One of the major limitations in Fused Filament Fabrication (FFF), a form of additive manufacturing, is the lack of composites with superior mechanical properties. Traditionally, carbon and glass fibers are widely used to improve the physical properties of polymeric matrices. However, the blending methods lead to fiber breakage, preventing generation of long fiber reinforced filaments essential for printing load-bearing components. Our approach to improve tensile properties of the printed parts was to use in-situ composites to avoid fiber breakage during filament generation. In the filaments generated, we used thermotropic liquid crystalline polymers (TLCPs) to reinforce acrylonitrile butadiene styrene (ABS) and a high performance thermoplastic, polyphenylene sulfide (PPS). The TLCPs are composed of rod-like monomers which are highly aligned under extensional kinematics imparting excellent one-dimensional tensile properties. The tensile strength and modulus of the 40 wt.% TLCP/ABS filaments was improved by 7 and 20 times, respectively. On the other hand, the 67 wt.% TLCP/PPS filament tensile strength and modulus were improved by 2 and 12 times, respectively. The filaments were generated using dual extrusion technology to produce nearly continuously reinforced filaments and to avoid matrix degradation. Rheological tests were taken advantage of to determine the processing conditions. Dual extrusion technology allowed plasticating the matrix and the reinforcing polymer separately in different extruders. Then continuous streams of TLCP were injected below the TLCP melting temperature into the matrix polymer to avoid matrix degradation. The blend was then passed through a series of static mixers, subdividing the layers into finer streams, eventually leading to nearly continuous fibrils which were an order of magnitude lower in diameter than those of the carbon and glass fibers. The composite filaments were printed below the melting temperature of the TLCPs, and the conditions were determined to avoid the relaxation of the order in the TLCPs. On printing, a matrix-like printing performance was obtained, such that the printer was able to take sharp turns in comparison with the traditionally used fibers. Moreover, the filaments led to a significant improvement in the tensile properties on using in FFF and other conventional technologies such as injection and compression molding. / Doctor of Philosophy / In this work two thermoplastic matrices, acrylonitrile butadiene styrene (ABS) and polyphenylene sulfide (PPS), were reinforced with higher melting thermoplastics of superior properties called thermotropic liquid crystalline polymers (TLCPs). This was done so that the resulting filaments could be 3D-printed without melting the TLCPs. The goal of this work was to generate nearly continuous reinforcement in the filaments and to avoid matrix degradation, and, hence, a technology called dual extrusion technology was used for the filament generation. The temperatures required for filament generation were determined using rheology, which involves the study of flow behavior of complex fluids. Dual extrusion technology allows processing of the constituent polymers separately at different temperatures, followed by a continuous injection of multiple TLCP-streams into the matrix polymers. In addition, the use of static mixers (metallic components kept in the path of flow to striate incoming streams) leads to further divisions of the TLCP-streams which are eventually drawn by pulling to orient the TLCP phase. The resulting filaments exhibited specific properties (normalized tensile properties) higher than aluminum and contained fibers that were nearly continuous, highly oriented, and an order in magnitude lower in diameter than those of carbon and glass fiber, which are commonly used reinforcements. High alignment and lower fiber diameter are essential for printing smoother printed parts. The filaments were intended to be printed without melting the TLCPs. However, previous studies involving the use of TLCP reinforced composites in conventional technologies have reported the occurrence of orientation relaxation on postprocessing, which decreases their tensile v properties. Therefore, temperatures required for 3D printing were determined using compression molding to retain filament properties on printing to the maximum extent. On printing using an unmodified 3D printer, parts were printed by taking 180º turns during material deposition. Contrarily, the use of continuous carbon fibers required a modified 3D printer to allow impregnation during 3D printing. Moreover, the performance comparison showed that the continuous carbon fibers could not be deposited in tighter loops. The properties of the printed parts were higher than those obtained on using short fibers and approaching those of the continuous fiber composites.

The objective of this study is to synthesize nematic-thermotropic liquid crystalline polymers (LCP) and determine their possible application areas. In this context, thirty different LCP&rsquo / s were synthesized and categorized with respect to their fiber formation capacity, melting temperature and mechanical properties. The basic chemical structure of synthesized LCP&rsquo / s were composed of p-acetoxybenzoic acid (p-ABA), m-acetoxybenzoic acid (m-ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA) and isophthalic acid (IPA) and alkyl-diacids monomers. In addition to mentioned monomers, polymers and oligomers were included in the backbone such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) polymers, and polybutylene naphthalate (PBN), polyhexylene naphthalate (PHN) and poly butylene terephthalate (PBT) oligomers that contain different kinds of alkyl-diols. We adjusted the LCP content to have low melting point (180oC-280oC) that is processable with thermoplastics. This was achieved by balancing the amount of linear (para) and angular (meta) groups on the aromatic backbones together with the use of linear hydrocarbon linkages in the random copolymerization (esterification) reaction. LCP species were characterized by the following techniques / Polarized Light Microscopy, Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Analysis (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), X-ray Scattering (WAXS, Fiber diffraction), surface free energy, end group analysis (CEG), intrinsic viscosity (IV) and tensile test. According to these analysis LCPs were classified into five main categories / (I) fully aromatics, (II) aromatics+ PET/PEN, (III) aromatics + oligomers (IV) aromatics + short aliphatic diacids, (V) aromatics + long aliphatic diacids. The foremost results of the analysis can be given as below. DSC analysis shows that some LCPs are materials that have stable LC mesogens under polarized light microscopy. In TGA analysis LCPs that have film formation capacity passed the thermal stability test up to 390oC. NMR results proved that predicted structures of LCPs from feed charged to the reactor are correct. In FTIR due to the inclusion of new moieties, several peaks were labeled in the finger-print range that belongs to reactants. In X-ray analysis, LCP24 (containing PET) was found to be more crystalline than LCP25 (containing PEN) which is due to the symmetrical configuration. Block segments were more pronounced in wholly aromatic LCP2 than LCP24 that has flexible spacers. Another important finding is that, as the amount of the charge to the reactor increases CEG value increases and molecular weight of the product decreases. Selected group V species were employed as reinforcing agent and mixed with the thermoplastics / acrylonitrile butadiene styrene (ABS), nylon6 (PA6), polyethylene terephthalate (PET), polypropylene (PP) and appropriate compatibilizers in micro compounder and twin screw extruder. The blends of them were tested in dog-bone and/or fiber form. In general LCPs do not improve the mechanical properties except in composite application with polypropylene. A significant increase in tensile properties is observed by LCP24 and LCP25 usage. Capillary rheometer studies show that the viscosity of ABS decreases with the inclusion PA6 and LCP2 together. In addition to the composite applications, some LCPs are promising with new usage areas. Such as nano fibers with 200nm diameter were obtained from LCP27 by electrospinning method. The high dielectric constant of LCP29 has shown that it may have application areas in capacitors.