Supramolecular structure of highly oriented wet-spun polyacrylonitrile fibers used in the preparation of high-performance carbon fibers

Highly oriented polyacrylonitrile (PAN) fibers, which are used in the preparation of high-performance carbon fibers, were prepared via a wet spinning process. The supramolecular structure-i.e., the degree of crystallinity, crystal size, and crystallite orientation-of the PAN fibers was characterized by X-ray diffraction (XRD) using fiber and powder techniques. Two equatorial diffraction peaks with 2 theta similar to 17 degrees and 29.5 degrees were observed in the fiber XRD patterns, which confirmed that the crystalline structure of the PAN fibers was pseudohexagonal with only two-dimensional order in the transverse direction. The powder XRD patterns were resolved into three constituent Lorentz peaks to determine the relative degree of crystallinity. In order to increase the reproducibility of the value for the crystallinity of the fibers, the Gupta-Singhal method was modified by assuming that the degree of crystallinity could be determined from the area under peak 1 (with 2 theta similar to 17 degrees), rather than the combined area of peaks 1 and 3. The evolution of the supramolecular structure of the PAN fibers during the spinning process was also investigated. Results indicated that drying and steam stretching play important roles in the formation and growth of the crystalline structure of the PAN fibers, while the orientation of the structure was only strongly related to the degree of stretching. The effects of the supramolecular structure on the thermal properties and mechanical properties of the PAN fibers were also studied. The perfection of the supramolecular structure influenced the feasibility of cyclization reactions within the PAN fibers and the thermal decomposition of those fibers. The mechanical properties of the PAN fibers were significantly enhanced by increasing the perfection of the supramolecular structure.