Nafion質子交換膜是目前使用於燃料電池最普遍的膜材。本論文
使用DuPont公司生產Nafion溶液分別以醇/水溶液及DMF溶液置換後，在室溫及120℃下揮發成膜。室溫下揮發的薄膜，薄膜性質是易脆的無法完整從培養皿中取出其機械性質差﹔用DMF置換DuPont公司Nafion溶液中醇/水溶液在高溫下揮發成膜，有較好的機械性質，經水膨潤後外型是柔軟、有彈性、有凝聚性的。薄膜溶劑含量測定數據顯示，室溫揮發形成的薄膜溶劑含量明顯高於在高溫下揮發形成的薄膜，室溫成膜後加熱annealing時間越久產生的物理交聯越多且結晶度越大，膜材越不容易被水膨潤，水含量也較低，薄膜膨潤過程中溫度也會影響其含水率。DSC熱分析數據顯示，加熱annealing處理可促進Nafion分子產生規則排列形成很大的結晶區，且隨著加熱annealing時間增加，其結晶區熔解吸熱也越大。以AC-impedance量測得到的導電度，我們可看到導電度隨著膜材加熱的時間增加而降低。在WAXD分析數據顯示，結晶度隨著加熱時間增加而增加，且Nafion膜以水膨潤後會使結晶度稍微下降。以SAXS研究Nafion薄膜的微結構：隨著加熱annealing時間增加，屬於主鏈氟碳化合物產生部份結晶的長區間間距增加，ionic cluster的長區間間距卻隨著加熱annealing時間增加而減小，用水膨潤後溼膜ionic cluster的長區間間距明顯大於乾膜。分析Nafion膜內的結晶粒子及離子聚集區可能是介於lamellae及球體﹙spherulite﹚結構之間。

Nafion ion exchange membrane is widely used as membrane of polymer electrolyte membrane fuel cell (PEMFC). In this thesis, we prepare Nafion solutions by replacing solvents of Nafion solutions with methanol/H2O, ethanol/H2O, propanol/H2O, and DMF (N,N-dimethyl formamide) solvents.The Nafion/alcohol/ H2O solutions were evaporated at room temperature to prepare Nafion membranes, which were brittle and had poor mechanical properties. However, these membranes crystallized after annealing at 120℃. The Nafion/DMF solutions were evaporated at 120℃ to prepare membranes. DSC and WAXD data revealed that the degree of crystallinity of Nafion membrane increased with increasing annealing time, which leaded to decreases in the degree of swelling of membrane in water and the ionic conductivity as annealing time increased. SAXS data showed that the long spacing of crystalline domain increased and the long spacing of ionic cluster decreased with increasing annealing time. The long spacing of ionic cluster increased after the membrane were swelled with water.

目 錄
摘要
目錄 i
表目錄 iii
圖目錄 iv
Nafion溶液成膜的物理性質與形態學研究
一、緒論 1
1.1 Nafion簡介 1
1.2 研究目的 4
1.3 文獻回顧 5
1.4 高分子小角度X光散射分析 9
1.4.1 相關函數(correlation function)分析 9
1.4.2 布拉格公式計算長區間間距 11
1.4.3 I(q)在低限q值的近似 11
1.4.3-1 Debye-Bueche theory 11
1.4.3-2 Guinier approximation 13
1.4.4 I(q)在無限大q值的近似 13
二、實驗方法 16
2.1 藥品 16
2.2 薄膜製作 17
2.2.1 溶劑的置換 17
2.2.2 室溫成膜 17
2.2.3 高溫成膜 17
2.3 使用儀器設備 20
2.4 實驗步驟 21
2.4.1 溶劑含量測定 21
2.4.2 DSC熱分析 21
2.4.3 導電度測定 21
2.4.4 廣角X光繞射分析(WAXD) 24
2.4.5 小角X光散射儀實驗 (SAXS) 26
三、結果討論 29
3.1 溶劑含量測定 29
3.2 DSC熱分析 37
3.3 導電度測定 46
3.4 廣角X光繞射分析(WAXD) 52
3.5 小角X光散射(SAXS)數據分析 62
3.5.1 小角度X-光散射原始數據 62
3.5.2 SAXS量測參數物理意義示意圖 75
3.5.3 低q與高q近似值計算<η2>、lp、Kp及σ 78
3.5.3-1 lp數據討論 78
3.5.3-2 σ數據討論 79
3.5.4 布拉格公式計算長區間間距L 93
3.5.5 一維及三維相關函數計算長區間間距L 93
3.5.6 由長區間間距L計算離子團聚集半徑及
-SO3H官能基數目 115
3.5.6 小角度X-光散射數據討論 120
四、結論 123
五、參考文獻 125

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