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研究生: 林依娟
Lin, I-Chuan
論文名稱: 同步加速器X-微光束繞射分析半結晶生物高分子週期性柵狀結構
Synchrotron X-ray Microbeam Diffraction Analyses on Periodically Grating Structures of Semicrystalline Biopolymers.
指導教授: 吳逸謨
Woo, Eamor M.
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2023
畢業學年度: 111
語文別: 中文
論文頁數: 77
中文關鍵詞: 聚羥基丁酸酯聚己二酸二乙酯環帶狀球晶結晶形貌晶板排列同步加速器微光束分析
外文關鍵詞: D-(-)-poly(3-hydroxybutyrate), poly(ethylene adipate), ring-banded spherulite, crystalline morphology, lamellae assembly, synchrotron microbeam X-ray
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  • 本研究利用偏光顯微鏡(polarized-light optical microscopy, POM)、掃描式電子顯微鏡(scanning electron microscopy, SEM)、小角度X光散射儀(microbeam small-angle X-ray scanning, SAXS)以及廣角度X光繞射儀(microbeam wide-angle X-ray diffraction, WAXD)探討生物可分解性高分子聚羥基丁酸酯(D-(-)-poly(3-hydroxybutyrate), PHB)摻合聚己二酸二乙酯(Poly(ethylene adipate), PEA)後的結晶行為,控制結晶溫度使PEA成不定形狀態作為稀釋劑之角色。首先改變組成比例、熔融溫度及結晶溫度,透過POM初步觀察球晶形貌,以環帶寬度較大且環帶最規則之Tc=48 oC進一步分析,以SEM觀察球晶上表面與內部晶板排列,上表面觀察到順時針彎曲之裂縫與浮凸結構,內部則是細長型的直立式晶板排列形成ridge後快速彎曲成水平方向形成valley,同時於反方向長出水平分枝填滿球晶。接著利用microbeam SAXS及WAXD確認內部晶板排列之正確性及晶格的轉變,輔助證明在SEM下觀察到的晶板排列,推測PHB環帶狀球晶內部晶體的週期性排列與其不連續性,進而建立完整的球晶生長機制。Neat PEA於交替結晶下形成帶有枝狀(ringless)與雙環帶狀(ring-band)之人造環帶狀球晶,透過SEM觀察兩者內部晶板排列之差異,ringless為分形分枝的結構,ring-band則是規則的柵狀排列,並透過microbeam SAXS及WAXD輔助說明。最後進行光反射實驗,歸納出環帶間距小且環帶整齊之球晶,能反射出強烈的虹彩結構光;而人造環球晶因ringless部分不具有整齊的週期性結構,使得整體反射的結構光不連續且色彩微弱。

    A semi-crystalline biopolymer, D-(-)-poly(3-hydroxybutyrate) (PHB), was crystallized in the presence of poly(ethylene adipate) (PEA). Control the crystallization temperature (Tc) to make PEA into an amorphous state as a diluent in the blend system. By using polarized optical microscopy (POM), scanning electron microscope (SEM), and synchrotron microbeam X-ray to observe the crystalline morphology and analyze mechanisms of lamellae arrangement. In PHB/PEA, spherulites show the most regular ring bands at Tc=48 oC. From the top surface of view, the needle-like crystals in the ridge region are arranged along the radial direction and bend clockwise to the valley with relief patterns. The correlation between top surface and interior lamellar arrangement is that the lamellae grow perpendicular to the substrate at the ridge region and then bend to the valley arranges in flat-on lamellae. Simultaneously, the ridge grows lamellae parallel to the substrate in the opposite direction to fill the valley. Then, synchrotron microbeam SAXS and WAXD were used to confirm results observed by SEM. PEA was subjected to alternating crystallization cycles between 21 oC and 35 oC to form artificial ring bands. Observe the differences of interior lamellar arrangement between ringless and ring-band through SEM. Then, the critical proofs via microbeam X-ray signals in the ringless vs. ring-band morphologies confirm the SEM results in agreement with the crystal assembly characteristics revealed by microbeam X-ray analyses. Finally, it shows iridescent color from the sample in PHB/PEA blend system due to its periodic and ordered structure. On the contrary, PEA artificial ring-banded system exhibits the weak and discontinuous iridescence properties due to the dendritic regions with the absence of regularity.

    中文摘要 I Abstract II 致謝 XIV 目錄 XVI 圖目錄 XVIII 表目錄 XXVI 第一章 研究目的與文獻回顧 1 1.1 簡介 1 1.2 週期性環帶結構之相關研究 2 1.3 小角度及廣角度X-ray散射之相關研究 8 1.4 虹彩光性質之測試 12 1.5 聚羥基丁酸酯之相關研究 15 1.6 聚己二酸二乙酯之相關研究 18 1.7 研究動機與方向 19 第二章 實驗材料與方法 20 2.1 實驗藥品與材料 20 2.2 樣品製備 21 2.3 實驗使用之儀器與方法 22 2.3.1 偏光顯微鏡 (Polarized-light optical microscopy, POM) 22 2.3.2 高解析度場發射式掃描式電子顯微鏡 (High-resolution field-emission scanning electron microscopy, HR-FESEM) 22 2.3.3 同步加速器X光 (Synchrotron microbeam X-ray) 22 2.3.3.1 微光束小角度X光散射儀 (Microbeam small-angle X-ray scattering, SAXS) 23 2.3.3.2 微光束廣角度X光繞射儀 (Microbeam wide-angle X-ray diffraction, WAXD) 23 第三章 結果與討論 24 3.1 PHB/PEA摻合系統之探討 24 3.1.1 球晶形貌觀察 24 3.1.2 環帶狀球晶之上表面分析 28 3.1.3 環帶狀球晶內部晶板排列分析 32 3.1.4 Microbeam SAXS分析 36 3.1.5 Microbeam WAXD分析 40 3.1.6 不同環帶形貌之Microbeam分析比較 47 3.1.7 虹彩性質分析 51 3.2 PEA人造環帶狀球晶之探討 53 3.2.1 球晶形貌觀察 53 3.2.2 球晶上表面形貌及內部結構分析 54 3.2.3 Microbeam SAXS分析 56 3.2.4 Microbeam WAXD分析 59 3.2.5 虹彩性質分析 62 第四章 結論 64 參考文獻 67 附錄 (Supporting information) 75

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