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dc.contributor.authorSimmons, Heather
dc.contributor.otherQueen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))en
dc.date.accessioned2019-04-23T20:06:40Z
dc.date.available2019-04-23T20:06:40Z
dc.identifier.urihttp://hdl.handle.net/1974/26099
dc.description.abstractThis thesis proposes strategies to improve the crystallinity and mechanical properties of poly(lactic acid) (PLA) and investigates the effects of these modifications on hydrolytic degradation. The effect of long-chain branching (LCB) on the hydrolytic degradation at 60°C was monitored through the mass loss, molar mass distributions, and thermal properties of degraded specimens. A three-week induction period prior to the onset of mass loss coupled with an immediate loss in molar mass of over 80% in the same timeframe pointed to a bulk erosion mechanism. The highest loss in molar mass was observed in the z-average molar mass (Mz) of LCB PLA, exceeding 90% in the first three-weeks, and was attributed to the cleavage of the LCB segments from the polymer chain. Degradation-induced crystallinity resulted from the enhanced chain mobility at the experimental conditions, owing to the combined influence of annealing and the plasticizing effect of water. Although the hydrolysis profile differed between the linear and branched PLAs, branching did not affect negatively the extent of degradation over a 12-week period. Increases in the crystallinity of PLA from 5% to 20% were achieved through reactive extrusion and the addition of biofiller (BF), a novel type of cross-linked PLA-based nucleating agent. The crystallinity of the nucleated formulations was further increased to over 50% by annealing at temperatures between 80 and 120C. The BF additive was particularly effective in improving the crystallinity due to its PLA-based nature, which provided good compatibility with the matrix material. Owing to the improved crystallinities, the annealed materials demonstrated over 30% increases in flexural moduli compared to the neat material, while impact strength was maintained. Annealing of the modified PLA also resulted in 10°C increases in the glass transition temperatures followed by improvements in the heat deflection temperature (HDT) by as much as 7°C. An annealing temperature of 100C was selected as optimum, due to evidence of thermal degradation taking place above this temperature. When subjected to hydrolysis over a 12-week period, the nucleated and annealed PLA degraded to the same extent as the untreated PLA, with over 30% loss in mass and 90% loss in molar mass.en_US
dc.language.isoenen_US
dc.relation.ispartofseriesCanadian thesesen
dc.rightsQueen's University's Thesis/Dissertation Non-Exclusive License for Deposit to QSpace and Library and Archives Canadaen
dc.rightsProQuest PhD and Master's Theses International Dissemination Agreementen
dc.rightsIntellectual Property Guidelines at Queen's Universityen
dc.rightsCopying and Preserving Your Thesisen
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectpoly(lactic acid)en_US
dc.subjecthydrolytic degradationen_US
dc.subjectbranchingen_US
dc.subjectnucleationen_US
dc.subjectannealingen_US
dc.subjectcontrolled crystallizationen_US
dc.subjectmechanical propertiesen_US
dc.titleDegradation and Crystallization Studies of Branched PLA Prepared by Reactive Extrusionen_US
dc.typethesisen
dc.description.degreeMaster of Applied Scienceen_US
dc.contributor.supervisorKontopoulou, Marianna
dc.contributor.departmentChemical Engineeringen_US


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