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研究生: 林明昌
Lin, Ming-Champ
論文名稱: 結晶性嵌段式共聚物之結晶行為與階層性結構研究
Crystallization Behavior and Hierarchical Structure of Crystalline Block Copolymers
指導教授: 陳信龍
Chen, Hsin-Lung
口試委員: 陳信龍
Chen, Hsin-Lung
蘇安仲
Su, An-Chung
何榮銘
Ho, Rong-Ming
鄭有舜
Jeng, U-Ser
蔡敬誠
Tsai, Jing-Cherng
蔣酉旺
Chiang, Yeo-Wan
學位類別: 博士
Doctor
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2012
畢業學年度: 100
語文別: 英文
論文頁數: 213
中文關鍵詞: 結晶性-無定形嵌段式共聚物雙結晶性嵌段式共聚物結晶行為階層性結構奈米結構晶體取向
外文關鍵詞: crystalline-amorphous block copolymer, crystalline-crystalline block copolymer, crystallization behavior, hierarchical structure, nanostructure, crystal orientation
相關次數: 點閱:3下載:0
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  • Crystallization of diblock copolymer composing one or two crystallizable components has attracted significant attention in recent decades. In this study, we center on the crystallization behavior and morphological structure of the diblock copolymers containing one crystalline and one amorphous block (i.e., the C-A diblocks) and two crystalline blocks (i.e., the C-C diblocks). We intend to unravel how the interplay between the crystallization event and the driving force of microphase separation influences the kinetics and thermodynamics of crystallization as well as on the hierarchical structure formation of the systems.
    First of all, we investigate the crystallization behavior of isotactic polypropylene (iPP) under the influence of nanoscale confinement templated by the microphase-separated structure of an iPP-based C-A diblock copolymer system, isotactic polypropylene-block-atactic polystyrene (iPP-b-aPS). Three types of iPP microdomains, i.e., lamellae, cylinder and sphere, were generated by controlling the composition of the diblock. The effect of microdomain morphology on the nucleation mechanism, crystallization kinetics, self-nucleation behavior, the population of the helical sequence of iPP block in the melt state and crystal orientation have been systematically studied.
    The strongly-segregated lamellae-forming poly (lactide)-block-polyethylene (PLA-b-PE) diblocks (including C-A polyethylene-block-poly(LD-lactide) (PE-b-PDLLA) and C-C poly(L-lactide)-block-polyethylene (PLLA-b-PE)) constituting analogous molecular weight of PE block have been systematically investigated and compared. In both systems, the crystallization process was virtually confined within the respective lamellar microdomains. Moreover, the microdomain morphology prescribed by the melt mesophase was essentially unperturbed upon crystallization, irrespective of the crystallization history, as a consequence of large segregation strength in nature.
    In addition to the strongly-segregated C-C diblocks with a symmetric composition, we further focus on the crystallization kinetics and crystallization-induced morphological formation of a weakly-segregated asymmetric C-C diblock copolymer, syndiotactic polypropylene-block-poly(ε-caprolactone) (sPP-b-PCL). The system was subjected to crystallization over a broad range of conditions for tuning the competitiveness and interplay of the two crystallization events. It was found that the degree of morphological perturbation induced by sPP crystallization caused a special “interactive crystallization kinetics” in this type of material, where the crystallization temperature the leading crystalline component, sPP, drastically affected the crystallization kinetics of PCL block.
    Apart from the correlation between crystallization behavior and morphological transformation, we further examined the preferential orientation of crystals (i.e., the crystalline molecular order) formed in lamellar microdomains of strongly-segregated PLA-b-PE diblocks. Orientation of PE crystals formed over a broad range of undercooling in a C-A PE-b-PDLLA diblock copolymer has been critically examined. It was found that the PE crystalline stems in the lamellar microdomains always orient parallel to the lamellar interface when there is a preferred orientational order. We have organized the thermodynamic and kinetic factors that may govern the preferred crystal orientation in diblock copolymers and concluded that the orientational order should be controlled by the competition between nucleation density and crystal growth kinetics.
    Considering that most research so far has focused on the crystal orientation in C-A systems, here we investigate a C-C PLLA-b-PE diblock to explore the orientation of crystals formed within the lamellar domains over a broad range of crystallization conditions. It was found that the preferred crystal orientations were identical to those observed for the corresponding C-A systems and were not affected by the crystallization history, indicating that PLLA and PE blocks crystallized independently in their respective microdomains as a consequence of large segregation strength.


    Abstract I Acknowledgement IV Table of Contents VI List of Tables X List of Figures XI Chapter 1. Introduction of Phase Behavior and Crystallization of Block Copolymers 1.1 Microphase Separation of Block Copolymers 1 1.2 Crystallization in Crystalline-Amorphous (C-A) Diblock Copolymers 2 1.2.1 Crystallization Kinetics and Thermodynamics Associated with the Confined Crystallization in C-A Diblocks 3 1.2.2 Morphological Perturbation Induced by Crystallization in C-A Diblocks 4 1.2.3 Crystal Orientation in C-A diblocks 4 1.3 Crystallization in Double-Crystalline (C-C) Diblock Copolymers 8 1.4 Overview of the Dissertation 9 1.5 References 12 Chapter 2. Crystallization of Isotactic Polypropylene under the Spatial Confinement Templated by Block Copolymer Microdomains 2.1 Introduction 25 2.2 Experimental Section 28 2.3 Results and Discussion 34 2.3.1 Morphological Perturbation Induced by Crystallization in C-A Diblocks 34 2.3.2 Crystallization Behavior 37 2.3.3 Self-Nucleation Study 38 2.3.4 Population of Helical Segments of iPP Block in Different Microdomain 42 2.3.5 Crystal Orientation in Lamellae-forming iPP-b-aPS Diblock Copolymer 44 2.4 Conclusions 48 2.5 References 49 Chapter 3. Confined Crystallization and Morphology of Strongly-Segregated PLA-b-PE Diblock Copolymers 3.1 Introduction 72 3.2 Experimental Section 76 3.3 Results and Discussion 78 3.3.1 Standard DSC Results 78 3.3.2 Self-Nucleation Studies for the PLLA Block 81 3.3.3 Morphology 84 3.4 Conclusions 90 3.5 References and Notes 91 Chapter 4. Interactive Crystallization Kinetics in Double-Crystalline Block Copolymer 4.1 Introduction 108 4.2 Experimental Section 112 4.3 Results and Discussion 115 4.3.1 Melt structure and crystallization-induced structure perturbation 115 4.3.2 Interactive crystallization kinetics in the two-stage crystallization process 118 4.3.3 Crystallization behavior in the one-stage crystallization process 126 4.4 Conclusions 130 4.5 References 130 Chapter 5. Critical Analysis of the Crystal Orientation Behavior in Polyethylene-based Crystalline-Amorphous Diblock Copolymer 5.1 Introduction 152 5.2 Experimental Section 155 5.3 Results and Discussion 157 5.4 Conclusions 164 5.5 References 165 Chapter 6. Orthogonal Crystal Orientation in Double-Crystalline Block Copolymer 6.1 Introduction 177 6.2 Experimental Section 179 6.3 Results and Discussion 182 6.3.1 Crystal Orientation Displayed under Two-stage Crystallization 183 6.3.2 Crystal Orientation Displayed under One-stage Crystallization 185 6.4 Conclusions 192 6.5 References 193 List of Publications 210

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