本研究係透過微觀尺度的顯微及X 射線微束技術，針對生物可分解類高分子、共聚高分子或摻合體之球晶形貌進行探討。利用具有雙環帶球晶的生物可分解類聚羥基丁酸酯共聚羥基戊酸酯 [poly(3-hydroxybutyrate-co-3-hydroxyvalerate)，PHBV] 與 30 wt% 的不定形高分子聚醋酸乙烯 [poly(vinyl acetate)，PVAc] 進行混摻後，以偏光顯微鏡 (polarized light optical microscope，POM)、掃描式電子顯微鏡 ( scanning electron microscope，SEM)、原子力顯微鏡 (atomic force microscope，AFM) 及X 射線微束繞射技術 (micro-beam X-ray diffraction) 進行觀察。研究中將 PHBV/PVAc 70/30 組成的環帶狀球晶沿線性方向以每 5 μm 為一個間距進行X 射線微束繞射分析。另外，研究中亦透過斷裂及溶劑進行選擇性蝕刻，幫助研究摻合體球晶內部之晶板排列狀況。三維空間的 PHBV 環帶狀球晶其內部細緻的晶板排列方向，在此研究中進行揭露。由 SEM 及 X 射線微束繞射結果顯示，PHBV 的晶板排列沿球晶成長方向逐漸朝右手手性方向進行偏轉。因 PVAc 摻入而引發之 PHBV 環帶間距及其環帶規則度上的差異，在此研究中亦進行討論。後續利用聚己二酸二乙酯 [poly(ethylene adipate)，PEA]、聚己二酸二丁酯 [poly(1,4-butylene adipate)，PBA]、聚己二酸二己酯 [poly(1,6-hexamethylene adipate)，PHA] 及聚己内酯 [poly(epsilon-caprolactone)，PCL] 等聚酯類高分子，透過 POM 及 AFM 觀察其薄膜狀態在不同特性的玻璃基板上之球晶形貌。利用旋轉塗佈技術將聚酯類高分子薄膜製備於未改質及兩種聚甲基丙烯酸酯類高分子 [聚甲基丙烯酸苄酯 poly(benzyl methacrylate)，PBzMA 及聚甲基丙烯酸甲酯 poly(methyl methacrylate)，PMMA] 接支的玻璃基板表面。研究發現，在改質的基板上進行熔融結晶的 PEA、PBA 及 PHA 薄膜所生成的球晶形貌與在未改質基板上生成的球晶形貌相同。然而，在 PCL 系統則發現兩種新的球晶形貌 (一種為混合有負型雙折射及不具雙折射特性的球晶形貌，另一種為具正型雙折射特性且外形似水芙蓉的球晶形貌)。由 AFM 的研究結果發現，具負型雙折射特性的 PCL 晶體是由晶板以 edge-on 方式堆疊而成，而正型雙折射特性及不具雙折射特性的 PCL 晶體則是由晶板以略微傾斜的 flat-on 方式 (朝球晶成長方向前傾或後傾) 堆疊而成。此外，PCL 在 PCL/PBzMA 及 PCL/PMMA 摻合體中的熔融及結晶表現，也在本研究中透過微差掃描熱卡計 (differential scanning calorimetry，DSC) 進行觀察，由研究結果可進一步推斷，PCL 在聚甲基丙烯酸酯類高分子接支的玻璃基板表面之結晶度仍可維持在 50% 左右。

This study has been focused on the spherulitic morphology of biodegradable polyesters, copolymer, and blends by using microscopic and microbeam X-ray techniques. Double ring-banded spherulites of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV with 12 wt% 3HV) blending with 30 wt% amorphous poly(vinyl acetate) (PVAc) were examined using polarized light optical microscopy (POM), scanning electron microscopy (SEM), atomic-force microscopy (AFM), and micro-beam X-ray diffraction. A ring-banded spherulite of PHBV/PVAc 70/30 blend was linearly scanned across the bands in 5 μm steps by means of microbeam X-ray diffraction. Solvent-etching and fracturing were utilized for probing the interior lamellar textures of the blend samples. Detail interior lamellar orientations in bulk film of PHBV three-dimensional ring-banded spherulites were revealed. SEM and micro-beam X-ray diffraction results suggest that the PHBV lamellar orientation gradually change along the radial growth direction with right-handed rotation sense. The blending effect in band pattern (width and regularity) of PHBV/PVAc blend was also discussed. Subsequently, the spherulitic morphology of poly(ethylene adipate) (PEA), poly(1,4-butylene adipate) (PBA), poly(1,6-hexamethylene adipate) (PHA), and poly(epsilon-caprolactone) (PCL) thin films on different glass substrates were investigated by using POM and AFM. Polyester films were prepared by spin coating technique onto unmodified and two types of polymethacrylate (poly(benzyl methacrylate), PBzMA and poly(methyl methacrylate), PMMA) grafted glass slides. Melt-crystallized PEA, PBA, and PHA thin films on modified substrates exhibited the same spherulitic morphologies with their film samples on unmodified glass slides. However, two types of newfound spherulitic morphologies (negative- and non-birefringence mixed pattern and positive-type water lettuce-like pattern) were observed in PCL film samples. AFM observation shows that the negative-type birefringence crystals of PCL are composed of edge-on lamellae and the positive-type or non-birefringence crystals are composed of tilted flat-on lamellae (forward or backward along their radial direction). Furthermore, the melting and crystallization behaviors of PCL in PCL/PBzMA and PCL/PMMA blends have investigated in this study by using differential scanning calorimetry (DSC). DSC results suggest that the crystallinity of PCL on polymethacrylate grafted glass slides can be maintained at nearly 50% still.

Chapter 1
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Chapter 3
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Chapter 4
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