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The transient shear and elongational flow behavior of HPC EF, G, and HBA/HNA (Vectra A900) have been measured in order to determine the behavior of liquid crystalline polymer systems and to establish whether this behavior is different from that for isotropic flexible-chain polymer melts and isotropic systems of rodlike polymers. In order to accomplish this a rotary clamp extensional rheometer was constructed which is capable of measuring the elongational flow behavior of polymer melts up to 320 °C and which can measure elongational viscosities as low as 1000 Pa's. Tests were conducted on HPC EF at 190 and 210 °C, on HPC G at 200 and 240 °C, and on HBA/HNA at 301 and 320 °C. It was determined that the transient shear stress behavior of the LCP systems scales with strain or alternately, reduced time and that the reduced stress is independent of shear rate over the range of rates investigated. This behavior is different from that for isotropic melts of flexible-chain and rodlike polymers in that the reduced stress for these systems is dependent on deformation rate. The transient elongational viscosity behavior of the LCPs was determined and found to follow linear viscoelastic response at very low strains and then shows mild strain hardening with increasing strain, which is qualitatively similar to the behavior of certain linear polyolefins such as PS and HDPE. From the elongational viscosity behavior determined for both isotropic and anisotropic HPC melts it was found that differences in the melt state can result in qualitative differences in the measured behavior. However, the presence of residual crystallinity in the systems studied makes it uncertain whether the results determined here are general for all LCP systems. The prediction of the Doi theory for both steady and transient shear and elongational flow were calculated in order to establish whether the theory can predict or model the flow behavior of LCPs and to establish whether the elongational flow behavior of LCPs can be predicted from their shear flow behavior. The Doi theory was evaluated with the viscous drag or rod-solvent friction term retained in the equation for the stress tensor. It was found that the Doi theory cannot predict the shear or elongational flow behavior of LCPs with parameters determined only from molecular properties. At the same time, the Doi theory was found to be able to semi-quantitatively model the steady shear viscosity behavior of isotropic and anisotropic systems of rodlike polymers with retention of the viscous drag contribution to the stress tensor. Also, the Doi theory was able to qualitatively model the transient flow behavior of the same systems, though agreement for the anisotropic systems depended on the use of a multidomain average to represent the globally unoriented state of the material at equilibrium. However, the Doi theory was not able to predict the transient elongational flow behavior of either isotropic or anisotropic systems with parameters fit to shear flow data. Furthermore, the predictions of the Doi theory for elongational flow showed only marginal qualitative agreement with the experimentally determined behavior of both isotropic and anisotropic systems. / Ph. D.

Solutions of cellulose esters with different concentrations in dimethylacetamide (DMAc) and with different types of substituents were studied in relation to their liquid crystalline (LC) solution behavior. Classical LC behavior was revealed for all solutions. Critical polymer concentration (V_p^c) is highest for cellulose acetate (CA) and lowest for cellulose acetate butyrate (CAB) with highest degree of butyration. This is opposite to the classical model by Flory which predicts an increase in V_p^c with decreasing aspect ratio (L/d). Fibers were spun from isotropic and anisotropic DMAc solutions of cellulose esters by dry jet/wet spinning process. The mechanical properties, orientation, and crystallinity of the fibers increased as spinning progressed from the isotropic to the anisotropic solution state. High butyryl content enhances both overall solubility and the formation of LC solutions at lower concentration, but it results in lower fiber properties. Unmodified cellulose (C) and cellulose hexanoate (CH) also exhibited LC behavior. The V_p^c value for CH was lower than that obtained for CAB with maximum degree of butyration. This indicates that bulky substituents may lower V_p^c values. The formation of high modulus (152 g/d) cellulose fibers from LC solutions is attributed to the air-gap that exists in the dry jet/wet spinning process. Presence of lithium chloride (LiCl) in the LC solutions of CAB exhibited ionic interactions. Mechano-sorptive creep behavior of the fibers spun from these solutions decreases in the presence of residual LiCl salt. Fibers from blends of CAB and of C with lignin (L) were spun from Lc solution. Morphological investigations demonstrate that CAB and L formed intimately mixed blends whereas C and L were partially mixed. The mechanical properties of the fibers with L increased due to good phase mixing of CAB and L molecules in the fiber matrix. / Ph. D.

Injection Molding The effects of partial miscibility on the mechanical properties and morphology of thermotropic liquid crystalline polymer blends were investigated in this part of the work. Blends of an immiscible (Vectra A900) and partially miscible (HX1000) thermotropic liquid crystalline polymer (TLCP) with a polyetherimide (PEI) were used in the investigations. The blends were injection molded into mini-tensile bars and rectangular plaques, and their mechanical properties were evaluated. Interfacial, rheological, and morphological properties along with molecular orientation analysis were carried out in order to explain the mechanical properties of the blends. Mechanical tests showed that both the tensile and flexural modulus deviate positively from the law of mixtures. However, for the PEI/HX1000 system the deviation from the law of mixtures appeared at lower TLCP concentrations compared to the PEI/Vectra A900 system. It was found that the tensile modulus correlated well with the structure developed during injection molding. Morphological tests show that finer higher aspect ratio TLCP fibers developed in the PEI/HX1000 system relative to the PEI/Vectra A system. In addition, both blends showed a maximum in the tensile modulus at 90 wt% TLCP. Rheological tests indicated that for TLCP-rich compositions, a higher viscosity was observed for the blends in comparison to the neat TLCPs. Therefore, due to a greater viscosity, higher magnitudes of stresses, consequently inducing a higher degree of molecular orientation, were experienced by the blends relative to the neat TLCPs. Although partial miscibility seemed to affect more strongly the stiffness of the in situ composite, the ultimate properties of the TLCP strongly dominated the ultimate properties of the PEI/TLCP composite. Mechanical tests showed that the ultimate properties of Vectra A were at least twice those of HX1000. Consequently, for TLCP-rich compositions, higher values of toughness, elongation at break and tensile strength were observed for PEI/Vectra A blends compared to PEI/HX1000 blends. The study presented here seems to suggest that the selection of a TLCP to reinforce a polymeric matrix is not only dependent upon whether partial miscibility or compatibility between the TLCP and matrix polymer exist, but also on the mechanical properties of the TLCP. Shearfree Elongational Deformation The effects of uniaxial, planar and biaxial deformations on the morphology and mechanical properties of bends of a polyetherimide with thermotropic liquid crystalline polymers were investigated in this part of the work. Extruded sheets and molded plaques of PEI/Vectra A and PEI/HX1000 blends were used in the studies. In the case of injection molded plaques, in which the initial morphology was that of fibers and droplets, the direction of the applied deformation relative to the initial direction of the TLCP fibrils was an important factor in affecting the resultant morphology and corresponding mechanical properties of the blends. If the direction of the applied uniaxial deformation was parallel to the initial fiber direction, the deformation tended to increase the average aspect ratio of the TLCP fibers and mechanical properties were enhanced along the direction of deformation. However, if the deformation was applied transverse to the initial fiber direction, the fibers tended to follow the deformation and a 90° rotation was observed. In terms of mechanical properties, an increase in the transverse direction properties accompanied by a reduction in the flow direction properties followed the realignment of the fibers. In addition, equal flow and transverse mechanical properties appeared at 0.5 units of transverse uniaxial strain. Planar deformation led to the spreading of the fibers in the plane of deformation and a ribbon-like morphological structure developed. However, at comparative magnitudes of planar strains, transverse planar compression tends to promote a greater spreading of the fibers relative to planar compression applied parallel to the initial direction of the fibers. In addition, planar stretching applied in a direction perpendicular to the initial direction of the TLCP fibers was effective in reducing the mechanical anisotropy of the molded plaques. Samples showing equal flow and transverse properties were obtained when planar strains greater than 0.5 units were applied in a direction perpendicular to the initial direction of the fibers. In the case of extruded sheets, in which the initial morphology was that of drops, it appeared that partial miscibility was an important factor in affecting the final morphology of the sheet. For the immiscible PEI/Vectra A system, longer and more stable TLCP fibrils were found compared to PEI/HX1000 system. It is believed that, due to lower interfacial tension, stress induced fiber breakup occurred during stretching of the PEI/HX1000 blend. Thermoforming of In Situ Composites The use of in situ thermoplastic composites based on blends of a polyetherimide with an amorphous and a semicrystalline liquid crystalline polymer in the thermoforming process was explored in this part of the work. Injection molded and extruded samples, in which the initial morphology of the dispersed TLCP phase was either in the form of fibers or droplets, were subjected to thermoforming. It was found that in the case where the initial morphology of the dispersed TLCP phase was that of droplets, the elongational stresses generated during forming were capable of deforming the TLCP phase into fibers, and the aspect ratio of the fibers was increased with depth of draw. However, when the initial morphology of the the TLCP phase was in the form of fibers, then the relative alignment of the fibers with respect to the forming direction was an important factor in affecting the final structure of the TLCP phase in the formed tray. When the fibers were aligned parallel to the forming direction, the elongational strains generated during forming tended to further increase the aspect ratio of the fibers. In the case where the initial TLCP fibers were aligned transversely to the forming direction, the fibers tended to spread into a ribbon-like structure after forming. Pre-stretching of the samples prior to thermoforming tended to contribute to an increase in the aspect ratio of the TLCP fibers. As a result, an enhancement in the deflection resistance of the prestretched/formed samples was observed. In situ thermoplastic composites seemed to be advantageous compared to glass reinforced thermoplastics in thermoforming applications. The elongational stresses generated during forming tended to deform the TLCP phase into a specific morphology. Depending on the relative direction of the deformation, either fibers or a ribbon-like structure may be developed. This is in contrast to glass reinforced PEI, in where breakage of the glass fibers occurred upon forming, which may contribute to a reduction in the mechanical performance of glass reinforced materials. / Ph. D.

The investigation of structure-property behavior of extruded cast films prepared from blends of thermotropic liquid crystalline copolyesters with polyethylene terephthalate (PET). Data were obtained which showed not only the temperature dependence of the moduli and stress-strain behavior but also the orientation effects that must be prevalent in order to explain the differences between the moduli measured parallel and perpendicular to the extrusion direction. Only at high liquid crystal polymer (LCP) compositions is the modulus particularly increased. The modulus enhancement with lower LCP content and utilization of process variables are discussed. Specifically, the extruder gear pump speed did not enhance Young's modulus at the same LCP content as extensively as did the effect of extruder screw speed. Also a study to synthesize and characterize new segmented copolymers that could produce unusual film properties are discussed. The approach involved the synthesis of high Tg (220 C) isotropic poly (aryl ether sulfone) oligomers of varying segment molecular weights. The thermal and mechanical studies of the copolymers have been carried out to probe the potential of these copolymers for signs of liquid crystalline character and to note their ability to thermally crystallize as well as to crystallize by solvent or strain inducement. Along these lines, thermal analysis, polarizing hot-stage microscopy, wide angle x-ray scattering and mechanical testing were utilized in this investigation / Master of Science

Temperature is a parameter which is important because of its influence on other material properties. Many temperature measurement techniques are available but few of them permit a direct visualization of surface temperature Variation. The Liquid crystal method is one of the rare methods that permits a complete color mapping of surface temperature and that is also fast enough to respond to surface temperature Variation on plates heated by cyclic bending. A mathematical model for irreversible mechanical heating of plates is developed to support the experimental investigation. The results, which include comparison of the theory and the experiment, show that liquid crystals allow good qualitative measurements and can lead, with certain precautions, to quantitative results. / Master of Science

Master of Science