多苯環結構的聚芳香醚高分子是一個具有高度立體障礙性的結構，搭配不同的官能基團在結構上能有更多磺酸根接枝的位置，可具有較大的離子交換量 (Ion Exchange Capacity，IEC)，且經由高分子主鏈結構的剛性設計，能擁有良好的熱穩定性及機械性質，近年來已被研究應用在燃料電池的質子交換膜上。而分子動力學模擬 (Molecular Dynamics Simulation) 是利用電腦模擬的方式，研究分子或原子在一段時間內的運動情形，現今已被廣泛應用在材料，生化，機械，及藥物研究。
本論文以具有高度立體障礙性的九苯環二醇為主體，搭配兩種不同二氟單體作為主要模擬的材料 (SP、JSP)，分別在溶劑為DMAC與H2O中進行模擬，觀察其微相分離型態與原子間分布情形，進而比較兩種高分子在質子導電度上之優劣。其結果可知，在DMAC系統中，SP高分子所形成的團簇 (cluster) 較為明顯，分子間的空間寬裕，而JSP高分子則顯得擁擠，相分離程度不比SP來的明顯。而在H2O系統中，SP高分子在單位範圍內的磺酸根個數雖較少，但其具有的高度立體障礙性結構，能容下更多的水分子，使得氫質子能在磺酸根與水分子間傳遞，而JSP高分子結構的共平面性，相對壓縮了水分子分布的空間，所聚集的水分子較少，因此我們推估在質子導電度上SP高分子會來的比JSP優異，這結果也與實驗上所測得的質子導電度相符。

The poly aromatic ether polymer of multi-benzene ring is a high steric hindrance structure. By matching different functional groups, they can offer more position that sulfonated acid group grafted, and owning a high Ion Exchange Capacity (IEC). After designing the rigid structure of polymer main chain, the polymer will be good thermal stability and mechanical properties. Over the past year, these materials have been the subject of many research studies on Proton exchange membrane fuel cell (PEMFC).Molecular dynamic simulations (MD) is a computer simulation of physical movements of atoms and molecules. MD has now been widely used in materials, biochemical and pharmaceutical research.
In this study, we adopt the structure of a high degree of nine benzenoid bisphenol with steric hindrance as the main body, with two different bisfluoro monomers for the materials of simulated (SP、JSP). We prepare two kinds of solvent system for simulation, which are DMAC and H2O, to observe the microphase separation and distribution of atoms, and further compare the proton conductivity of two materials. The result shows that the cluster of SP is more pronounced than JSP on DMAC system. We find the intermolecular of SP is so commodious than JSP that there are more water aggregate nearby sulfonated acid group. In H2O system, even though the sulfonated acid group of SP is less than JSP in cutoff radius, there are more water around sulfonated acid group for steric hindrance structure and let hydronium ions transport between sulfonated acid group and water. The intermolecular space of JSP is narrow for coplanar structure, so there is less water around sulfonated acid group. For these reasons, we inferred the proton conductivity of SP is better than JSP, and the tendency conformed to the experiment data.

致謝 iii
摘要 iv
Abstract v
目錄 vii
表目錄 ix
圖目錄 x
第壹章 緒論 1
1.1 前言 1
1.2 燃料電池之發展與類別 1
1.3 質子交換膜燃料電池工作原理 5
1.4 質子交換膜特性文獻回顧 7
1.5 分子動力模擬 17
1.6 研究動機 18
第貳章 理論方法 20
2-1 模擬方法 20
2-1-1 簡介 20
2-1-2 分子動力學基本架構 22
2-2 系統作用力場 25
2-3 數值方法 26
2-3-1 Verlet’s Algorithm[64]-[66] 28
2-3-2 Leap-Frog Algorithm[64]-[66] 29
2-3-3 Velocity Verlet Algorithm[64]-[66] 30
2-3-4 Beeman’s Algorithm[64]-[66] 31
2-3-5 Gear’s Predictor-Corrector algorithm [64]-[66] 32
2-4 模擬系統的設定 34
2-5 週期性邊界條件 35
2-6 Rescaling溫度修正 38
2-7 分子動力學模擬的流程 39
第參章 系統建構方法及參數設定 40
3-1系統建構 40
3-1-1 主體材料 40
3-1-2 分子個數設定 43
3-2 參數設定 45
3-2-1 結構最佳化參數設定 46
3-2-2 分子動力模擬參數設定 46
第肆章 結果與討論 47
4-1 SP分子在溶劑DMAC中特性分析 47
4-2 SP分子在溶劑H2O中特性分析 57
4-3 JSP分子在溶劑DMAC中特性分析 66
4-4 JSP分子在溶劑H2O中特性分析 73
第伍章 結論 83
第陸章 參考文獻 84

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