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Title Page

Contents

Chapter 1. Introduction of this Dissertation 19

Chapter 2. Theoretical Background 24

2.1. Nano/micro Building Block Toward Functional Polymeric Architecture 24

2.2. Synthesis of the 0D Nanoparticle 28

2.3. Microemulsion Method to Prepare 0D Microparticle 33

2.4. Electrospinning for Preparing 1D Nanofiber 37

2.5. Difficulties of Conventional Electrospinning Process 45

2.6. Preparation of 1D Microfiber and 3D Architecture 49

Chapter 3. Preparation of 0D nano/micro building blocks and their applications 53

3.1. Introduction 53

3.2. Preparation of 0D Silica Nanoparticle 56

3.2.1. Experimental Details 56

3.2.2. Simultaneous Size Control and Functionalization of 0D Nanoparticle 59

3.2.3. Confirmation of Amine Functionality on The Particles 67

3.2.4. Catalytic Application of Amino Silica Obtained by GM 71

3.3. Preparation of Polymeric 0D Micro Building Block and its Application 73

3.3.1. Experimental Details 73

3.3.2. Preparation of 0D Microparticle via Microemulsion Method 76

3.3.3. Preparation of Prussian Blue-decorated 0D Microparticle for Cs Removal via in-situ Chemical Treatment 83

3.4. Conclusion 95

Chapter 4. Preparation of Non-woven 1D Nanofiber and its Applications 96

4.1. Introduction 96

4.2. Preparation of 1D Functional Nano Building Block and its Applications 98

4.2.1. Experimental Details 98

4.2.2. Preparation of 1D Nanofiber via Syringeless Electrospinning 103

4.2.3. Material Versatility of Syringeless Electrospinning 108

4.2.4. Fabrication of nanofibers using polymeric solutions inducing nozzle blocking 113

4.2.5. Functionalization of Amine Compound on PAN Nanofiber via Chemical Vapor Deposition 117

4.2.6. Electrospinning of Composite 1D Nanofiber using Syringeless Electrospinning System 128

4.2.7. Preparation of SiOx-carbon Nanofiber from Composite Nanofiber 132

4.2.8. LIB Application of SiOx-carbon Nanofiber 140

4.3. Conclusion 148

Chapter 5. 1D Microfiber and Micro 3D Architecture and Their Applications 149

5.1. Introduction 149

5.2. Preparation of 1D Microfiber and its Applications 152

5.2.1. Experimental Details 152

5.2.2. Preparation of Helical 1D Micromaterial Using Dual Collector 154

5.2.3. Applications of Helical 1D Microfiber 160

5.3. Preparation of Micro 3D Architecture via Charge-reversed System 167

5.3.1. Experimental Details 167

5.3.2. Charge-reversed System for 3D Micro Architecture 170

5.3.3. 3D Jet-writing via Charge-reversed System 176

5.3.4. Material Diversity and 3D Build-up of Heterogenous Structure 183

5.3.5. Preparation of Multi-compartmental 1D Microfiber 192

5.3.6. Microfiber-based 3D Architecture Toward Advanced Applications 196

5.4. Conclusion 205

Chapter 6. Conclusion of this Dissertation 206

References 209

국문초록 218

List of Tables

Table 3-1. Formation of PB in DW-hydrogel particle depending on pH value 86

Table 3-2. Summary of calculated kinetic parameters fitted by Pseudo first order model and... 94

Table 4-1. Summary of composition of prepared nanofibers detected by EDS and XPS 137

Table 5-1. Composition of polymeric solutions and experimental parameters for charge... 186

List of Figures

Figure 1-1. Schematic diagram of overall works on this dissertation. 23

Figure 2-1. Nano/micromaterials according to their dimension. 25

Figure 2-2. Schematic diagram of preparing nanomaterial via top-down approach and... 27

Figure 2-3. Schematic diagram of Stöber method to prepare the silica nanoparticle. 30

Figure 2-4. Schematic illustration of condensation reaction of silane coupling reagent. 32

Figure 2-5. Schematic illustration of critical packing parameter (CPP). 34

Figure 2-6. Schematic diagram of mechanism of microemulsion; a) One microemulsion... 36

Figure 2-7. Schematic diagram of general set-up of electrospinning system. 39

Figure 2-8. Schematic illustration of generation of Taylor cone depending on applied... 40

Figure 2-9. Schematic illustration of droplet explosion by applying electrical potential. 41

Figure 2-10. Schematic illustration of a) Whipping motion of polymeric jet, b) Rayleigh... 44

Figure 2-11. Schematic illustration of generation of polymeric droplet on surfaces at needle,... 48

Figure 3-1. Schematic illustration of preparation of silica particles and amino-silane treatment... 60

Figure 3-2. SEM images represent the growth of silica particles via gradually injecting... 62

Figure 3-3. Schematic illustration of reaction frequency between the surface of seed particle... 64

Figure 3-4. SEM images of amino silane treated silica nanoparticle depending on different... 66

Figure 3-5. CLSM images of selective conjugation of different dyes; a) Rhodamine B... 68

Figure 3-6. Photoluminescence spectra depending on amount of treated amino silane coupling... 70

Figure 3-7. a) Schematic illustration of Knoevenagel reaction with benzaldehyde and ethyl... 72

Figure 3-8. Overall process for hydrogel particle via iron-reduction process, a) Drop-wised... 77

Figure 3-9. a) Digital image of DW-hydrogel particle; b) Optical image of EM-hydrogel... 79

Figure 3-10. Magnetic properties of DW-hydrogel particle and EM-hydrogel particle. 81

Figure 3-11. Magnetic property of prepared DW-hydrogel particle and EM-hydrogel particle,... 82

Figure 3-12. XRD spectra of PB-EM-hydrogel particle and EM-hydrogel particle. 85

Figure 3-13. a) digital image of PB-DW-hydrogel particle; b) optical microscope image of... 88

Figure 3-14. Comparison of Cs uptake efficiency of commercial PB nanoparticle, PB-DW-... 91

Figure 3-15. Linearly fitted graph of cesium adsorption efficiency of PB-EM-hydrogel... 93

Figure 4-1. SEM images of PAN nanofibers fabricated by probed cylinder with different... 105

Figure 4-2. a) Schematic illustration of helically probed cylinder, b) SEM image of PAN... 107

Figure 4-3. SEM images of nanofiber fabricated by syringeless electrospinning with helically... 109

Figure 4-4. SEM images of PVP nanofibers with diameter controlling depending on... 110

Figure 4-5. a) Digital image of TPU nanofiber web prepared via syringeless electrospinning. 112

Figure 4-6. a) SEM image of PVDF nanofiber prepared via syringeless electrospinning, and... 114

Figure 4-7. a) schematic illustration of colloidal electrospinning via the syringeless... 116

Figure 4-8. Schematic diagram of preparing E.PAN nanofiber web using syringeless... 118

Figure 4-9. SEM images of the nanofibers fabricated by the syringeless electrospinning... 120

Figure 4-10. a) FT-IR spectra of PAN nanofiber and EDA-treated PAN nanofibers (80 and... 123

Figure 4-11. Photoluminescent (PL) spectra of PAN, E.PAN, and FITC-treated E.PAN... 125

Figure 4-12. Digital images of thin-layered chromatography using silica gel, PAN nanofiber... 127

Figure 4-13. SEM images of electrospun nanofibers; a) PAN, b) TEOS10, and c) TEOS20. 129

Figure 4-14. FT-IR spectra of PAN nanofiber, TEOS10, and TEOS20 nanofiber. all the... 131

Figure 4-15. a) XRD spectra of PAN nanofiber, CPAN, and CTEOS20, respectively. b)... 134

Figure 4-16. SEM images of a) CPAN; b) CTEOS10; c) CTEOS20 after carbonization... 136

Figure 4-17. XPS spectra of TEOS20 and CTEOS20; a) silicon of TEOS20; b) oxygen of... 139

Figure 4-18. Initial Charge/discharge profile of electrodes using a) CPAN, b) CTEOS10, and... 142

Figure 4-19. a) Voltage profile comparison of initial 2 cycles of carbonized electrodes and b)... 143

Figure 4-20. Cycle performances of prepared electrodes depending on amount of TEOS; a)... 145

Figure 4-21. Rate performance of fabricated electrodes depending on the amount of TEOS 147

Figure 5-1. CLSM images of helically compartmentalized microfibers with a) left and b) right... 155

Figure 5-2. SEM images of a) microfibers with helical rails on its shell (preparation of twisted... 157

Figure 5-3. a) Schematic illustration of apparatus for in-situ preparing helical microfiber 159

Figure 5-4. a) CLSM image and b) optical microscopy images of helical microcylinders... 161

Figure 5-5. Movement of microcylinders containing magnetic nanoparticles with helical... 162

Figure 5-6. a) CLSM images of helical microcylinders decorated with a red dye in one... 164

Figure 5-7. a) SEM image of 1D microparticle prepared by shape evolution of the helical... 166

Figure 5-8. Schematic illustration of charge reversed system for preparation of fiber-based... 171

Figure 5-9. Digital images of Taylor cones for a) a single phasic microfiber and b) a biphasic... 174

Figure 5-10. Digital image of whipping motion during the EHD jetting system with a) forward... 175

Figure 5-11. SEM images of electro-jet-written patterns using forward system and reversed... 177

Figure 5-12. a, b) digital image and SEM image of 3D printed triangular structure prepared... 179

Figure 5-13. Digital images of the charge reversed system combined with the conventional... 181

Figure 5-14. Digital images of the 3D architectures which prepared by a) charge reversed... 182

Figure 5-15. SEM images of 3D architectures prepared by various polymeric materials. a)... 185

Figure 5-16. Digital images of side view for macroscopic 3D structures fabricated by the... 188

Figure 5-17. Digital images of the Taylor cones of 7 polymeric jets and SEM images of the... 190

Figure 5-18. Digital images of a) simultaneous jetting of 3 architectures using the charge... 191

Figure 5-19. a) 3D confocal laser scanning microscope image of PLGA/TPU biphasic 3D... 194

Figure 5-20. Schematic diagram of a, b) chemical structure of Azide-TPU and alkyne-... 195

Figure 5-21. a) schematic diagram of jetting on the architecture using different polymers; the... 198

Figure 5-22. SEM images of the 3D TPU architecture with EGaIn nanoparticle depending on... 201

Figure 5-23. Digital images of the stretchable 3D architecture a) before and b) after stretching. 202

Figure 5-24. The resistance test depending on the number of stacks. 203

Figure 5-25. Stretching test of the conductive 3D architecture, a) relative resistance according... 204

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