Accelerated multistep thermal stabilization of polyacrylonitrile fibers using an ethylenediamine pretreatment

Abstract

The polyacrylonitrile multifilament yarn underwent a multistep heat treatment process including stabilization times ranging from 5 to 75 min following impregnation with a 30% ethylenediamine (EDA) aqueous solution. A series of measurements were employed to determine the structure and properties of thermally stabilized PAN samples. These included fiber thickness, fiber density, flame testing, tensile testing, X-ray diffraction, thermal analysis (differential scanning calorimetry and thermogravimetric analysis), and infrared spectroscopy. The results from XRD and IR spectroscopy indicated that the rate of aromatization reactions increased with longer stabilization times. A detailed examination of the XRD curves obtained through curve-fitting procedures suggested a rapid transformation of the original structure into a disordered amorphous phase containing pre-graphitic domains, evidenced by a gradual reduction in the degree of apparent crystallinity of the original PAN sample. The integration of EDA before the thermal stabilization stage significantly reduced the cyclization time of nitrile groups in the PAN polymer structure, thereby accelerating the stabilization reactions. This chemical pretreatment also improved the thermal stability of the samples by promoting oxidative cross-linking of the PAN polymer chains. After a 75 min multistep stabilization, the carbon yield at 1000 °C was 70.5%. Conversion index values, calculated using IR, XRD, and DSC methods, were 98.3%, 94.8%, and 89.5% respectively for the 75 min sample. These findings highlight the importance of EDA in accelerating the formation of an aromatic structure, which is critical for withstanding the high temperatures of subsequent carbonization stages. Graphical abstract