The conjugated plane formed in polyacrylonitrile during thermal stabilization

The formation process and mechanism of the pseudo‐graphite sheets of polyacrylonitrile (PAN) during thermal treatment in inert atmosphere were investigated by thermo‐gravimetry (TG) and X‐ray diffraction (XRD). According to the results, the conjugated plane originally formed during stabilization was proposed as the basic planar structure of the pseudo‐graphite sheets, and it was connected and stacked to form pseudo‐graphite microcrystal through chain scission reaction and non‐carbon atoms elimination reaction in 280–450 °C and 800–1300 °C respectively. The in situ measurements for time dependence of ultraviolet‐visible (UV‐vis) and Fourier transform infrared spectra (FTIR) were applied to study the conjugated plane of PAN during isothermal stabilization. It was found that with the higher temperature the conjugated plane forms more rapidly, and it has higher conjugated extent with the extending of heating time. The FTIR data showed that both cyclization and dehydrogenation are beneficial to the evolution of conjugated plane in the first 3 h, but only cyclization continues after 3 h at 250 °C. Further investigation indicated that stabilized PAN with large quantity and high conjugated extent of the conjugated plane would contribute to get large size of pseudo‐graphite microcrystal after carbonization, which is consistent with the former assumption. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43890.