Insights into the carbonization mechanism of PAN-derived carbon precursor fibers and establishment of a kinetics-driven accelerated reaction template for atomistic simulation.

To better understand the chemistry behind the carbonization process of the polyacrylonitrile (PAN)-based precursor fibers and provide a more authentic virtual counterpart of the process-inherited model for process optimization and rational performance design, we develop arrow-pushing reaction routes for primary exhaust gas product (H2O/H2/HCN/N2/tar vapor) formation and a pragmatic kinetics-driven accelerated reaction template for atomistic simulation of the carbonization process overcoming traditional challenges in time scale discrepancy of the reaction-diffusion system. The results of enthalpy barriers from hybrid first principles calculations validate the rationality and sequence of conjectured reactions during the two-stage carbonization process. Conversion rates of the rate-determining steps under 300 s carbonization are also estimated based on Eyring's transition state theory realizing kinetics equivalency of the reaction extent. Process-control measurements are further demonstrated corresponding to the proposed mechanism. The iterative densified crosslinking scheme specially designed for the surface layer is implanted into the topological reaction molecular dynamics template and a series of highly devisable structural models during the whole evolutionary process from the pre-oxidized fiber to the pristine carbon fiber surface are successfully predicted. The ultimate structure of the model presents excellent similarity in carbon yield and elemental composition with the type II high strength carbon fiber surface.