Establishing the Conditions for Stable Extrusion of Melt Spun Polyacrylonitrile with Water Based Plasticizers

Polyacrylonitrile (PAN) fiber is one of the most important synthetic fibers in the world because it is a precursor to carbon fiber. Compared to the traditional solution spinning process, the melting spinning process of PAN is less costly and can further reduce the price of PAN fiber. This dissertation is concerned with the objective of establishment of conditions (temperature, plasticizer type, and plasticizer composition) that a PAN copolymer is able to be stable melt spun with water based plasticizers. More specifically, PAN/water/acetonitrile (70/15/15) mixture is considered as reference sample in this study because it was proposed in a BASF patent in which it was claimed it could be stably melt spun. We are looking for a more benign plasticizer so that the use of acetonitrile can be avoided and PAN can still be stably melt spun.

To achieve this objective, the first step is to measure the melting point (Tm) of PAN copolymer with various plasticizers and compositions by using differential scanning calorimetry (DSC). The results indicate the Tm of PAN copolymer can be reduced to around 160 oC with water only as a plasticizer, which is lower than the degradation temperature of PAN (180 oC). Moreover, using a water/ethanol mixture and water/acetonitrile as plasticizers can further reduce the melting point of PAN to 150 oC and 135 oC, respectively.

The second step is conducting rheological measurements on the PAN/plasticizers mixture. A pressure chamber was designed and attached to the capillary rheometer in order to prevent the foaming and evaporation of plasticizers during the viscosity experiments. Both steady-shear and time-dependent viscosity measurements were conducted. The rheological measurement results indicate that PAN can keep stable for more than 120 minutes with all plasticizers under 170 oC, and it starts to degrade in 60 minutes at 180 oC, except samples plasticized with 30 wt% of water (which keep stable for 120 minutes as well). The steady-shear viscosity results indicate the shear-thinning behavior is observed for the PAN/plasticizer mixtures at a temperature ranging from 170 oC to 190 oC and provide the fundamental viscosity data which can be applied to the extrusion process. In conclusion, the rheological measurements show PAN/Water (70/30 wt%) at 180 oC and PAN/EtOH/Water (70/15/15) at 170 oC are two potential systems for carrying out the PAN melt spinning process.

Scanning electron microscopy (SEM) images were taken for the reference state and potential conditions. These images show that the copolymer strands have more and larger voids when plasticized with water only compared to those plasticized with water/acetonitrile and water/ethanol mixture. In this case, PAN/EtOH/Water (70/15/15) at 170 oC is considered to be the most benign system for that PAN melt spinning.