臺灣博碩士論文加值系統

在本研究中，我們觀察在等溫與非等溫結晶過程中,在聚氧化乙烯(PEO)?和銀奈米板所造成的影響。在等溫結晶複合物中，我們發現銀奈米板的加入PEO會使得球晶成長速率上升。另外，銀奈米板阻礙了PEO一級成核而導致結晶速率的下降。 從實驗結果可知銀奈米板在複合物的結晶過程中扮演抗成核基團。利用Lauritzen-Hoffman的理論分析實驗數據能發現，成核常數和表面自由能隨著摻和奈米盤的量增加而下降。這是因為銀奈米板在結晶和基板之間, 對於高分子在表面結晶的促進比在聚合物內部來的多。此外，純PEO和它的複合物表現出類似的q，此現象指出銀奈米板的存在對於PEO之二級成核結構並沒有太大的影響，但卻能引發高分子結晶的形成。
我們利用熱卡掃描儀(DSC)對複合物進行非等溫結晶行為的研究。對純PEO而言Avrami指數 (n) 範圍介於2.51~2.53，對複合物卻微高於此數值, 大約2.54~3.16，表示這些複合物表現出球型結晶構型。從結晶半生期(t1/2)觀察則指出，純PEO和其複合物的結晶速率隨著冷卻速率而增加，且純PEO結晶速率比複合物來的快。經由成核活性的分析，我們發現成核能力隨的銀奈米板的量上升而增加。和之前的研究比較我們倒出, 在添加不同形狀及大小的銀奈米板的情況下會造成不定型的結晶行為，而這現象這完全取決於高分子鏈和填充物之間的作用力。

This research was accomplished to investigate the effect of the incorporation of silver nanoplates on both the isothermal and non-isothermal crystallization of poly(ethylene oxide) (PEO)/nanoplate composites. In isothermal crystallization of composites, it was obtained that the addition of the nanoplates into the PEO causes an increase in the spherulite growth rate. In addition, the silver nanoplates hinder the primary nucleation of PEO and thus reduce the crystallization rate. This result suggests that silver nanoplates act as an anti-nucleation agent for the crystallization of composites. By analyzing the experimental data using the Lauritzen-Hoffman’s theory, both the nucleation constant (Kg) and surface free energy (σσe) decrease with the incorporation amount of nanoplates. This is because the nanoplates promote the creation of the corresponding free polymer crystal surface more dominant than that of the interface between polymer crystals and substrate. Additionally, the neat PEO and its composites exhibit similar q, indicating that the existence of silver nanoplates has no significant effect on the formation of the secondary nuclei of PEO, but induce the formation of free polymer crystals.
Differential scanning calorimetry (DSC) was employed to investigate the non-isothermal crystallization of these composites. The Avrami exponent (n) for neat PEO ranged from 2.51 to 2.53 whereas that for composites showed slightly higher values between 2.54 to 3.16, indicating that these composites exhibit spherical crystal morphology. The half time for crystallization (t1/2) showed that the crystallization rate of neat PEO and its composites increase with increasing cooling rate and the crystallization rate of neat PEO is faster than that of composites. By analyzing the nucleation activity, we obtained that the nucleation ability increases with an increase in the content of silver nanoplates. Derived from the comparison with a few previous researches, the crystallization behavior of polymer with the addition of nanoparticles with different shape and size is atypical. It depends highly on the interaction between the polymer chains and the fillers.

LIST OF CONTENTS

ABSTRACT (In CHINESE) iii
ABSTRACT (In ENGLISH) iv x
LIST OF CONTENTS vi
LIST OF TABLES viii
LIST OF FIGURES ix
ACKNOWLEDGEMENT xii
CHAPTER 1 INTRODUCTION 1
References 3
CHAPTER 2 LITERATURE REVIEW 4
2.1. Polymer Nanocomposites 4
2.1.1. Manufacturing Techniques for Composites 10
2.1.2. Characterization Techniques for Nanocomposites 13
2.2. Properties of Nanocomposites 15
2.2.1. Thermal Properties 15
2.2.1.1. Melting Point 15
2.2.1.2. Thermal Stability and Degradation 15
2.2.1.3. Coefficient of Thermal Expansion (CTE) 16
2.2.1.4. Heat Distortion Temperature (HDT) 16
2.3. Polymer/clay Nanocomposites 16
2.4. Polymer/Carbon Nanotubes (CNT) Composites 19
2.4.1. Structure and Properties of Carbon Nanotubes 19
2.5. Polymer-inorganic Particle Nanocomposites 21
2.5.1. Preparation and Processing 22
2.5.2. Properties, Manufacturing, and Applications 22
2.6. Polymer Crystallization 24
2.6.1. Thermodynamics of Crystallization and Melting 29
2.6.2. Polymer Nucleation 30
2.6.3. Kinetics of Polymer Crystallization 32
2.6.3.1. Spherulite Growth Rate 32
2.6.3.2. Bulk Crystallization Kinetics 33
2.6.3.3. Lauritzen and Hoffman Parameter 34
2.7. References 35
CHAPTER 3 RESEARCH OBJECTIVES 41
3.1. Scope of Research 41
3.2. Overview of the Thesis 42
CHAPTER 4 ISOTHERMAL CRYSTALLIZATION OF POLY(ETHYLENE OXIDE)/SILVER NANOPLATE COMPOSITES 43
4.1. Abstract 43
4.2. Introduction 44
4.2.1. Lauritzen-Hoffman’s theory 47
4.3. Experimental part 52
4.3.1. Materials 52
4.3.2. Synthetic procedure of silver nanoplates 52
4.3.3. Preparation of PEO/silver nanoplate composites 53
4.3.4. Dispersion of silver nanoplates in PEO 53
4.3.5. Characterization of PEO/silver nanoplate composites 53
4.4. Results and Discussion 53
4.4.1. Silver nanoplates 53
4.4.2. Isothermal crystallization of PEO/silver nanoplate composites 55
4.4.3. Spherulite growth rate 56
4.4.4. Lauritzen and Hoffman Parameters 60
4.5. Conclusion 66
4.6. References 67
CHAPTER 5 NON-ISOTHERMAL CRYSTALLIZATION OF POLY(ETHYLENE OXIDE) / SILVER NANOPLATE COMPOSITES 69
5.1. Abstract 69
5.2. Introduction 69
5.2.1. Theory of non-isothermal crystallization 72
5.2.2. Nucleation activity (φ) 74
5.3. Experimental Part 75
5.3.1. Materials 75
5.3.2. Synthetic procedure of silver nanoplates 75
5.3.3. Preparation of PEO/silver nanoplate composites 76
5.3.4. Dispersion of silver nanoplates in PEO 76
5.3.5. Characterization of PEO/silver nanoplate composites 76
5.4. Results and Discussion 77
5.4.1. Silver nanoplates 77
5.4.2. Non-isothermal crystallization of PEO/silver nanoplate composites 78
5.5. Conclusion 100
5.6. References 101
CHAPTER 6 CONCLUSION 103

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