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中文論文名稱 以掺合-溶洗法製備聚偏二氟乙烯及其共聚物之多孔型薄膜與薄膜之物性分析
英文論文名稱 Preparation and characterization of porous PVDF and PVDF copolymer membranes by using blending-leaching method
校院名稱 淡江大學
系所名稱(中) 化學工程與材料工程學系碩士班
系所名稱(英) Department of Chemical and Materials Engineering
學年度 94
學期 2
出版年 95
研究生中文姓名 姚良欽
研究生英文姓名 Liang-Chin Yao
學號 693361312
學位類別 碩士
語文別 中文
口試日期 2006-07-13
論文頁數 81頁
口試委員 指導教授-鄭廖平
委員-林達鎔
委員-楊台鴻
中文關鍵字 聚偏二氟乙烯  共聚物  多孔型薄膜  高分子摻合 
英文關鍵字 poly(vinylidene fluoride)  porous membrane  copolymers  polymer blend 
學科別分類
中文摘要 本研究利用高分子摻合技術配合溶劑移除法,製備PVDF或其共聚物之多孔型薄膜,並分析薄膜物性與孔隙結構以評估其應用性。首先將三種氟系高分子:(1)聚偏二氟乙烯(Kynar 740, Elf Ato Chem),(2)偏二氟乙烯-六氟丙烯共聚物(Kynar 2750),(3)偏二氟乙烯-四氟乙烯-六氟丙烯三聚物(Kynar 9301)以溶液摻合法,兩兩成對予以混摻,製成複合膜,探討各組成比例對複合膜之相容性,熱性質、結晶性等物性之影響。然後利用適當溶劑與溫度,溶洗出其中之ㄧ成分,以製備多孔型薄膜。藉由混摻比例的不同,預期可製作出不同孔隙結構之對稱或非對稱型薄膜,並以SEM、XRD、Contact Angle等來作膜材物性與結構分析。同時利用水通量與截留分子量之測試來判定薄膜之適用分離程序。
英文摘要 In this research, polymer blending technique will be incorporated with the solvent leaching method to prepare porous membranes of PVDF or its copolymer. The physical properties of the formed membranes will be characterized and their porous structures be analyzed, such as to find out their suited areas of applications. Firstly, three polymer pairs being chosen from the three fluoro-polymers: (1) poly(vinylidene fluoride) (Kymnar 740, Elf Ato Chem), (2) copolymer of vinylidene fluoride and hexafluoro propylene (Kynar 2750, Elf Ato Chem), (3) terpolymer of vinylidene fluoride, tetrafluoro ethylene, and hexafluoro propylene (Kynar 9301, Elf Ato Chem), will be solution blended to prepare composite membranes. The effect of composition of the blends on the compatibility, level of phase separation, thermo behavior, crystallinity, and mechanical strength of the membranes will be investigated. Thereafter, a suitable solvent will be adopted to extract one polymer component out of the composite at an appropriate temperature to yield a porous membrane. By varying the compositions of the blends, symmetric or asymmetric membranes of a wide spectrum of porous morphology are expected to be produced. SEM, DSC, XRD, DMA, and Contact Angle analyses will be carried out on the formed membranes to obtain the physical and morphological data of the membranes. In addition, water fluxes and molecular weight cut off (MWCO) of the membranes will be determined to judge their applicability in various separation processes.
論文目次 目錄
論文提要內容 I
Abstract II
目錄 III
表目錄 VI
圖目錄 VIII
第一章 序論 1
1-1 前 言 1
1-2 研究動機 3
1-3 研究目的 5
第二章 基礎理論 6
2-1 高分子摻合 6
2-1-1 定義 6
2-1-2 摻合體的製備方法 6
2-1-3 高分子摻合之相容性 7
2-2 高分子薄膜 10
2-2-1 薄膜之定義 10
2-2-2 薄膜的製備方法 11
2-2-3 摻合-溶出法製備多孔型薄膜 13
第三章 實驗方法 16
3-1 藥品 16
3-2 實驗儀器 18
3-3實驗方法與步驟 21
3-3-1 薄膜的製備 21
3-3-2 孔型薄膜的製備 22
3-3-3 移除效率 22
3-3-4 薄膜結構與物性分析 23
第四章 結果與討論 26
4-1 掺合膜之相容性與物性分析 26
4-1-1 掺合膜相容性分析 26
4-1-1-1 動態機械分析(DMA) 27
4-1-1-2 微差熱卡計(DSC) 33
4-1-2 掺合膜結晶行為 34
4-1-2-1 廣角X光繞射儀(WAXD) 34
4-1-2-2 微差熱卡計(DSC) 40
4-2 多孔型薄膜之製備與物性分析 45
4-2-1 溶洗條件與移除效率 45
4-2-2 薄膜SEM結構分析 50
4-2-3 薄膜孔隙度之量測 61
4-2-4 接觸角測試 63
4-2-5 拉伸測試 64
4-2-6 水通量檢測 66
4-2-7 截留率測試 68
第五章 結論 70
參考文獻 71
附錄 A 76

表目錄
表1-1 不同以壓力為驅動力的薄膜分離程序的通量與壓力範圍 2
表1-2 薄膜分離程序與其對應的驅動力 2
表3.1 不同掺合系統之製膜溫度 21
表4-1 Kynar 740 / Kynar 9301摻合體的玻璃轉移溫度 30
表4-2 Kynar 2750 / Kynar 9301摻合體的玻璃轉移溫度 31
表4-3 PVDF結晶型態 35
表4-4 PVDF其不同結晶型態於FTIR的吸收峰 37
表4-5 各比例Kynar 740 / Kynar 9301掺合膜之熔點與結晶度 42
表4-6 各比例Kynar 2750 / Kynar 9301掺合膜之熔點與結晶度 43
表4-7 以丙酮在35oC下,對於740 / 9301掺合膜的移除效率 46
表4-8 以90%丙酮水溶液在25oC下,對2750 / 9301掺合膜的移除效率 47
表4-9 以88%丙酮水溶液在25oC下,對2750 / 9301掺合膜的移除效率 48
表4-10 以85%丙酮水溶液在25oC,對2750 / 9301掺合膜的移除效率 48
表4-11 以90%丙酮水溶液在5oC下,對2750 / 9301掺合膜的移除效率 49
表4-12 各比例之多孔型薄膜的孔隙度 61
表4-13 各比例多孔型薄膜的抗張強度與其伸長量 64

圖目錄
圖2-1 DSC測量玻璃轉移溫度對相容性的關係示意圖 9
圖2-2 不同類型薄膜橫截面示意圖2 11
圖4-1 偏二氟乙烯(Kynar 740)的動態機械分析 28
圖4-2聚偏二氟乙烯共聚物(Kynar 2750)的動態機械分析 28
圖4-3 三成份含氟共聚物(Kynar 9301)的動態機械分析 29
圖4-4 Kynar 740 / Kynar 9301系統之tan δ和溫度關係圖 30
圖4-5 Kynar 2750 / Kynar 9301系統之tan δ和溫度關係圖 32
圖4-6 Kynar 2750 / Kynar 9301系統之DSC圖 33
圖4-7 各比例Kynar 740 / Kynar 9301掺合膜之XRD圖 35
圖4-8 各比例Kynar 2750 / Kynar 9301掺合膜之XRD圖 36
圖4-9 Kynar 740(PVDF)之紅外線光譜圖 38
圖4-10 Kynar 2750之紅外線光譜圖 38
圖4-11 Kynar 9301之紅外線光譜圖 39
圖4-12 各比例Kynar 740 / Kynar 9301掺合膜之DSC圖(Ⅰ) 41
圖4-13 各比例Kynar 740 / Kynar 9301掺合膜之DSC圖(Ⅱ) 41
圖4-14 各比例Kynar 2750 / Kynar 9301掺合膜之DSC圖(Ⅰ) 43
圖4-15 各比例Kynar 2750 / Kynar 9301掺合膜之DSC圖(Ⅱ) 44
圖4-16 Kynar 740:9301比例為80:20掺合膜溶洗後之SEM圖 51
圖4-17 Kynar 740:9301比例為70:30掺合膜溶洗後之SEM圖 52
圖4-18 Kynar 740:9301比例為60:40掺合膜溶洗後之SEM圖 53
圖4-19 Kynar 740:9301比例為50:50掺合膜溶洗後之SEM圖 54
圖4-20 Kynar 2750:9301比例為80:20掺合膜溶洗後之SEM圖 57
圖4-21 Kynar 2750:9301比例為70:30掺合膜溶洗後之SEM圖 58
圖4-22 Kynar 2750:9301比例為60:40掺合膜溶洗後之SEM圖 59
圖4-23 Kynar 2750:9301比例為50:50掺合膜溶洗後之SEM圖 60
圖4-24各比例多孔型薄膜之厚度 62
圖4-25各比例多孔型薄膜之孔隙度 62
圖4-26各比例多孔型薄膜的接觸角 63
圖4-27各比例多孔型薄膜的抗張強度 65
圖4-28各比例多孔型薄膜的伸長量 65
圖4-29各比例多孔型薄膜的水通量 67
圖4-30各比例多孔型薄膜的的透過性質 67
圖4-31各混摻比例薄膜之不同分子量對R%之關係圖 69
圖A-1 分子量200萬之葡聚糖 (a)折射率變化圖;(b)檢量線 77
圖A-2 分子量40至50萬之葡聚糖 (a)折射率變化圖;(b)檢量線 78
圖A-3 分子量64000~76000之葡聚糖 (a)折射率變化圖;(b)檢量線 79
圖A-4 分子量35000~45000之葡聚糖 (a)折射率變化圖;(b)檢量線 80
圖A-5 分子量8500~11500之葡聚糖 (a)折射率變化圖;(b)檢量線 81

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