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研究生： 吳佳蓉
Wu, Jia-Jung
論文名稱： 具多重功能半球型中孔洞雙邊不對稱球體之研究
Hemispheric Mesoporous Janus Particles with Multi-functionalities
指導教授： 郭昌恕
Kuo, Chang-Shu
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2016
畢業學年度： 104
語文別： 英文
論文頁數： 90
中文關鍵詞： 多功能 、中孔洞 、雙重保護 、雙邊不對稱球體 、異向性 、磁操控 、光致發光
外文關鍵詞： Multi-function, Mesoporous, double-protection, Janus particles, Magnetic Manipulation, Photoluminescence
相關次數： 點閱：132  下載：0 
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    • 本研究探討具備光學及磁性兩種性質之中孔洞雙邊不對稱二氧化矽球體的合成製備方式與性質，以及其在外加磁場操控下所表現之光學特性改變。中孔洞二氧化矽球體是以直徑480奈米的二氧化矽球體為主體，利用高分子化合物聚乙烯吡咯烷酮（Poly(vinylpyrrolidone), PVP）在球體表面形成保護層，並接著利用氫氧化納 (NaOH) 進行選擇性蝕刻以形成中孔洞結構。 此「表面保護」之方式能在維持材料尺寸的狀況下形成中孔洞結構。
    在此具多重功能半球型中孔洞雙邊不對稱球體之製備方式中，運用氣相沉積之方式將具有耐酸鹼特性的石蠟做為二次保護材料以保護先行改質之半球，分別將兩個半球改質上吲哚青綠(Indocyanine green, ICG)及氧化鐵(Fe3O4)。與原有之透過部分鑲埋及表面改質方式相比，此「雙重保護」之方法使得製程更加彈性靈活，並可應用於任何材料之改質。
    最後利用磁性操控的方式偵測球體上螢光染料的發光特性。在施加外加磁場的狀況下，球體表現出明顯的光學異向性以及磁場驅動之運動行為。因為吲哚青綠及氧化鐵都是存在於球體內部，表面仍能夠提供其它化學改質之可能性。

    Asymmetric mesoporous Janus particles with anisotropic optical and magnetic properties were synthesized and characterized in this research work. Mesoporous silica particles with 480 nm in diameters as the core materials were first prepared via the controlled etching to silica particles under the so-called surface-protected strategy. By the incorporation of poly(vinyl pyrrolidone) (PVP) to the silica particle surfaces, the subsequent preferential etching of silica were carried out with the use of the NaOH(aq) etching agent. This surface protection method allowed the formation of the porous silica structure while the particle outer diameter remained the same.
    In the following fabrication of multi-functionalized Janus particles, the vapor deposition of wax as the secondary blocking material was also introduced to protect one hemisphere surface of the mesoporous silica particles. Two mesoporous hemispheres were successfully functionalized with an organic dye, Indocyanine green (ICG) and magnetic Fe3O4 particles. Different from the original partial-embedded and surface modification method developed in our group for the Janus particle synthesis, the new Janus particle fabrication demonstrated the double protection strategy that allowed more options to the desired surface functionalities.
    ICG/Fe3O4 mesoporous Janus particles were further investigated with the magnetic manipulation and their anisotropic responses. Under the external magnetic field, ICG/Fe3O4 mesoporous Janus particles revealed their anisotropic photoluminescence performance, as well as the magnetically-induced particle rotation. Since the ICG molecules and Fe3O4 nanoparticles were both within the mesoporous silica particles, the particle hemispheric surfaces remained available to other chemical functionalities.

    致謝 I 中文摘要 II Abstract IV Table of Contents V List of Illustrations VII List of Tables X Chapter 1. Introduction 1 1.1 Janus Particles and Asymmetric micro- and nano-Materials 1 1.1.1 Janus-like Materials 2 1.1.2 Fabrications of Janus Particles 7 1.1.3 One-dimensional Electrospun Fibers as Particle Embedding Substrates 17 1.1.4 Applications 19 1.2 Mesoporous Materials 23 1.2.1 Silicate Mesoporous Materials 25 1.2.2 Mechanisms of Formation Mesoporous Materials 26 1.2.3 Applications 28 1.3 Manipulation of Janus Particles by Magnetic Field 31 1.3.1 Particle Orientation 31 1.3.2 Anisotropic Optical Properties 33 1.3.3 Applications of Magnetically-driven Janus Particles 34 Chapter 2. Motivation 36 Chapter 3. Experimental 39 3.1　Chemicals 39 3.2　Instruments 41 3.3　Fabrication of Fe3O4/Dye Mesoporous Janus Silica Particles 42 3.3.1 Preparation of 480nm Silica Particle Solution 42 3.3.2 Fabrication of Mesoporous Silica Particles 42 3.3.3 Electrospinning of PMMA/P4VP Blend Fibers 43 3.3.4 Dipping Process of 480nm Silica Particles 44 3.3.5 Heat Treatment Process (Thermal Embedding Process) 44 3.3.6 APS Modification Process 44 3.3.7 Dye Grafting Process 45 3.3.8 Wax Protection Process 46 3.3.9 Polymer Fibers Dissolving Process 46 3.3.10 Magnetite (Fe3O4) Nanoparticles Filling Process 47 3.3.11 Dewaxing Process 47 3.4　Analytical Instruments 48 3.4.1 UV-vis Spectrometer (UV-vis) 48 3.4.2 Photoluminescence Spectroscopy (PL) 48 3.4.3 Scanning Electron Microscopy (SEM) 50 3.4.4 Particle Size Distribution (Dynamic Light Scattering) 50 3.4.5 Zeta Potential Analyzer 51 Chapter 4. Results and Discussions 52 4.1 Synthesis and Verification of Mesoporous Silica Particles 52 4.1.1 Surface-Protected Etching 52 4.1.2 Influence of Reaction Time and Temperature on Etching Process 53 4.1.3 Mesoporous Silica Particles and Their Embedding Behaviors 59 4.2 Fabrication and Characterization of Multi-functionalized Mesoporous Janus Particles 61 4.2.1 Dye Characterization 61 4.2.2 Protection of Paraffin Wax via CVD 63 4.2.3 Magnetite (Fe3O4) Nanoparticle Filling 68 4.2.4 Dye-functionalization and Optical Properties 72 4.3 Magnetic Manipulation of Multi-functionalized Mesoporous Janus Particles 75 4.3.1 Anisotropic Optical Properties 75 4.3.1 Dynamic Anisotropic Optical Properties 79 Chapter 5. Conclusion 82 References 83

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