Stabilization and carbonization studies of polyacrylonitrile/carbon nanotube composite fibers

Carbon fibers contain more than 90 wt. % carbon. They have low density, high specific strength and modulus, and good temperature and chemical resistance. Therefore, they are important candidate as reinforcement materials. Carbon fiber is made by pyrolysing precursor polymers. Polyacrylonitrile (PAN) which has been used as precursor to produce high strength carbon fiber is used as precursor in this study. The theoretical tensile strength of carbon fibers can reach over 100 GPa. Currently, the best commercial carbon fibers reach only 7.5 GPa. To make good quality carbon fiber and to narrow the gap between theoretical values and currently achieved experimental properties, the entire manufacturing process including fiber spinning, stabilization and carbonization, needs to be improved optimized. In this dissertation, the stabilization processes of gel-spun PAN/carbon nanotubes (CNTs) composite fibers are studied. PAN/CNT (1 wt. % CNT) composite fibers are spun by dry-jet gel-spinning. Three types of CNTs with different number of walls and varying catalyst content are used as additives. The effect of different types of CNTs on the properties of the stabilized fibers was compared. It is found that the CNTs with the highest surface area shows the best reinforcement efficiency on the tensile modulus, and reduces the formation of β-amino nitrile. The residual catalyst in the range of 1 to 4 wt. % shows little effect on the mechanical properties of the stabilized fibers. Stabilization involves complex chemical reactions, including cyclization, oxidation, dehydration, and cross-linking. These complex reactions are separated by using different gas environments during stabilization. The cross-linking reaction has the highest activation energy among all stabilization reactions, and requires a temperature higher than 300 °C to be completed. The effect of applied tension on the stabilized fiber properties are investigated, and it is found that higher tension leads to better properties for the stabilized fiber, including higher Young’s modulus, higher orientation, less formation of β-amino nitrile, and less shrinkage. The relationship between stabilization conditions and the mechanical properties of the carbonized fiber is investigated, and the methods to identify optimum stabilization conditions are proposed. It is observed that the highest tension should be applied during both stabilization and carbonization, and the mechanical properties of the resulting carbon fibers are increased if fibers are further stabilized at a temperature of ∼ 320 °C to improve the cross-linking degree as compared with the fibers only stabilized at 255 °C. The optimum stabilization time depends on both the stabilization temperature and on the applied tension. A new characterization method by monitoring the dynamic mechanical properties, while stabilization is in progress is used to narrow down the range of the optimum stabilization time. Also, the effect of carbonization temperature on the ultimate carbon fiber properties is studied in the batch process carbonization. Preliminary studies are carried out to find the relationship between the structure and properties of precursor fibers and the tensile strength of carbon fibers, including mechanical properties and co-monomers of precursor fibers.