Abstract:The rheological behavior of amino-functionalized multi-walled carbon nanotubes (amino-CNTs)/polyacrylonitrile (PAN) concentrated solutions in the dimethyl sulphoxide solvent and the effects of the amino-CNTs on the PAN precursor fibers by wet-spinning method were investigated. The amino-CNT/PAN concentrated solutions prepared by in situ solution polymerization with homogeneous dispersion of amino-CNTs have higher complex viscosity, storage modulus and loss modulus as compared to the control PAN concentrated solutions containing 22% PAN polymer by mass. The composite fibers with amino-CNTs of 1 wt % have lower degree of crystallization, crystal size and crystal region orientation compared to the control PAN precursor fibers. However, the amino-CNT/PAN composite fibers with diameter of about 10.5 µm exhibit higher mechanical properties than the control PAN precursor fibers with diameter of about 8.0 µm. Differential scanning calorimetry analysis demonstrated that the cyclization reaction in composite fibers have broad exothermic temperature range and low exothermic rate. These results indicate that the addition of amino-CNTs into PAN precursor fibers is beneficial to controlling the process of thermal stabilization and obtaining the higher performance of composite fibers.

Amino-functionalized multi-walled carbon nanotube (amino-CNT)/polyacrylonitrile (PAN) microspheres with diameter of about 300-400 nm were prepared by in situ polymerization under aqueous solution. The morphology, crystal structure, and thermal properties of amino-CNTs on a PAN homopolymer were investigated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectra, X-ray diffraction, and differential scanning calorimetry. The results showed that the amino-CNTs had a significant influence on the morphology of microspheres, and the PAN matrix were grafted onto the surface of amino-CNTs with interfacial bonding between them. The XRD studies showed that the crystal size of amino-CNT/PAN microspheres with lower crystallinity was bigger than in the control PAN homopolymer. The analysis of thermal properties indicated that the amino-CNT/PAN microspheres with lower glass transition temperature had a lower initial temperature and velocity of evolving heat during the exothermic processing as compared with the PAN homopolymer. These results suggested that the incorporation of amino-CNTs into the PAN homopolymer matrix was beneficial for controlling the heat released during the stabilization processing.

The composition and structure of polyacrylonitrile (PAN) precursors play an important role during thermal stabilization, which influences the properties of the resulting carbon fibers. In this paper, PAN homopolymer and PAN-itaconic (IA) copolymers with different IA contents were synthesized by aqueous phase precipitation polymerization. The effects of IA content on the structure and thermal properties were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The morphology of PAN polymers showed that the average size of the PAN particles increased with the increase of IA content in the feed. The content of the IA comonomer on the copolymers was quantitatively characterized by the relative absorbance intensity (A1735/A2243) in FTIR spectrum. With the increase of IA content in the feed, PAN-IA copolymers exhibited lower degree of crystallinity and crystal size than the control PAN homopolymer. The results from DSC curves indicated that PAN-IA1.0 copolymers had lower initial exothermic temperature (192.4 °C) and velocity of evolving heat (6.33 J g−1 °C−1) in comparison with PAN homopolymer (Ti = 238.1 °C and ΔH/ΔT = 34.6 J g−1 °C−1) in an air atmosphere. TGA results suggested that PAN-IA1.0 copolymers had higher thermal stability than PAN homopolymer, which can form a ladder structure easier during thermal processing. Therefore, PAN-IA1.0 copolymers would be a suitable candidate for preparing high performance PAN based carbon fibers.

Polyacrylonitrile (PAN) grafted amino-functionalized multi walled carbon nanotubes (amino-MWCNTs) were synthesized by in situ polymerization under aqueous solvent. The grafted MWCNT/PAN nascent composite fibers were prepared by the wet spinning method. Fourier transform infrared spectroscopy and Raman spectroscopy indicated that the amino-MWCNTs and PAN macromolecular chains had interfacial interactions and formed chemical bonds. The grafting content of the PAN polymer on the amino-MWCNTs was up to 73.2% by thermo gravimetric analysis. The incorporation of the grafted MWCNTs improved the degree of crystallization and crystal size of PAN nascent fibers, and changed the thermal properties during exothermic processing in an air atmosphere. Morphology analysis and testing of mechanical properties showed that the grafted MWCNT/PAN nascent composite fibers with a more uniform diameter distribution and larger diameter had higher tensile strength and tensile modulus than the control PAN nascent fibers.