雙嵌段共聚物(diblock copolymers)可藉由調整各鏈段不同體積分率而自組裝形成不同有序排列的微相分離結構，可提供一個較簡易形成的奈米結構來探討結晶性高分子在混摻系統中侷限環境下的結晶行為。不同於高分子混摻系統中常見的同質性混摻 (homogeneous blends)，我們採用較少見的異質性混摻(heterogeneous blends)並選擇溶解度參數相近的結晶性材料聚環氧乙烷(PEO)與嵌段共聚物聚苯乙烯聚二乙烯吡啶(PS-P2VP)來研究，發現混摻入不同分子量PEO時，於PS-P2VP的微相分離環境下選擇性地分散聚集在極性P2VP鏈段中形成不同的形態如六角排列圓柱堆積結構或是奈米層狀微結構。不同於半結晶性雙嵌段共聚物(semi-crystalline diblock copolymers)之化學侷限(chemical confinement)系統由於結晶性PEO鏈段和PS-P2VP間並無化學鍵結因素存在，所以在此混摻系統中PEO的結晶行為是受到物理侷限(physical confinement)環境下形成局部偏析聚集而產生球狀、柱狀之結晶，抑或是太過分散而形成無法結晶的PEO。本研究利用穿透式電子顯微鏡之形態觀察以及微差掃描熱卡計所測定之混摻系統下的結晶熔點與相應之侷限結晶形態之關聯性，並配合小角X光散射與廣角X光繞射提供統計性的數據用以確認嵌段共聚物之微相分離結構以及PEO之結晶行為，發現混摻高分子量PEO之系統傾向自我聚集成球狀結晶在P2VP鏈段區中，透過不同的除核溫度，可以得到不同尺寸的球狀侷限結晶，並在混摻低分子量PEO系統中，雖然形成不均勻之聚集分布在P2VP鏈段區中，但低分子量PEO卻因侷限效應而呈現出不結晶之行為。

Owing to various nanoscale structures from self-assemble block copolymers (BCPs), it could provide a facile means to study polymer crystallization under nanoscale confinement. Different from the studies using homogeneous blends (A-B/HA or A-B/HB system) with an additive homopolymer identical to one of the blocks in block copolymers, here we employed heterogeneous blends (A-B/HC system) with the additive homopolymer chemically different from the constituted blocks. Crystalline homopolymers, polyethylene oxide (PEO) with different molecular weights (MWs), were introduced into amorphous BCPs, polystyrene-block-poly(2-vinyl pyridine) (PS-P2VP). Investigation was carried out for the PEO crystallization physically confined within different nano-sized morphologies including lamellae and hexagonally-packed cylinders. We found that thermal treatments with different elimination temperatures (Tmax) of crystallization, crystallization of high-MW PEO could be confined within distinct geometry of spheres or pillar-shaped cylinders, due to the variation of the chain mobility of the PEO blocks. This results in significant difference in crystallization and melting behavior under these physically confined nanostructures. To examine the compatibility effect, low-MW PEO is also blended with the PS-P2VP BCP. We observed the coexistence of uniform and nonuniform localizations of low-MW PEO chains within the P2VP nanodomain. Owing to well solubilization, low-MW PEO chains exhibit non-crystallizable behavior under physical confinement.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
Contents vi
List of Figures viii
List of Tables xi
Chapter 1. Introduction 1
1.1 Self-Assembly 1
1.2 Block Copolymer (BCP) Self-assembly 4
1.3 High-MW BCPs/ Homopolymer Blending System 6
1.4 Solubility Limit 10
1.5 Crystallizable BCPs with chemical confinement 12
1.6 Physical confinement 14
Chapter 2. Objectives 18
Chapter 3. Materials and Experimental Methods 19
3.1 Materials 19
3.2 Sample Preparation 19
3.2.1 Bulk samples prepared by solution casting 19
3.2.2 PS-P2VP/PEO Polymer Blending System 20
3.3 Microstructural Characterization 20
3.3.1 Transmission electron microscopy (TEM) 20
3.3.2 Differential scanning calorimetry (DSC) 21
3.3.3 Small-angle X-ray scattering (SAXS) and Wide-angle X-ray diffraction (WAXD) 22
Chapter 4. Results & Discussion 23
4.1 Self-assembling Morphology of High-MW PS-P2VP BCP in Bulk 23
4.2 Physical Confinement of PS-b-P2VP/PEO Blends 26
4.2.1 Morphologies in PS-b-P2VP / PEO Heterogeneous Blends 26
4.2.2 Effect of Molecular Weight of PEO in Heterogeneous Blends 33
4.3 Thermal behaviors of Heterogeneous blends 35
4.3.1 Thermal Properties of PS-P2VP BCP and PEO homopolymers 35
4.3.2 Thermal Properties of PS-P2VP/PEO100 Blends 37
4.3.3 Thermal properties of PS-b-P2VP / PEO20 Blends 49
Chapter 5. Conclusion 53
Chapter 6. References 55

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