Morphological Studies of Semi-fluorinated Block Copolymeric Thin Films and Ordering of Nanoparticles in Thin Films
- Alternative Title
- 부분 불소계 블록공중합체 박막과 이를 이용한 나노입자 배열의 모폴로지에 관한 연구
- Abstract
- 정렬된 나노구조를 광범위하게 제조할 수 있는 분자 수준에서 블록 공중합체의 위상 분리는 그들의 독특한 물리적, 광학적, 전기적 특성 때문에 엔지니어링 관점에서 특히 중요하다. 블록공중합체 박막은 고유의 나노미터 크기, 합성의 용이함, 위상 거동에 기인하기 때문에 상당한 주의가 요구된다. 이 논문은 부분불소화된 블록공중합체 마이셀 박막의 배열에 관한 것이다. 부분불소화된 블록공중합체 Poly(ethylene oxide)-b-poly(1H,1H dihydrofluorooctyl methacrylate) (PEO-b-PFOMA)는 용매에서 마이셀을 형성하고, 다른 모폴로지의 제조를 위해 지지체 위에 떨어뜨려 실험하였다. 부분 불소화된 블록공중합체 분자량의 변화를 포함하여 공중합체의 농도, 용매의 종류, 다른 블록에 선택적인 용매 증기에서의 어닐링, 마이셀 용액으로 단일중합체의 첨가, 다른 공중합체 마이셀 용액의 혼합 등의 실험을 통하여 성공적으로 고분자 박막의 크기, 배열, 모폴로지를 변화시켰다. (PEO-b-PFOMA) 마이셀 박막의 모폴로지 형성을 시간에 따른 용매 증기 효과를 광범위하게 연구하였다. 부가적으로, (PEO-b-PFOMA)/PEO와 (PEO-b-PFOMA)1/(PEO-b-PFOMA)2 이성분 혼합 시리즈의 모폴로지 거동은 단일중합과 블록공중합체의 다양한 무게 분율로 연구하였다. 또한, 부분 불소화된 블록공중합체 마이셀 시스템을 이용하여 무기 나노입자를 합성하였고, 용매 증기 어닐링을 이용하여 박막에 나노입자를 배열시켰다. 용매 증기 어닐링에 따른 모폴로지 변화 과정과 혼합은 간단하고, 흥미로우며 그것 자체가 매력이 있다. 부분불소화된 블록공중합체 박막의 규칙적인 구조는 나노스케일 제조를 위한 새로운 기회를 제공할 수 있다.
- Issued Date
- 2011
- Awarded Date
- 2011. 2
- Type
- Dissertation
- Publisher
- 부경대학교 대학원
- Department
- 대학원 이미지시스템공학과
- Advisor
- 임권택
- Table Of Contents
- CHAPTER 1. General Introduction 1
1.1. Aim and Outline of This Thesis 1
1.2. Block Copolymers 2
1.2.1. Semi-fluorinated block copolymers 3
1.2.2. Synthesis of Semi-fluorinated Block Copolymers 4
1.3. Phase Behavior 6
1.3.1. Block copolymers in solid state 6
1.3.2. Block copolymers in solution 8
1.4. Solvent Vapor Annealing 10
1.5. Mechanism and Kinetics of Ordering Pathways 11
1.6. Blends of Block Copolymers 12
1.6.1. Block copolymers and homopolymers blend 12
1.6.2. Binary blends of block copolymers 14
1.7. Nanocomposite and Ordering 15
1.8. References 16
CHAPTER 2. Nanodomain Development of Semi-fluorinated Diblock Copolymeric Thin Films via Solvent Vapor Annealing 21
2.1. Introduction 21
2.2. Experimental Details 22
2.2.1. Synthesis of block copolymers 22
2.2.2. Thin film preparation and annealing 23
2.2.3. Characterization 23
2.3. Results and Discussion 24
2.4. Conclusions 28
2.5. References 28
CHAPTER 3. Robustness of Morphology of Semi-fluorinated Block Copolymer Films by Selecting Solvent and Annealing 30
3.1. Introduction 30
3.2. Experimental Details 31
3.2.1. Synthesis of block copolymers by ATRP 31
3.2.2. Thin film preparation 32
3.2.3. Solvent vapor treatment of the prepared film 32
3.2.4. Characterization 32
3.3. Results and Discussion 33
3.3.1. Concentration-induced vesicles-to-cylindrical transition in micelles 33
3.3.2. The morphology change of PEO20k-b-PFOMA40k films prepared from chloroform upon annealing in solvent vapor 35
3.3.3 The morphology change of PEO20k-b-PFOMA40k films prepared from TFT upon annealing in solvent vapor 37
3.4. Conclusion 39
3.5 References 40
CHAPTER 4: Effect of Solvent Vapor on the Morphology of Fluorinated Block Copolymer Films from Different Casting Solvent 42
4.1. Introduction 42
4.2. Experimental Details 43
4.3. Results and Discussion 43
4.4. Conclusions 48
4.5. References 49
Chapter 5: Formation of Spherical and Lamellar Arranged Structures in Semi-fluorinated Block Copolymer Thin Films Induced by Solvent Vapor 50
5.1. Introduction 50
5.2. Experimental Details 52
5.2.1. Synthesis of block copolymers by ATRP 52
5.2.2. Thin film preparation 52
5.2.3. Solvent vapor treatment of the prepared film 53
5.2.4. Characterization 53
5.3. Results and Discussion 53
5.3.1. Inverted-spherical morphology after PF-5080 solvent vapor annealing 53
5.3.2. Phase-inversion pathways for inverted-spherical morphology 56
5.3.3. Lamellar morphology after TFT solvent vapor annealing 59
5.4. Conclusions 63
5.5. References 63
CHAPTER 6: Control of Order, Size and Morphology in Thin Films of Semi-fluorinated Block Copolymer/Homopolymer Blends 66
6.1. Introduction 66
6.2. Experimental Details 67
6.2.1. Materials 67
6.2.2. Thin film preparation 67
6.2.3. Solvent vapor annealling 68
6.2.4. Characterization 68
6.3. Results and Discussion 69
6.3.1. Controlling domain size by blending with homopolymer 69
6.3.2. Effect of blend composition on size uniformity and domain spacing 71
6.3.3. Solvent vapor annealing studies 72
6.3.4. The morphology of films prepared from TFT 75
6.4. Conclusion 75
6.5. References 76
CHAPTER 7: Morphological studies of binary mixtures of poly(ethylene oxide)-b-poly(1H,1H-dihydroperfluorooctyl methacrylate) semifluorinated block copolymers 78
7.1. Introduction 78
7.2. Experimental Details 79
7.2.1. Materials 79
7.2.2. Sample preparation 79
7.2.3. Solvent vapor annealing 80
7.2.4. Characterization 80
7.3. Results and Discussion 81
7.3.1. The morphology of blend prepared in chloroform 81
7.3.2. The morphology of blend prepared in TFT/CH2Cl2 83
7.3.3. Solvent vapor annealing studies 85
7.4. Conclusion 87
7.5. References 88
CHAPTER 8: Semi-fluorinated Block Copolymers for Ordering of Gold Nanoparticles in Thin Films via Solvent Vapor Annealing 90
8.1. Introduction 90
8.2. Experimental Details 92
8.2.1. Synthesis of block copolymers by ATRP 92
8.2.2. In-situ synthesis of gold nanoparticles 92
8.2.3. Ordering of the prepared micellar thin film 92
8.2.4. Characterization 93
8.3. Results And Discussion 93
8.3.1. Ordering of micellar thin films in Spherical 93
8.3.2. Ordering of micellar thin films in Lamellar 94
8.3.3. In-situ synthesis of gold nanopartilcles 95
8.3.4. Ordering of gold nanoparticles in nanodomains 97
8.3.5. Ordering of Gold Nanoparticles in Lamellar Thin Films 98
8.4. Conclusion 99
8.5. References 100
CHAPTER 9: Summary and Recommendations for Future Work 102
9.1. Summary 102
9.2. Recommendations for Future Work 104
Publications 105
- Degree
- Doctor
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