Birefringence of Crystalline Block Copolymers Templated by Crystallization

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研究生：	張光威 Guang-Wei Chang
論文名稱：	Birefringence of Crystalline Block Copolymers Templated by Crystallization 結晶行為對半結晶性團聯共聚物雙折射之調控
指導教授：	何榮銘 Rong-Ming Ho
口試委員:
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：	2008
畢業學年度：	96
語文別：	英文
論文頁數：	104
中文關鍵詞：	雙折射、結晶、團聯共聚物
外文關鍵詞：	birefringence, crystallization, block copolymer
相關次數：	點閱：2 下載：0
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A series of semicrystalline block copolymers, poly(4-vinylpyridine) -block-poly(ε-caprolactone) (P4VP-PCL), with lamellar microstructure have been synthesized. Owing to the vitrified P4VP microdomains and strongly segregated microphase separation, the crystallization of the PCL blocks in P4VP-PCL can be carried out under nanoscale confinement at various temperatures. Specific PCL crystalline orientation can be achieved by confined crystallization under the vitrified P4VP microdomains. Considering the practical applications, large-scale oriented microphase-separated microdomains is required to provide well-defined structure for anisotropic macroscopic properties. A novel orientation process combining rimming coating and shearing was employed to achieve the large-scale orientation for microphase-separated microdomains.
Simultaneous SAXS and WAXD experiments are carried out to examine the anisotropic properties of microphase separated microstructure and corresponding crystalline orientation. The scattering results suggested that the crystalline chains are normal to microphase-separated lamellar microdomains at various temperatures from -10℃ to 40℃ because of the nanoscale confinement for crystallization; namely, a perpendicular orientation can be achieved. As evidenced by DSC measurements, the confined size effect varying from different molecular-weight samples is significant on confined crystallization. Interestingly, as observed by polarized light microscopy, uniform birefringence pattern can be identified in the oriented block copolymer thin films after crystallization.
The birefringence of the crystalline block copolymer thin films was examined as a function of crystallization temperature. Real-time birefringence measurement of the thin-film samples with the crystallization process was obtained by using a polarizer-sample-polarizer system. The enhancement on the birefringence of the block copolymer thin films corresponded well with the increase on the crystallinity of confined crystallization. We speculate that the growth of oriented crystallites with perpendicular morphology is attributed to the confinement effect. As a result, the birefringence of the thin-film samples increased with the crystallinity developing within the confined microdomains because of the specific anisotropic character.
Our results indicated that significant birefringence variation in the semicrystalline P4VP-PCL block copolymers can be templated by controlling the orientation and crystallinity of the crystalline microdomains due to the formation of preferential crystalline orientation. Also, it is noted that this birefringence variation is a reversible process by simply controlling the annealing temperature. Consequently, this block copolymer thin film can provide a temperature-controlled birefringence film and also a controllable birefringence film with the crystallization time because of the unique anisotropic crystallites of confined crystallization.

Abstract    I
Contents    III
List of Tables     V
List of Figures    VI
Chapter 1 Introduction    1
1 Self-Assembly    1
2 Self-assembly of Block Copolymers    2
3 Crystallization of Semicrystalline Diblock Copolymers    3
4 Polymeric Crystallites under Confinement    5
4.1 Crystalline Orientation under Confinement    6
4.2 Crystallization of P4VP-PCL Block Copolymers    7
5 Large-scale Orientation of BCP Microdomains    8
5.1 Shear-Induced Orientation    9
6 Optical Birefringence    11
6.1 Definition of Birefringence    11
6.2 Isotropic and Anisotropic    12
6.3 Optical Properties of Anisotropic    13
6.4 Birefringence in Crystalline Polymers    19
6.5 Birefringence in Ordered Block Copolymers    21
Chapter 2 Objectives    38
Chapter 3 Experimental    40
1 Instrumentation    40
2 Synthesis of P4VP-b-PCL    40
2.1 Preparation of Benzyl Ester End-functionalized PCL-OHs    40
2.2 Preparation of PCL Macroinitators, PCL-Cls    40
2.3 Synthesis of PCL-P4VP Diblock Copolymers    41
3 Bulk Sample Preparation of Diblock Copolymers    42
4 Alignment (Mechanical Shear Device)    42
5 Transmission Electron Microscopy (TEM)    43
6 Synchrotron X-ray Experiments    43
7 Differential Scanning Calorimetry (DSC)    44
8 Polarizing Optical Microscopic (POM)    45
9 Birefringence Measurement    45
Chapter 4 Results and Discussion    54
1 Thermal Behavior of P4VP-PCL    54
2 Lamellar Morphologies of P4VP-PCL with Various Molecular Weights    54
3 Oriented Lamellar Morphology    55
4 Crystalline Orientation under Confinement    56
5 Crystallization of P4VP-PCL    58
6 Specific Optical Behavior under Nanoscale Confinement    58
6.1 Birefringence in Oriented Block Copolymers    58
6.2 Correspondence of Crystallization and Birefringence    59
Chapter 5 Conclusions    95
Chapter 6 Future Work    97
Chapter 7 References    99

                                

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