Title Page
Abstract
Contents
Chapter 1. Introduction 18
1.1. Study Background 19
1.1.1. Superstructures of colloidal particles 19
1.1.2. Supracolloidal chains from linear assembly of colloidal particles 21
1.1.3. Property and application of supracolloidal chains 25
1.1.4. Supracolloidal chains of block copolymer micelles 28
1.1.5. Supracolloidal chains as nanoscale analogues of conventional polymers 31
1.2. Purpose of Research 34
1.2.1. Motivation 34
1.2.2. Aim and objectives 34
Chapter 2. Step-growth polymerization of patchy micelles of diblock copolymers 42
2.1. Introduction 43
2.2. Experimental Section 44
2.3. Results and Discussion 49
2.4. Conclusion 55
Chapter 3. Porous self-supporting film of semi-flexible supracolloidal chains of diblock copolymer micelles 70
3.1. Introduction 71
3.2. Experimental Section 72
3.3. Results and discussion 75
3.4. Conclusions 81
Chapter 4. PS-b-P4VP micelles incorporating cobalt nanoparticles as building blocks for supracolloidal chains 90
4.1. Introduction 91
4.2. Experimental Section 92
4.3. Results and Discussion 95
4.4. Conclusion 100
Bibliography 108
국문 초록 126
Chapter 1. Introduction 10
Figure 1.1. Superstructures of colloidal particles: (a) colloidal crystal; (b) two-dimensional colloidal superlattice; (c) colloidal cluster. 37
Figure 1.2. Supracolloidal chains from linear assembly of colloidal particles: (a) Magnetic dipolar interaction; (b) Electrostatic dipolar assembly; (c)... 38
Figure 1.3. Properties of supracolloidal chains: (a) plasmonic coupling; (b) magnetic coupling; (c) one-dimensional photonic crystal; (d) micromotor 39
Figure 1.4. Self-assembled nanostructures of block copolymers: (a) bulk assembly; (b) solution assembly. 40
Figure 1.5. Supracolloidal chains of patchy micelles of block copolymers: (a) poly(ethyleneoxide)-b-polystyrene-b-poly(2-vinylpydine); (b)... 41
Chapter 2. Step-growth polymerization of patchy micelles of diblock copolymers 11
Figure 2.1. Schematic illustration of linear assembly of supracolloidal chains of PS-b-P4VP micelles 57
Figure 2.2. TEM images of spherical micelles of PS(51)-b-P4VP(18): (a) after staining P4VP with I₂; (b) after staining PS with RuO₄. The scale bars are 100... 58
Figure 2.3. Patchy micelles (top row) and supracolloidal chains (bottom row) of PS(51)-b-P4VP(18): (a) and (d) TEM image after staining P4VP with I₂;... 59
Figure 2.4. Distributions of degree of polymerization x of supracolloidal chains after polymerization: (a) 0.5 h; (b) 2 h; (c) 3 h; (d) 6 h. The... 60
Figure 2.5. Evolution of xn and PDI during polymerization: (a) xn; (b) PDI. The dotted lines in (a) and (b) are calculated by the conventional step-growth...[이미지참조] 61
Figure 2.6. Distributions of degree of polymerization x of supracolloidal chains after 6 h by varying the initial concentration: (a) 1.25 x 10-2 wt%; (b)...[이미지참조] 62
Figure 2.7. Polymerization of supracolloidal chains by varying the initial concentration: (a) xn vs. time; (b) dxn/dt vs. [A]0. The dotted lines in (a) are...[이미지참조] 63
Figure 2.8. TEM image of cyclic supracolloidal chains after staining with I₂. The scale bar is 500 nm. The inset is an enlarged image of a representative... 64
Figure 2.9. Effect of the content of water on polymerization of patchy micelles: (a) SEM images after 3h polymerization with the scale bar of 500 nm; (b)... 65
Figure 2.10. GPC results of PS-b-P4VP used for assembly of supracolloidal chains. 66
Figure 2.11. TEM images of spherical micelles: (a) PS(25)-b-P4VP(7); (b) PS(145)-b-P4VP(40). TEM images were obtained after stained with I₂. The... 67
Figure 2.12. Colloidal polymerization of PS(25)-b-P4VP(7) (top row) and PS(145)-b-P4VP(40) (bottom row): (a) and (c) TEM images of patchy... 68
Figure 2.13. Evolution of xn for patchy micelles with different size of patches: (a) PS(25)-b-P4VP(7); (b) PS(145)-b-P4VP(40). The dotted lines are...[이미지참조] 69
Chapter 3. Porous self-supporting film of semi-flexible supracolloidal chains of diblock copolymer micelles 14
Figure 3.1. TEM images of PS(51)-b-P4VP(18) micelles after staining with I₂: (a) spherical micelles; (b) patchy micelles. The scale bars are 100 nm. The... 82
Figure 3.2. Supracolloidal chains of PS(51)-b-P4VP(18): (a) SEM image; (b) TEM image after staining the PS corona with RuO₄; (c) TEM image after... 83
Figure 3.3. SEM image of supracolloidal chains spin-coated on a substrate. The scale bar is 500 nm. 84
Figure 3.4. Size distributions of supracolloidal chains: (a) contour length; (b) degree of polymerization. The dotted line in (b) corresponds to a most-... 85
Figure 3.5. Semi-flexible supracollodial chains: (a) Rg vs. L; (b) Re vs. L. The dashed lines in (a) and (b) are calculated by Equations 3.2 and 3.3 of the...[이미지참조] 86
Figure 3.6. SEM images of supracolloidal chains marked with solid circles in Figure 3.5. They are displayed in order of contour lengths. The scale bar is... 87
Figure 3.7. SEM images of supracolloidal chains on a substrate after repetitive spin-coating: (a) 5 cycles; (b) 20 cycles; (c) 50 cycles. The scale bars are 500... 88
Figure 3.8. SEM images of supracolloidal chains on a substrate after repetitive spin-coating: (a) 100 cycles; (b) 200 cycles. The scale bars are 500 nm. The... 89
Chapter 4. PS-b-P4VP micelles incorporating cobalt nanoparticles as building blocks for supracolloidal chains 16
Figure 4.1. Schematic illustration of linear assembly of supracolloidal chains by using PS-b-P4VP micelles incorporating CoNPs as colloidal monomers. 101
Figure 4.2. Cobalt nanoparticles (CoNPs): (a) TEM image; (b) Histogram showing the diameters of CoNPs. The scale bar is 50 nm. 102
Figure 4.3. Spherical micelles of PS-b-P4VP incorporating CoNPs: (a) TEM image; (b) Histogram of the number of CoNPs in a micelle. The scale bar is... 103
Figure 4.4. Patchy micelles of PS-b-P4VP incorporating CoNPs: (a) TEM images; (b) TEM images after staining with RuO₄; (c) Histogram of the... 104
Figure 4.5. TEM image of supracolloidal chains of PS-b-P4VP incorporating cobalt nanoparticles. The scale bar is 200 nm. 105
Figure 4.6. TEM images of CoNPs and micelles incorporating CoNPs after dried in the presence of a magnetic field: (a) CoNPs; (b) spherical micelles;... 106
Figure 4.7. TEM image of supracolloidal chains incorporating CoNPs after dried in the presence of a magnetic field. The scale bar is 2 µm. 107