臺灣博碩士論文加值系統

本研究擬針對PEO-b-PB系統，利用原先呈現層狀形態之
PEO-b-PB，藉著摻入不同分子量之PB，分別造成”wet brush”與”dry brush”的效果。除了探討此兩種摻合體的結晶動力學的差異之外，並觀察PEO結晶後，對整體形態所造成的影響。
於”wet brush”系統，呈現層狀的團聯式共聚合物PEO-b-PB，摻入分子量遠低於其中PB鏈段的均聚物PB，其微相分離形態由層狀轉成體心立方堆積的球，其結晶溫度也降至低溫（-27~-28℃），顯示其成核機制應為均質成核。而當PEO結晶後，PEO microdomain由球轉變成橢圓，但並未出現連結的跡象，為”Confined”之結晶模式。
於”dry brush”系統，摻入分子量與團聯式共聚合物中PB鏈段相近的均聚物PB，其微相分離形態仍維持原先的層狀，PB層則由於均聚物PB的摻入而增厚，而增厚至某一程度使層狀開始出現扭曲，形成閉迴路或cylindrical vesicle，最後轉變為spherical vesicle。純的團聯式共聚合物PEO-b-PB，PEO結晶時穿越PB層與另一PEO層產生連結，產生穿層現象而其Avrami n = 2.79，顯示為異質成核且晶體成長在三個方向並未受到挶限，此屬”Breakout”結晶模式。隨著PB層的增厚，抑止住PEO結晶所造成的穿層現象，晶體成長只能於grain boundary處傳遞，n值下降至1.8 ~ 2.2，雖仍出現大範圍的晶體成長，但熔融形態被大幅地保存住，此屬”Templated”結晶模式。當形態轉成spherical vesicle，PEO結晶行為被挶限在圓球的殼層中，結晶並未改變其熔融態之形態，在結晶動力上符合一級反應方程式，顯示其結晶機制轉為均質成核控制，此屬
"Confined”結晶模式。

We studied the crystallization behavior in a block copolymer/homopolymer blend system exhibiting “dry-brush” phase behavior in the melt. A nearly symmetric poly(ethylene oxide)-block-polybutadiene (PEO-b-PB) was blend with a PB homopolymer (h-PB) having approximately the same molecular weight as that of the PB block, thereby yielding the dry-brush blends wherein h-PB was localized in the PB microdomain, causing thickness expansion of the PB domain without introducing transformation in microdomain morphology. Even though the lamellar identity of PEO domain retained throughout the blend composition, the global structure of the lamellar unit transformed from lamellar to cylindrical to spherical vesicles with increasing h-PB composition. The fixed cooling rate experiment in the differential scanning calorimetry (DSC) revealed that the crystallization of PEO in the lamellar phase proceeded at the undercooling comparable to that of PEO homopolymer over the major composition range (wh-PB £ 0.7). The corresponding isothermal crystallization kinetics was properly described by the classical Avrami equation, indicating that the crystallization started from heterogeneous nucleation followed by long-range crystal growth. In neat PEO-b-PB, the long-range growth was driven by breaking out the melt morphology (which led to percolated lamellar structure and spherulitic), while in the blends it was assisted by the connected PEO lamellae in the melt (which led to preservation of melt structure). At very high h-PB composition (wh-PB ³ 0.8) where the PEO lamellae formed spherical vesicles in the melt, a crystallization exotherm located at very large undercooling (ca. 90K) emerged upon cooling. The isothermal crystallization experiment revealed that the corresponding crystallization followed a simple first-order kinetics prescribed by a homogeneous nucleation-controlled crystallization wherein the crystallization started from homogeneous nuclei followed by essentially instantaneous crystal growth to fill domain space. Crystallization modes in the present dry-brush system may thus be breakout, templated, or confined depending upon the composition of h-PB. In general, the confinement effect exerted by dry-brush blending was far less effective than the corresponding wet-brush blending in which the confinement started to operate at wh-PB ≈ 0.48 (i.e. the composition where the PEO domains transformed into cylinders).

目錄
摘要……………………………………………………………………I
Abstract………………………………………………………………II
目錄……………………………………………………………………III
圖目錄…………………………………………………………………V
表目錄…………………………………………………………………IX
一、文獻回顧……………………………………………………………1
1.1前言……………………………………………………………1
1.2無定形團聯式共聚合物之形態轉換…………………………2
1.3結晶性團聯式共聚合物結晶行為對形態之影響……………10
1.4團聯式共聚合物摻合體之形態……………………………22
二、實驗部分………………………………………………………30
2.1研究目的與動機………………………………………………30
2.2樣品………………………………………………………31
2.3實驗流程………………………………………………………32
2.4儀器原理………………………………………………………33
2.4-1微分熱卡計………………………………………………33
2.4-2小角度X光散射儀………………………………………33
2.4-3穿透式電子顯微鏡………………………………………34
三、結果與討論………………………………………………………36
3.1 Wet Brush（PEO-b-PB/PB）摻合體熔融態之微相分離形態……36
3.2 Wet Brush（PEO-b-PB/PB）摻合體結晶後之形態變化……47
3.2-1 12k85摻合體結晶後之形態變化………………………47
3.2-2 1k85摻合體結晶後之形態變化………………………52
3.3 Dry Bursh（PEO-b-PB/PB）摻合體之熔融形態……………63
3.3-1 Dry Brush摻合體熔融形態之SAXS圖譜………………63
3.3-2 Paracrystalline analysis…………………………66
3.4 Dry Brush（PEO-b-PB/PB）摻合體之結晶行為……………71
3.4-1 Dry Brush摻合體結晶後之TEM圖……………………71
3.4-2 結晶動力學……………………………………………78
3.4-3 Dry Brush摻合體結晶後之SAXS圖譜…………………87
四、結論………………………………………………………………95
五、參考文獻…………………………………………………………97

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