Evolution of Microstructure and Performance in Polyacrylonitrile Precursor Fibers: A Comparison of Spinning Processes

The microstructure of polyacrylonitrile (PAN) precursor fibers has a profound influence on the performance of carbon fibers and depends on the spinning processes and processing conditions. This study compared the evolution of the microstructures and performance of PAN fibers between the wet-spinning and dry-jet wet-spinning processes, utilizing scanning electron microscopy, small/wide-angle X-ray scattering, dynamic mechanical analysis, and single-fiber tensile testing. Both spinning processes promoted the oriented alignment of microfibrils and fibrils, improved the crystal arrangement and molecular regularity, and facilitated the transition from a two-phase (crystalline/amorphous) structure to a single-phase structure, thereby gradually improving the fibers' elastic character and mechanical properties. However, wet-spun fibers exhibited inherent defects (skin-core structure and large voids), which caused surface grooves, radial mechanical heterogeneity, and low breaking elongation during post-spinning. In contrast, dry-jet wet-spun fibers initially had a smooth surface and a homogeneous radial structure, which evolved into well-oriented, radially homogeneous structures during post-spinning. Furthermore, the dry-jet wet-spinning process produced greater increases in crystallinity (46%), crystal size (258%), and orientation index (146%) than the wet-spinning process did. The dry-jet wet-spinning process's superiority in forming and optimizing the fiber microstructure gives it greater potential for producing high-quality PAN precursor fibers.