本實驗主要利用聚偏二氟乙烯(PVDF)膜經由臭氧表面處理的方式，使得聚偏二氟乙烯膜表面產生過氧化氫等官能基，再藉由升溫使過氧化官能基斷鍵形成自由基，並引發丙烯酸(AA)單體上的C=C官能基進行聚合反應，接枝至聚偏二氟乙烯膜上。再以末端帶有胺基之N-異丙基丙烯醯胺(PNIPAAm)與部分AA上之COOH官能基反應鍵結。最後以四氧化三鐵(Fe3O4)與COOH官能基反應鍵結，得到具有溫敏性和磁敏性的聚偏二氟乙烯薄膜。實驗結果利用磁鐵、紅外線光譜儀(FTIR)、化學分析電子儀(ESCA)、掃描式電子顯微鏡(SEM)確認此改質聚偏二氟乙烯改質膜的結構。
利用聚N-異丙基丙烯醯胺之溫敏性質，使得表面改質聚氟化二乙烯膜在不同溫度環境下進行過濾實驗，其水流通透量突然有顯著的改變。由實驗結果發現，當溫度提高時，水流通透量會增加，並利用水流通透量(Flux)與溫度關係作圖，找出LCST(lower critical solution temperature)介於40~41.5℃。在不同PH值環境下，LCST隨著PH值下降而降低，並且當PH值高於8.93時無LCST性質。將改質聚氟化二乙烯膜置於交變磁場下(Alternative magnetic field)，使得磁性奈米粒子產生熱能，進而達到溫度變化而使得N-異丙基丙烯醯胺型態改變。
以水流通透實驗裝置進行蛋白質吸附實驗，利用已改質之PVDF膜進行水洗。於外高溫去離子水並加入一固定磁場條件下，可獲得較高的水流通透恢復率(flux recovery ratio)。

In this study, thermo-responsive and magnetic poly(vinyldiene fluoride) (PVDF) membranes grafted with branched poly(N-isopropylacrylamide) (PNIPAAm) chains and magnetic Fe3O4 particles have been prepared.
The preparation method includes three reactions. The first step is grafts of poly(acrylic acid) (PAA) chains to PVDF membrane surfaces. The PVDF membrane has been treated by ozone to generate peroxide and hydroperoxide groups on the PVDF membrane surface. Surface-initiated radical polymerization of acrylic acid (AA) is then carried out to introduce PAA chains to PVDF membrane surface. The second step is incorporation of PNIPAAm chains using amino-terminated PNIPAAm as areagent through the addition reaction between the carboxylic acid groups of PAA and the amine groups of PNIPAAm. Then Fe3O4 nanoparticles are then attached onto the surface of PVDF-AA-NIPAAm through the condensation reaction between the hydroxyl groups of Fe3O4 nanoparticles and the carboxylic acid groups of PAA. The chemical structures of the surface-modified PVDF membranes have been characterized with FTIR, ESCA and SEM.
In water flux experiment, the water flux of the membrane increases with the increasing the temperatures because of the conformational change of the thermo-responsive PNIPAAm chains. The fluxes show a dramatically increase between 40 and 41.5 oC, which is corresponding to the the lower critical solution temperature (LCST) of the PNIPAAm chains. With solution under different pH values, the measured LCST’s increase with temperature increasing. Moreover, the PVDF-PAA-PNIPAAm-Fe3O4 membrane could be heated with an alternative magnetic field, as the presence of the magnetic Fe3O4 nanoparticles on the membrane surface. The magnmetothermal effect of the membrane is demonstrated.
In the membrane cleaning tests, the membrane is fouled with BSA and then cleaned under different condition. A high flux recovery ratio has been obtained with the PVDF-PAA-PNIPAAm-Fe3O4 membrane to demonstrate its ease cleaning property. The thermally and magnetically-induced structure changes of the grafted layer of PVDF-PAA-PNIPAAm-Fe3O4 membrane contribute to the release of BSA from the membrane surface and the cleaning performance of the membrane.

目錄
誌謝 I
摘要 II
Abstract IV
目錄 VI
第一章 導論 1
1.1 過濾膜簡介[1-3] 1
1.1.1過濾膜分類 2
1.2磁性材料簡介 4
1.2.1磁性材料的起源 4
1.2.2磁性物質的分類[5,6] 6
1.2.3磁性質與磁滯曲線 11
1.2.4磁異相性 12
1.3嵌段聚合物(block copolymer) 15
1.3.1刺激應答型高分子(stimuli-responsive polymer)[10] 16
1.4研究動機 22
第二章 文獻回顧 23
2.1磁性奈米粒子 23
2.1.1 Fe3O4表面修飾及應用 27
2.2過濾膜 36
2.2.1薄膜改質方式 36
2.2.2 溫敏性過濾膜 40
第三章 藥品與實驗步驟 45
3.1 藥品 45
3.2 薄膜材料 46
3.3 實驗儀器 47
3.4 實驗步驟 52
3.4.1 Fe3O4製備[19] 52
3.4.2 PNIPAAm-NH2製備[35] 52
3.4.3 PVDF-AA製備 53
3.4.4 PVDF-AA-NIPAAm製備 53
3.4.5 PVDF-AA-NIPAAm-Fe3O4製備 54
3.4.6 水流通透實驗 55
第四章 結果與討論 57
4.1 FE3O4之結構鑑定 57
4.2 PNIPAAM-NH2之結構鑑定 60
4.3 PVDF-AA之結構鑑定 63
4.4 PVDF-AA-NIPAAM之結構鑑定 68
4.5 PVDF-AA-NIPAAM-FE3O4之結構鑑定 72
4.6 PVDF-AA-NIPAAM-FE3O4膜水流通透實驗 79
結論 88
參考資料 89

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