Wet spinning of polyacrylonitrile/carbon nanotubes (PAN/CNT) composite fibers was studied and the effect of spinning conditions on structure and properties of as-spun fibers influenced by the presence of CNTs investigated. Unlike PAN fibers, shear force had a larger effect on crystalline structure and physical and mechanical properties of PAN/CNT composite fibers compared to the elongational force inside a coagulation bath. Under shear force CNTs induced nucleation of new crystals, whereas under elongational force nucleation of new crystals were hindered but the already formed crystals grew bigger. To our knowledge, this key effect has not been reported elsewhere. At different shear rates, strength, Young’s modulus and strain at break of PAN/CNT as-spun fibers were improved up to 20% compared to PAN fibers. Application of jet stretch had less influence on physical and mechanical properties of PAN/CNT fibers compared to PAN fibers. However, the improvement of interphase between polymer chains and CNTs as a result of chain orientation may have contributed to enhancement of Young’s modulus of jet stretched composite fibers.

Polyacrylonitrile (PAN) fibers with unique properties are becoming increasingly important as precursors for the fabrication of carbon fibers. Here, we suggest the preparation of porous PAN composite fibers to increase the homogeneity and thermal stability of the fibers. Based on the thermodynamics of polymer solutions, the ternary phase diagram of the PAN/H₂O/Dimethylformamide (DMF) system has been modeled to introduce porosity in the fibers. Adding a conscious amount of water (4.1 wt.%) as a non-solvent to the PAN solution containing 1 wt.% of graphene oxide (GO), followed by wet spinning, has led to the preparation of porous composite fibers with high thermal stability and unique physicochemical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) results elucidate that PAN/GO/H₂O porous composite fibers have a higher thermal decomposition temperature, increased residual weight, reduced heat release rate, and higher crystallinity in comparison with the pristine PAN fibers, being a promising precursor for the development of high-performance carbon fibers. The results show a promising application window of the synthesized PAN fibers in electronic and electrochemical devices.

Wet-spun polyacrylonitrile fibres are the main precursor for high strength carbon fibres. The properties of carbon fibres strongly depend on the structure of the precursor fibre. Polyacrylonitrile fibres were spun from solutions with varying solvent/nonsolvent content and different draw ratios. Wet-spinning is an immersion precipitation process, thus thermodynamic affinity of spinning dope to the coagulation medium was considered as the driving force of phase-separation, while viscosity of the solution accounted for the resistive force against phase separation and growth of the nucleated voids. Thermodynamic affinity was estimated by modifying Ruaan’s theory and viscosity of the solution was assessed on-line by measuring flow rate and back pressure at the spinneret. Hence, the parameter (thermodynamic affinity/viscosity) was introduced to predict the porous morphology of the fibres. Generally, an increase in led to fibres with higher porosity. A combination of electron scanning microscopy (SEM), porosimetry and thermoporometry was applied to fully characterize microstructure of fibres. Based on image analysis of SEM micrographs and data obtained from thermoporometry and porosimetry fractions of dense polymer ligament, micrometer size voids (macrovoids) and nanometer size voids (nanovoids) were estimated. Increasing polymer content or nonsolvent content in the spinning dope caused an increase in the solution viscosity and resulted in fibres with lower porosity. Imposing drawing on the as-spun fibres further decreased the porosity. Drawing also shifted the size distribution of nanovoids toward smaller values.

Thermal stabilization is an important step in production of carbon fiber from polyacrylonitrile (PAN) precursors. During thermal stabilization step different thermochemical reactions take place almost simultaneously. Understanding the onset and temperature range of the stabilization reactions is a key for adjusting processing parameters such as tension, stretching, etc. However, stabilization reactions are very complex and overlap with each other. In order to separate the stabilization reactions, we combined the results of different thermal analysis techniques, namely Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA) and Thermomechanical Analysis (TMA), to study behaviour of PAN precursors during stabilization. By means of combining the results of these techniques, we were able to determine the temperature range and occurrence order of each of stabilization reactions regardless of the composition of initial PAN fibers and history of fiber formation.