The modification before the stabilization process could tune the exothermic behavior and the structural evolution of PAN fibers during stabilization. In this study, we demonstrate that a rapid thermal pretreatment in nitrogen can effectively mitigate the exothermic behavior of PAN fibers, such as decreasing the initial temperature, broadening the exothermal peak, and decreasing the nominal heat release during heating the fibers in air. The color of fibers has shown gradual changes from white to light yellow, yellow and brown during thermal pretreatment in nitrogen with the increase of pretreating temperature and time. The differential scanning calorimetry (DSC), Fourier Transform Infrared Spectrometer (FTIR), X-ray diffraction (XRD), and Thermogravimetric Analysis (TG) characterization have been applied to analyze the thermal properties, chemical and physical structural difference between PAN, and thermally pretreated PAN fibers. The thermal pretreatment of PAN fibers in nitrogen could induce cyclization, dehydrogenation, and cross-linking reactions, in which the cyclization play an important role on improving the cyclization index of stabilized PAN fibers. Meanwhile, the pretreatment can result in noticeable changes of the aggregation structure of PAN fibers, as indicated by the increase of crystallinity and crystalline size. These structural modifications can benefit the main cyclization reaction during stabilization and enhance the carbon yield in resultant carbon fibers. The rapid thermal pretreatment in nitrogen could increase efficiency of modification on PAN fibers, and that could save much time and energy. It is beneficial to manufacture low-cost carbon fibers and to spread the applications of carbon fibers.

Thermal stabilization is a critical, yet time- and energy-consuming process during the preparation of PAN-based carbon fibers. In this work, automobile-grade carbon fibers with a 2.85 GPa tensile strength and a 203 GPa modulus are continuously produced with electron-beam (e-beam) irradiation pretreatment and 24 min thermal stabilization. Thermal and structural analyses reveal that e-beam irradiation can lower the onset temperature of the cyclization reaction and mitigate the heat release. Meanwhile, during the process of stabilization, e-beam irradiation can facilitate the evolution of both the chemical structure and the crystalline structure of polyacrylonitrile (PAN) fibers. Comparing to the industrial production of carbon fiber with a 40 min stabilization time, e-beam irradiated PAN fibers can achieve the same degree of stabilization with a 40% time savings.