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Linking the Rheological Behavior to the Processing of Thermotropic Liquid Crystalline Polymers in the Super-cooled StateQian, Chen 01 June 2016 (has links)
Thermotropic liquid crystalline polymers (TLCPs) have attracted great interest because of the combination of their promising properties, which includes high stiffness and strength, excellent processability, and outstanding chemical resistance. TLCPs exhibit inherently low viscosity relative to many other conventional thermoplastics. The low melt viscosity is detrimental to processes requiring high melt strength, such as extrusion blow molding, film blowing, thermoforming and multilayer coextrusion. Our laboratory has developed a unique method to increase the viscosity of TLCPs by first raising the temperature above the melting point (Tm) to exclude all solid crystalline structure, and then lowering the temperature below Tm to super cool the materials. Additionally, the super-cooling behavior of TLCPs allows them to be blended with other thermoplastics possessing lower processing temperatures.
The initial focus of this dissertation is to investigate the processing temperature of a representative TLCP in the super-cooled state, using the methods of small amplitude oscillatory shear (SAOS), the startup of shear flow and differential scanning calorimetry (DSC). The TLCP used in this work is synthesized from 4-hydroxybenzoic acid (HBA), terephthalic acid (TA), hydroquinone (HQ) and hydroquinone derivatives (HQ-derivatives). The TLCP of HBA/TA/HQ/HQ-derivatives has a melting point, Tm, of around 280 oC. Once melted, the TLCP can be cooled 30 oC below the Tm while still maintaining its processability. As the TLCP was cooled to 250 oC, a one order magnitude increase in viscosity was obtained at a shear rate of 0.1 s-
1. Additionally, super cooling the TLCP did not significantly affect the relaxation of shear stress after preshearing. However, the recovery of the transient shear stress in the interrupted shear measurements was suppressed to a great extent in the super-cooled state.
The second part of this work is concerned with the extrusion blow molding of polymeric blends containing the TLCP of HBA/TA/HQ/HQ-derivatives and high density polyethylene (HDPE), using a single screw extruder. The blends were processed at a temperature of 260 oC which is 20 oC below Tm of the TLCP such that the thermal degradation of HDPE was minimized. Bottles were successfully produced from the blends containing 10, 20 and 50 wt% TLCP. The TLCP/HDPE blend bottles exhibited an enhanced modulus relative to pure HDPE. However, the improvement in tensile strength was marginal. At 10 and 20 wt% TLCP contents, the TLCP phase existed as platelets, which aligned along the machine direction. A co-continuous morphology was observed for the blend containing 50 wt% TLCP. The preliminary effectiveness of maleic anhydride grafted HDPE (MA-g-HDPE) as a compatibilizer for the TLCP/HDPE system was also studied. The injection molded ternary TLCP/HDPE/MA-g-HDPE blends demonstrated superior mechanical properties over the binary TLCP/HDPE blends, especially in tensile strength. Consequently, it is promising to apply the ternary blends of TLCP/HDPE/MA-g-HDPE in the blow molding process for improved mechanical properties.
Finally, this work tends to determine how the isothermal crystallization behavior of a TLCP can be adjusted by blending it with another TLCP of lower melting point. One TLCP (Tm~350 oC) used is a copolyester of HBA/TA/HQ/HQ-derivatives with high HBA content. The other TLCP (Tm~280 oC) is a copolyesteramide of 60 mol% hydroxynaphthoic acid, 20 mol% terephthalic acid and 20 mol% 4-aminophenol. The TLCP/TLCP blends and neat TLCPs were first melted well above their melting points, then cooled to the predetermined temperatures below the melting temperatures at 10 oC/min to monitor the isothermal crystallization. As the content of the low melting TLCP increased in the blends, the temperature at which isothermal crystallization occurred decreased. Comparing with neat TLCPs, the blend of 75% low melting TLCP crystallized at a lower temperature than the pure matrices, and the blend remained as a stable super-cooled fluid in the temperature range from 220 to 280 oC. Under isothermal conditions, differential scanning calorimetry (DSC) was not capable of reliably detecting the the low energy released in the initial stage of crystallization. In contrast, small amplitude oscillatory shear (SAOS) was more sensitive to detecting isothermal crystallization than DSC. / Ph. D.
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Injection Molding of Pregenerated MicrocompositesMcLeod, Michael Allen 09 January 1998 (has links)
One portion of this work was concerned with injection molding pregenerated microcomposites composed primarily of poly(ethylene terephthalate) (PET) as the matrix and HX1000 as the thermotropic liquid crystalline polymer (TLCP). Several factors were examined to maximize the mechanical properties of these composites, including injection molding temperature, matrix viscosity, and nozzle tip exit diameter. In addition, concentrated strands of HX1000/PET (50/50 wt%) were diluted using both an injection molding grade of PET and an injection molding grade of PBT. From this work, it was determined that the best mechanical properties were produced when the microcomposites were processed at the lowest injection molding temperatures, diluted with PBT, and injection molded using a large nozzle tip exit diameter.
The pregenerated microcomposite properties were compared against theoretical predictions as well as glass-filled PET. It was found that the pregenerated microcomposites had tensile moduli of approximately 70% of theoretical expectations in the machine direction. Additionally, the comparisons against glass-filled PET revealed that at the same weight fraction of reinforcement, the pregenerated microcomposites had lower properties. Still, the composites were found to have smoother surfaces than glass-filled PET and at temperatures up to 150° C the storage and loss moduli of the pregenerated microcomposites were similar to those of glass filled PET. It was concluded that if the theoretically expected levels of reinforcement could be attained, the pregenerated microcomposites processing scheme would be a viable method of producing light weight, wholly thermoplastic composites with smoother surfaces than are obtained with glass reinforcement.
An additional focus of this research was to evaluate the ability to modify the crystallization behavior of a high melting TLCP (HX6000, Tm = 332° C) with a lower melting TLCP (HX8000, Tm = 272°C). It was found that it was possible to tailor the crystallization behavior of these TLCP/TLCP blends by varying the weight fraction of each component, as determined by rheological cooling scans and differential scanning calorimetric cooling tests. Based on the analysis of these TLCPs at the maximum injection molding temperature of 360° C, it was speculated that they had reacted with one another. / Ph. D.
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Generation of Recyclable Liquid Crystalline Polymer Reinforced Composites for Use in Conventional and Additive Manufacturing ProcessesChen, Tianran 21 May 2021 (has links)
The application of glass fiber reinforced composites has grown rapidly due to their high strength-to-weight ratio, low cost, and chemical resistance. However, the increasing demand for fiber reinforced composites results in the generation of more composite wastes. Mechanical recycling is a cost-effective and environmentally-friendly recycling method, but the loss in the quality of recycled glass or carbon fiber composite hinders the wide-spread use of this recycling method. It is important to develop novel composite materials with higher recyclability. Thermotropic liquid crystalline polymers (TLCPs) are high-performance engineering thermoplastics, which have comparable mechanical performance to that of glass fiber. The TLCP reinforced composites, called in situ composites, can form the reinforcing TLCP fibrils during processing avoiding the fiber breakage problem.
The first part of this dissertation is to study the influence of mechanical recycling on the properties of injection molded TLCP and glass fiber (GF) reinforced polypropylene (PP). The processing temperature of the injection molding process was optimized using a differential scanning calorimeter (DSC) and a rheometer to minimize the thermal degradation of PP. The TLCP and GF reinforced PP materials were mechanically recycled up to three times by repeated injection molding and grinding. The mechanical recycling had almost no influence on the mechanical, thermal, and thermo-mechanical properties of TLCP/PP because of the regeneration of TLCP fibrils during the mold filling process. On the other hand, glass fiber/PP composites decreased 30% in tensile strength and 5% in tensile modulus after three reprocessing cycles. The micro-mechanical modeling demonstrated the deterioration in mechanical properties of GF/PP was mainly attributed to the fiber breakage that occurred during compounding and grinding.
The second part of this dissertation is concerned with the development of recyclable and light weight hybrid composites through the use of TLCP and glass fiber. Rheological tests were used to determine the optimal processing temperature of the injection molding process. At this processing temperature, the thermal degradation of matrix material was mitigated and the processability of the hybrid composite was improved. The best formulation of TLCP and glass fiber in the composite was determined giving rise to the generation of a recyclable hybrid composite with low melt viscosity, low mechanical anisotropy, and improved mechanical properties.
Finally, TLCP reinforced polyamide composites were utilized in an additive manufacturing application. The method of selecting the processing temperature to blend TLCP and polyamide in the dual extrusion process was devised using rheological analyses to take advantage of the supercooling behavior of TLCP and minimize the thermal degradation of the matrix polymer. The composite filament prepared by dual extrusion was printed and the printing temperature of the composite filament that led to the highest mechanical properties was determined. Although the tensile strength of the TLCP composite was lower than the glass fiber or carbon fiber composites, the tensile modulus of 3D printed 60 wt% TLCP reinforced polyamide was comparable to traditional glass or carbon fiber reinforced composites in 3D printing. / Doctor of Philosophy / The large demand for high performance and light weight composite materials in various industries (e.g., automotive, aerospace, and construction) has resulted in accumulation of composite wastes in the environment. Reuse and recycling of fiber reinforced composites are beneficial from the environmental and economical point of view. However, mechanical recycling deteriorates the quality of traditional fiber reinforced composite (e.g., glass fiber and carbon fiber). There is a need to develop novel composites with greater recyclability and high-performance.
Thermotropic liquid crystalline polymers (TLCP) are attractive high performance materials because of their excellent mechanical properties and light weight. The goal of this work is to generate recyclable thermotropic liquid crystalline polymer (TLCP) reinforced composites for use in injection molding and 3D printing. In the first part of this work, a novel recyclable TLCP reinforced composite was generated using the grinding and injection molding. Recycled TLCP composites were as strong as the virgin TLCP composites, and the mechanical properties of TLCP composites were found to be competitive with the glass fiber reinforced counterparts. In the second part, a hybrid TLCP and glass fiber reinforced composite with great recyclability and excellent processability was developed. The processing conditions of injection molding were optimized by rheological tests to mitigate fiber breakage and improve the processability. Finally, a high performance and light weight TLCP reinforced composite filament was generated using the dual extrusion process which allowed the processing of two polymers with different processing temperatures. This composite filament could be directly 3D printed using a benchtop 3D printer. The mechanical properties of 3D printed TLCP composites could rival 3D printed traditional fiber composites but with the potential to have a wider range of processing shapes.
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Generation of Multi-Scale Thermoplastic Composites for Use in Injection Molding and Fused Filament FabricationHan, Jier Yang 07 January 2021 (has links)
Thermoplastic composites that have been reinforced by thermotropic liquid crystalline (TLCP) fibrils in the microscale and by nanoparticles in the nanoscale are defined as multi-scale wholly thermoplastic composites (WTCs). Multi-scale WTCs have been proposed as lightweight replacements with high performance for some traditional glass fiber (GF) and carbon fiber (CF) reinforced composites materials in various applications. TLCPs are known for performing mechanical properties similar to those of the lower end of CF but significantly better than those of GF. To enhance the mechanical properties of TLPC reinforced WTCs, carbon nanotubes (CNTs) are considered being used as a secondary enhancement in WTCs. CNTs have gathered significant interest in the last 30 years because of their high aspect ratio, high mechanical properties, and other high-performance properties. The focus of this work is on investigating the processing conditions of generating in situ injection-molded multi-scale WTCs, then extending the technology to dual-extrusion and fused filament fabrication (FFF) and obtain high-performance multi-scale WTC products.
This dissertation initially focused on investigating the processing conditions, in particular mixing histories and processing temperature profiles, of generating in situ injection-molded multi-scale WTCs, which consist of a representative TLCP, scCO2 aided exfoliated CNTs, and the thermoplastic matrix polyamide 6 (PA 6). The supercooling behavior of the TLCP and thermal stability of PA 6 are studied by applying the rheological methods of small amplitude oscillatory shear (SAOS). Multiple mixing histories with CNTs and processing temperature profiles are analyzed based on the criterion of maximizing tensile properties of multi-scale WTCs and minimizing thermal degradation of the matrix. Under the optimum processing conditions, the in situ injection-molded multi-scale WTCs exhibit a 26% and 34% tensile modulus and strength enhancement, compared to the in situ injection-molded WTCs with no CNTs. Scanning electron micrograph (SEM) images were used to understand the enhancement.
The second part of this work is to extend the scCO2 aided in situ multi-scale WTCs processing technology to dual-extrusion and FFF. Multi-scale WTC filaments, which consists of TLCP, CNTs, and polyamide copolymer (PAc), are generated by dual-extrusion, and 3D printed into rectangular specimens in FFF. The 1 wt% CNTs reinforced multi-scale WTC filaments generated by the means of dual-extrusion exhibit 225% and 80% improvement in tensile modulus and strength, respectively, compared to the WTC filaments with no CNTs. In FFF, 40 wt% TLCP/1 wt% CNT/PAc 3D printed specimens with filament laid in longitudinal direction exhibited excellent tensile modulus and strength of 38.92 GPa and 127.16 MPa, respectively. The well-dispersed exfoliated CNTs show high alignment with TLCP microfibrils in the multi-scale WTC filaments and their laid-down specimens, which causes the significant tensile modulus enhancement. Bridging elements are discovered between TLCP fibrils and PAc matrix to improve interfacial adhesion, which is attributed to the well-dispersed exfoliated CNTs.
Finally, the significant improvements in tensile properties attributed to scCO2 aided exfoliated CNTs in WTCs are verified on the multi-scale WTCs based on polypropylene (PP). Moreover, additional tensile properties improvements for exfoliated CNTs reinforced multi-scale WTCs are obtained with the use of maleic anhydride grafted polypropylene (MAPP). With 1 wt% CNTs and 16 wt% MAPP dual reinforcement, 20 wt% TLCP reinforced WTCs based on polypropylene (PP) exhibit 265%, 274%, and 182% improvement in the tensile modulus of the filaments, laid up specimens in the concentric pattern and laid up specimens in ±45° rectilinear pattern, respectively. The dual reinforcement also improves the tensile strength of 20 wt% TLCP reinforced WTC filaments by up to 73%. The high alignment between TLCP fibrils and CNTs are confirmed in the multi-scale WTCs based on PP. Besides the bridging elements attributed to CNTs found in the second part of this work, SEM images show that CNTs are partially trapped in TLCP fibrils. / Doctor of Philosophy / Considering the need for environmentally friendly materials, novel thermoplastic composites with high mechanical performance, lightweight, and potentially high recyclability properties were generated in this work. Two types of thermoplastic matrices, polyamide (PA or nylon) and polypropylene (PP) were reinforced with carbon nanotubes (CNTs) and rigid chain polymers known as thermotropic liquid crystalline polymers (TLCPs). CNTs are known for their high mechanical properties and high aspect ratio, which are helpful to reinforce thermoplastic composite materials. During injection molding and the dual-extrusion processes, TLCPs deform into almost continuous microfibrils and reinforce the thermoplastic matrices. Instead of using traditional glass fibers or carbon fibers to reinforce thermoplastics, TLCP reinforced thermoplastic composites, which are defined as wholly thermoplastic composites (WTCs), can retain their mechanical properties during the recycling process such as in injection molding and have better performance during the lay-down process in fused filament fabrication. The goal of this work was to generate CNTs reinforced WTCs for use in injection molding and fused filament fabrication with high mechanical performance.
In the injection molding process for generating CNTs reinforced WTC end-gated plaques, it was determined that the optimum thermal mixing histories for the CNTs could be identified by the inspections of the tensile property measurements and scanning electron microscopy (SEM). With the obtained optimum thermal mixing histories with CNTs, CNTs reinforced WTC filaments were generated by dual extrusion technology and used in fused filament fabrication. With 1 wt% addition of CNTs, the tensile properties of WTCs were significantly enhanced in both the filament materials and the laid-down parts. Especially, the CNT reinforced WTC filaments based on nylon matrices exhibited competitive tensile moduli to long carbon fiber reinforced nylon composite filaments, which was also competitive to the properties of aluminum alloys. In addition, the laid-down parts of CNTs reinforced WTC based on PP presented further tensile strength improvement due to the improved interfacial adhesion between the laid-down filaments and between layers, which was attributed to the addition of maleic anhydride grafted polypropylene.
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