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Yes / Highly oriented poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) blends were fabricated through solid hot stretching technology in an effort to improve the mechanical properties and blood biocompatibility of PLA as blood-contacting medical devices. It was found that the tensile strength and modulus of the blends can be improved dramatically by stretching. With the increase of draw ratio, the cold crystallization peak became smaller, and the glass transition and the melting peak moved to high temperature, while the crystallinity increased, and the grain size of PLA decreased, indicating of the stress-induced crystallization during drawing. The oriented blends exhibited structures with longitudinal striations which indicate the presence of micro-fibers. TPU phase was finely and homogeneously dispersed in the PLA, and after drawing, TPU domains were elongated to ellipsoid. The introduction of TPU and orientation could enhance the blood compatibility of PLA by prolonging kinetic clotting time, and decreasing hemolysis ratio and platelet activation.

Yes / Highly-oriented poly (lactic acid) (PLA) with bionic fibrillar structure and micro-grooves was fabricated through solid hot drawing technology for further improving the mechanical properties and blood biocompatibility of PLA as blood-contacting medical devices. In order to enhance the melt strength and thus obtain high orientation degree, PLA was first chain branched with pentaerythritol polyglycidyl ether (PGE). The branching degree as high as 12.69 mol% can be obtained at 0.5 wt% PGE content. The complex viscosity, elastic and viscous modulus for chain branched PLA were improved resulting from the enhancement of molecular entanglement, and consequently higher draw ratio can be achieved during the subsequent hot stretching. The stress-induced crystallization of PLA occurred during stretching, and the crystal structure of the oriented PLA can be attributed to the α′ crystalline form. The tensile strength and modulus of PLA were improved dramatically by drawing. Chain branching and orientation could significantly enhance the blood compatibility of PLA by prolonging clotting time and decreasing hemolysis ratio, protein adsorption and platelet activation. Fibrous structure as well as micro-grooves can be observed for the oriented PLA which were similar to intimal layer of blood vessel, and this bionic structure was considered to be beneficial to decrease the activation and/or adhesion of platelets.

Yes / Highly-oriented poly (lactic acid) (PLA) with bionic micro-grooves was fabricated through solid hot drawing technology for further improving the mechanical properties and blood biocompatibility of PLA. In order to enhance the melt strength and thus obtain high orientation degree, long chain branched PLA (LCB-PLA) was prepared at first through a two-step ring-opening reaction during processing. Linear viscoelasticity combined with branch-on-branch (BOB) model was used to predict probable compositions and chain topologies of the products, and it was found that the molecular weight of PLA increased and topological structures with star like chain with three arms and tree-like chain with two generations formed during reactive processing, and consequently draw ratio as high as1200% can be achieved during the subsequent hot stretching. With the increase of draw ratio, the tensile strength and orientation degree of PLA increased dramatically. Long chain branching and orientation could significantly enhance the blood compatibility of PLA by prolonging clotting time and decreasing platelet activation. Micro-grooves can be observed on the surface of the oriented PLA which were similar to the intimal layer of blood vessel, and such bionic structure resulted from the formation of the oriented shish kebab-like crystals along the draw direction.

Yes / Highly oriented poly(lactic acid) (PLA)/multi-walled carbon nanotubes (MWNTs) composites were fabricated through solid hot drawing technology in an effort to improve the mechanical properties and blood biocompatibility of PLA as blood-contacting medical devices. It was found that proper MWNTs content and drawing orientation can improve the tensile strength and modulus of PLA dramatically. With the increase in draw ratio, the cold crystallization peak became smaller, and the glass transition and the melting peak of PLA moved to high temperature, while the crystallinity increased, and the grain size decreased, indicating the stress-induced crystallization of PLA during drawing. MWNTs showed a nucleation effect on PLA, leading to the rise in the melting temperature, increase in crystallinity and reduction of spherulite size for the composites. Moreover, the intensity of (002) diffraction of MWNTs increased with draw ratio, indicating that MWNTs were preferentially aligned and oriented during drawing. Microstructure observation demonstrated that PLA matrix had an ordered fibrillar bundle structure, and MWNTs in the composite tended to align parallel to the drawing direction. In addition, the dispersion of MWNTs in PLA was also improved by orientation. Introduction of MWNTs and drawing orientation could significantly enhance the blood compatibility of PLA by prolonging kinetic clotting time, reducing hemolysis ratio and platelet activation.

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Synthesized polymer from bio-based and renewable resources reported as an attractive substitution for fossil-fuel based polymers. Therefore, this work has focused on using sustainable material for production of elastomers to reduce the environmental impact of fossil-based elastomers and overcome the shortage of non-renewable fuels. In this research (as thesis work) bio-based elastomers (resins synthesized by reacting of lactic acid with 1,4-butanediol in presence of toluene and methanesulfonic acid as solvent and catalyst, respectively. To trace the reaction, the Fourier transform infrared (FT-IR) spectrometer was used for structural characterization of the products. Furthermore, the degree of reaction followed by measuring of the acid value using alkali titration method. To achieve the desirable results, both condensed resins were reacted with caprolactone for ring opening polymerization. The produced resins were finally functionalized using methacrylic anhydride and the structures and thermal properties of the produced resin were characterized using FT-IR, DSC and TGA. In addition, the viscoelastic properties of the resins were investigated using dynamic mechanical analysis (DMA); and elasticity and viscosity of the elastomers measured using tensile testing machine and viscometer, respectively. The important result such as viscosity showed the resin with chain length n= 5 had higher viscosity when compared to the resin chain length n=3. This makes the resin (n=5) suitable for applications that need high viscosities. The resin with chain length n=3 had lower viscosity that is suitable for processing at room temperature. Furthermore, the tensile strength results show maximum elongation for resin with chain length n=3 is almost double compared to resin with chain length n=5. The results showed that these bio-based resins are compatible with petrochemical-based resins, due to desirable rubbery properties, melting temperature, also acceptable viscosity, and other good mechanical properties as will be mentioned below.

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<p>In this study, attempts were made to diversify the application of potato starch based biopolymer as foam-grade materials. To improve foamability, which is largely dependent on melt strength, it is possible to modify hydrolyzed starch based biopolymers by bulk modification with bi- and multi- functional epoxy chain extenders. The modification work was carried out using a twin screw extruder (TSE) and an internal batch mixer (Haake Mixer) with four different chain extenders. The modified blends were characterized by Parallel Plate Rheometry, DSC, Intrinsic Viscosity and SEM techniques. Finally, foamability of the modified blends was examined by using supercritical CO₂ as a physical blowing agent in a high-pressure batch vessel. Variables such as saturation pressure, saturation time and saturation temperature were adjusted to determine their influence on the cell morphology of the foamed parts.</p> <p>The multi-functional epoxy chain extenders effectively increased the bulk melt viscosity and reduced the crystalline content of both hydrolyzed starch based biopolymers. The intrinsic viscosity measurements were quantified the chain extension reaction, which primarily occurred in the PLA/AAC or PLA phase in both biopolymers and the starch phase made no contribution towards increased bulk melt viscosity. The multi-functional Joncryl^® ADR 4370S was the most effective chain extender for improving the stability of foams by yielding smaller cell size and higher cell density in comparison with the original biopolymer during the batch foaming process at 10 MPa saturation pressure and 30 min saturation time. The use of other chain extenders proved to be mostly ineffectual in producing uniform cellular structure in their corresponding modified biopolymer at those same processing conditions.</p> / Master of Applied Science (MASc)