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. / Doctor of Philosophy / The melt spinning process of polyacrylonitrile (PAN) has been studied in the past few decades. Compared to the traditional solution spinning process, it does not require toxic organic solvents. The major problem of the PAN melt spinning process is the melting point (Tm) of PAN is much higher than its degradation temperature. However, by adding plasticizers the Tm of PAN can be significantly reduced, which makes PAN melt spinning feasible. In this work we discuss the feasibility of the melt spinning process of polyacrylonitrile (PAN) copolymer plasticized with water based plasticizers by using differential scanning calorimetry (DSC) and rheological methods. The objective is to use water only as a plasticizer to melt spin PAN under specific conditions (composition, temperature etc). The melting point and rheological measurements have been conducted by DSC and a modified capillary rheometer, respectively, for this plasticized system. The DSC results show that the melting point of the PAN copolymer can be reduced below the degradation temperature of PAN, and the rheological results show that the PAN copolymer can be extruded with a reasonable viscosity at 15-20 o v above its melting point, and also the stability and viscosity are strongly dependent on temperature and the plasticizer type and content. Furthermore, the Scanning electron microscopy (SEM) images show the copolymer strands extruded from PAN/H2O mixture have many more and larger voids than PAN/H2O/EtOH mixture. In conclusion, the results indicate that the most appropriate condition for PAN melt spinning is PAN/H2O/EtOH mixture of 70/15/15 wt% ratio at a temperature of 170 oC

This investigation was started at the suggestion of Dr. P. C. Scherer who suggested that a film prepared from a cellulose xanthate, in which the fiber form had been destroyed by some action other than by dilute alkali, should have interesting properties. The possibilities of such a material might be much greater if the destruction of the fiber form were brought about by a kneading action. This investigation was purely a qualitative one and no attempt has been made to test any of the products other than by appearance and general properties. The main object was that of finding ways and means of handling the material in an attempt to prepare a product of some strength and plasticity. The results obtained in all of the preceding experiments emphasize the difficulty which is encountered in the attempt to plasticize a cellulose xanthate and the removing of the salts formed in the xanthate formation. The removal of the salts in the water treatment (B) required large amounts of water which also seemed to remove the plasticizer. Some of the plasticizers were soluble in alkaline solutions and in the dissolving out of the salts, the dissolved salts caused high causticity, thus removing the plasticizer also. The acid-treated samples (A) and (C) required from three to four hours to completely dissolve the salts present in the sample. This treatment probably caused a high degree of degradation since all of the samples were brittle and had less strength than the water-treated samples. Since the results of the investigation are all negative in so far as the main object was concerned, it is concluded that a plasticized cellulose cannot be obtained from. cellulose xanthate using the plasticizers and methods set forth in this investigation. / M.S.

Plasticizers are often interchanged with the idea that they will not affect the processing behavior of Polyvinyl Chloride (PVC). However, when the plasticizer type is changed, various complaints are made by the processors that the material no longer processes the same. This research was concerned with the effect of three different plasticizers on the plasticating extrusion behavior of PVC. Di-isodecyl pthalate (DIDP), di-hexyl pthalate (DHP) and 2-ethyl hexyl pthalate (DOP) are the three plasticizers used in this study. First some differences in the extrusion performance of the three differently plasticized PVC compounds were identified. In particular, it was observed that pressure build-up, flow rate and power requirement were affected by the plasticizer type with the DIDP plasticized materials generating higher pressures and requiring more power than the other two plasticized materials. The differences in extrusion characteristics have been observed for two different dies (1/8 and 1/16 inch diameter) attached to the extruder. The differences were most significant between the DIDP and the DHP plasticized mixes. Factors which could influence the processing behavior of plasticized PVC include viscosity, compaction, thermal conductivity, specific heat, and friction coefficient. It was found that all other properties other than the viscosity were unaffected by the plasticizer type. On the other hand, viscosities were significantly affected by the plasticizer type with the DIDP plasticized materials displaying higher values between 160 and 190 °C. The difference in viscosity was larger between the DIDP and DHP plasticized materials than between DIDP and DOP plasticized materials. The differences in viscosity between DIDP and DOP plasticized materials tend to diminish considerably at 190 °C. Two flow regions characterized by different degrees of fusion above and below 165 °C were identified for the plasticized PVC compounds. Plasticized PVC exhibited yield stresses with the DIDP plasticized materials having higher values. The yield stresses were responsible for the significant difference in viscosity at lower shear rates. The yield stress was a more dominant feature at temperatures below 160 °C and this fact was made use of in modeling the solids conveying zone as a fluid with yield stress. Correlation was established between the viscosities and the extrusion behavior of the plasticized PVC compounds. It was observed that the DIDP plasticized mixes had higher viscosities, fused earlier in the screw channel, gave rise to higher pressures, required more power and in general exhibited higher flow rates at the same screw speed. The finite element method was used for the numerical simulations. Based on the experimental results, the numerical modeling of the melt zone was performed in order to predict the differences in the extrusion characteristics. The melt zones were modeled as a temperature dependent power law fluid having two different viscosity expressions above and below 165 °C. The numerical predictions for pressures and flow rates in the extruder with the 1/8 inch diameter die were in good agreement with the experimental results. For the case of the 1/16 inch diameter die attached to the extruder, the numerical and experimental flow rates were in good agreement but the pressure predictions, although indicating the correct trends, were off by 15 to 20% from the experimental results. In general the differences in the physical properties, viz. viscosities, were used to predict the differences in the pressure build-ups and flow rates. Also the solid conveying zone was modeled using a Herschel Bulkley model. It was possible to match the experimental and numerical results for the solids conveying zone by using an average density value for the entire solids conveying zone, but more work needs to be done in order to establish greater validity and applicability of this model. / Ph. D.

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This project studied the biodegradation of a plasticizer, di-(2-ethylhexyl) adipate (DEHA), by two mammalian cell lines, HepG2 and WIF-B, in vitro . An MTT assay showed that DEHA had a toxic effect on both cell lines. Despite this, both hepatocyte cell lines successfully degraded the plasticizer. Metabolites were identified and quantified by gas chromatography. HepG2 cells showed minimal alcohol dehydrogense activity and this resulted in the accumulation of 2-ethylhexanol. WIF-B cells were able to breakdown the alcohol and produced 2-ethylhexanoic acid. It is important to note that an enzyme was essential for this step in the degradation of the plasticizer, as this proves that it was biodegradation and not physical degradation. By comparing the metabolites formed and the order of their appearance, the degradation pathway in these mammalian cells was found to be similar to the established degradation pathways for bacteria, fungi and yeast.

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Thesis (Ph. D.)--Institute of Paper Chemistry, 1951. / Includes bibliographical references (p. 185-188).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1949. / Includes bibliographical references (p. 104-106).