ; Hou, Haoqing ; Li, Qing ; Graham, Matthew J. ; Greiner, Andreas ; Reneker, Darrell H. ; Harris, Frank W. ; Cheng, Stephen Z. D.:
Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: Electrospun composite nanofiber sheets.
In: Journal of the American Chemical Society. Bd. 126 (2004) Heft 48 . - S. 15754-15761.
ISSN 1520-5126
DOI: https://doi.org/10.1021/ja048648p

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Abstract

Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers; were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CdropN:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to similar to1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 X 10(-6)/degreesC along the axis of aligned nanofibers containing 20 wt % MWNTs.