Exploring the Thermodynamic Aspects of Structure Formation During Wet-Spinning of Polyacrylonitrile Fibres

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 X (thermodynamic affinity/viscosity) was introduced to predict the porous morphology of the fibres. Generally, an increase in X 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.