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系統識別號 U0002-1701201413360700
中文論文名稱 以非恆溫浸漬沉澱法製備多孔型高分子薄膜
英文論文名稱 Preparation of porous polymer membranes via non-isothermal immersion precipitation 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 102
學期 1
出版年 103
研究生中文姓名 吳昱璇
研究生英文姓名 Yu-Hsuan Wu
學號 699400304
學位類別 碩士
語文別 中文
口試日期 2013-12-27
論文頁數 106頁
口試委員 指導教授-鄭廖平
委員-李亦淇
委員-張旭賢
中文關鍵字 聚乙烯乙烯醇  冷溶劑誘導相分離法  非溶劑誘導相分離法  驟冷深度  聚偏二氟乙烯  循環使用槽  製膜液厚度  多孔膜 
英文關鍵字 EVOH  cold-solvent induced phase separation(CIPS)  non-isothermal immersion precipitation method  quench depth  spinodal decomposition  poly(vinylidene fluoride)  reusable bath  casting thickness  porous membrane 
學科別分類
中文摘要 本研究首先利用冷溶劑誘導相分離法,由聚乙烯乙烯醇/1,3-丙二醇兩成分系統製備多孔型聚乙烯乙烯醇薄膜,並藉由改變沉澱槽之溫度及刮刀之厚度,探討此二參數對薄膜結構與物性的影響。當沉澱槽溫度落在結晶線之下及液-液分相線之上時(45℃),薄膜呈現微粒狀結晶結構,而落在spinodal分相曲線內部時(25℃),則呈現雙連續網狀結構且有些許微粒結晶之特徵,當更深入spinodal區域時(5℃&-20℃),則呈現單純雙連續網絡結構。以不同厚度刮刀塗佈製膜液並浸漬於5℃沉澱槽時,其薄膜結構皆呈現典型之spinodal decomposition所產生之雙連續網絡結構。而各項分析結果皆指出,水通量、水滲透時間與機械強度的測量結果和薄膜的型態、孔隙度和孔徑大小有關,此外,藉由XRD和DSC等儀器分析,測得薄膜結晶度大約在38~42%左右,並由DSC的測量得知薄膜的熔點為~184℃。本研究接著選用聚偏二氟乙烯/磷酸三乙酯(TEP)/純水三成分系統,結合了非溶劑誘導相分離法及熱誘導式相分離法兩種製膜法之特點,在相圖上找到一個特殊的製膜液組成,使得製膜液內溶劑/非溶劑以及沉澱槽溶劑/非溶劑之比例相同,成為循環使用槽(reusable bath),並利用其製備聚偏二氟乙烯多孔型高分子薄膜。藉由改變沉澱槽之成份以及刮刀之厚度,製作出一系列不同孔隙結構之薄膜,探討其物性及其過濾之效率。以reusable沉澱槽所製備之薄膜無皮層的產生,而以純水、30wt% TEP及60wt% TEP之沉澱槽所製備之薄膜皆有皮層生成,隨著沉澱槽TEP濃度的提升,皮層呈現越來越薄之趨勢。而皮層的厚度影響薄膜之孔隙度與機械強度,皮層越薄,孔隙度隨之提升,使得機械強度減弱。當以不同厚度刮刀塗佈製膜液並浸漬於reusable沉澱槽時,我們可從FE-SEM影像圖發現,隨著刮刀厚度越薄,其薄膜結構越趨向於蕾絲結構之型態。此外,藉由DSC的測量得知薄膜的熔點為~159℃,並由XRD的分析得知薄膜結晶度大約在63~64%左右。由水通量與過濾實驗得知,以reusable沉澱槽所製備之薄膜具有相當高的通量和良好之阻隔率。
英文摘要 The purpose of this study is to investigate the effect of bath temperature and casting thickness on the preparation of membranes from EVOH/1,3-propanediol binary mixture system via the cold solvent induced phase separation (CIPS) process. When the temperature of the precipitation bath (45℃) was below the crystallization line and above the liquid - liquid phase separation line, the membrane exhibited a crystalline particulate structure; when the bath temperature (25℃) was just below the spinodal decomposition temperature, it presented a bi-continuous network structure and bore slight crystallization characteristics of particles; when the bath temperature (5℃&-20℃) sit deeply in the spinodal zone, it presented a pure bi-continuous network structure. With different casting thickness and immersed in 5℃bath, the formed membranes all presented bi-continuous network structure typically arising from spinodal decomposition. The water permeation flux, wettability and tensile strength of the membranes were measured and the results indicated that they were correlated with the porosity, pore size, and membrane morphology. In addition, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses indicated that the membranes had crystallinity of 38~42 %. The DSC data also showed that all membranes had a similar crystal melting behavior with Tm close to 184℃.
We then chose the poly (vinylidene fluoride)/triethyl phosphate/water ternary system and used a method that combined features of non-solvent induced phase separation (NIPS) and thermal induction phase separation (TIPS) to prepare porous PVDF membranes. In the phase diagram we found on a special dope composition such that the solvent/non-solvent ratio in the dope was equal to that in the precipitation. Therefore, the composition of the bath could be held constant by itself, and the bath can be used repeatedly (termed reusable bath). By varying the composition of the precipitation bath and casting thickness, a series of membranes with different porous structures were formed. The effects of the membrane structure and filtration performance have been studied subsequently. Results showed that when water, 30wt% TEP and 60wt% TEP were used as the precipitation bath, the membrane presented a skin layer at the top surface. In contrast, when precipitation in the reusable bath, it did not show a skin layer near the top, and with increasing of the TEP concentration in the bath, thinner skin layer tended to form. The thickness of the skin layer was found to affect the porosity and mechanical strength of the membranes; the thinner the skin, the higher the porosity, and thus the lower the mechanical strength. When films with different thickness were immersed in the reusable bath, we found from the FE-SEM images that thinner casting thickness tended to yield membranes that bore lacy structure. In addition, DSC measurements showed that the melting points of the membranes were ~159℃, while XRD analyses indicated that the crystallinity of membranes was about 63 to 64%. The water flux and filtration experiments showed that the membranes prepared from the reusable bath exhibited both high permeability and selectivity.
論文目次 總目錄
誌謝.......................................................I
中文摘要....................................................Ⅱ
Abstract..................................................Ⅲ
總目錄.....................................................Ⅴ
圖目錄.....................................................Ⅶ
表目錄.....................................................Ⅹ

第一章 序論.................................................1
1-1 前言...................................................1
1-2 研究動機與目的...........................................3
1-3 參考文獻................................................4
第二章 聚乙烯乙烯醇薄膜之合成及其物性分析.........................5
2-1 前言...................................................5
2-2 實驗...................................................9
2-2.1 實驗材料..............................................9
2-2.2 實驗方法與步驟.........................................9
2-3 物性分析步驟.............................................9
2-4 結果與討論.............................................12
2-4.1 EVOH32-1,3-propanediol兩成分系統之相圖................12
2-4.2 探討沉澱槽溫度對EVOH薄膜之影響及其物性分析................14
2-4.2.1 薄膜結構與型態......................................14
2-4.2.2 薄膜厚度與孔隙度之量測................................25
2-4.2.3 孔隙影像分析........................................26
2-4.2.4 滲透性與水通量測試...................................28
2-4.2.5 拉力測試...........................................31
2-4.2.6 微差掃描式熱分析(DSC)之熱行為分析......................32
2-4.2.7 廣角X-ray繞射(WXRD)之結晶度計算......................34
2-4.3 製膜液厚度對EVOH薄膜物性之影響..........................36
2-4.3.1 薄膜結構與型態......................................36
2-4.3.2 薄膜厚度與孔隙度之量測................................42
2-4.3.3 孔隙影像分析........................................42
2-4.3.4 拉力測試...........................................43
2-4.3.5 微差掃描式熱分析(DSC)之熱行為分析......................43
2-4.3.6 廣角X-ray繞射(WXRD)之結晶度計算......................45
2-5 結論..................................................47
2-6 參考文獻...............................................48
第三章 聚偏二氟乙烯薄膜之合成及其物性分析........................54
3-1 前言..................................................54
3-2 實驗..................................................58
3-2.1 實驗材料.............................................58
3-2.2 實驗方法與步驟........................................58
3-2.2.1 薄膜的製備.........................................58
3-2.2.2 相圖之觀測.........................................59
3-3 物性分析步驟............................................61
3-4 結果與討論.............................................63
3-4.1 PVDF/TEP/WATER三成分系統之相圖.........................63
3-4.2 探討沉澱槽成分對PVDF薄膜之影響及其物性分析.................65
3-4.2.1 薄膜結構與型態......................................65
3-4.2.2 薄膜厚度與孔隙度之量測................................75
3-4.2.3 拉力測試...........................................76
3-4.2.4 水通量測試.........................................77
3-4.2.5 接觸角分析.........................................78
3-4.2.6 微差掃描式熱分析(DSC)之熱行為分析......................78
3-4.2.7 廣角X-ray繞射(WXRD)之結晶度計算......................80
3-4.2.8 薄膜過濾之應用......................................82
3-4.3 製膜液厚度對PVDF薄膜物性之影響..........................86
3-4.3.1 薄膜結構與型態......................................86
3-4.3.2 薄膜厚度與孔隙度之量測................................93
3-4.3.3 拉力測試...........................................94
3-4.3.4 水通量測試.........................................95
3-4.3.5 接觸角分析.........................................96
3-4.3.6 微差掃描式熱分析(DSC)之熱行為分析......................96
3-4.3.7 廣角X-ray繞射(WXRD)之結晶度計算......................98
3-4.3.8 薄膜過濾之應用......................................99
3-5 結論.................................................100
3-6 參考文獻..............................................102

圖目錄
Fig.2-1 Scheme of mass and thermal transfer occurring at the film/bath interfaceby CIPS.................................7
Fig.2-2 Phase diagram of the EVOH32/1,3-propanediol system ..........................................................13
Fig.2-3 Total cross sectional morphologies of the EVOH membranes precipitated from different temperature baths...18
Fig.2-4 Cross sectional morphology of the EVOH membranes precipitated from baths at different temperatures.........19
Fig.2-5 Top surface morphology of the EVOH membranes precipitated from baths at different temperatures.........21
Fig.2-6 Path of pourse membrane formation by CIPS.........22
Fig.2-7 Morphology of the cross section near the top surface of the EVOH membrane precipitated from 5℃bath............22
Fig.2-8 Bottom surface morphology of the EVOH membranes precipitated from baths at different temperatures.........23
Fig.2-9 Cross sectional morphology of an EVOH membrane prepared by the TIPS method. The polymer concentration in the dope was 20 wt% and the quenching temperature was 5℃ ..........................................................24
Fig.2-10 Cross sectional morphology of an EVOH membrane prepared by the CIPS method. The polymer concentration in the dope was 20 wt% and the bath was 1,3-propanediol at 5℃ ..........................................................24
Fig.2-11 Morphology of the membrane precipitated from bath at 25℃...................................................27
Fig.2-12 Water flux of membranes precipitated from different temperature baths at different pressure...................30
Fig.2-13 Tensile strengths of membranes precipitated from different temperature baths...............................32
Fig.2-14 DSC themograms of EVOH membranes precipitated from different temperature baths...............................33
Fig.2-15 XRD of EVOH membranes precipitated from different temperature baths.........................................34
Fig.2-16 Deconvolation of XRD patterns of EVOH membranes precipitated from different temperature baths.............35
Fig.2-17 Total cross section morphology of the EVOH membranes precipitated from 1,3-propanediol bath at 5℃...37
Fig.2-18 High magnification images of cross section morphology of the EVOH membranes precipitated from 1,3-propanediol bath at 5℃...................................38
Fig.2-19 Top surface morphology of the EVOH membranes precipitated from 1,3-propanediol bath at 5℃.............40
Fig.2-20 Bottom surface morphology of the EVOH membranes precipitated from 1,3-propanediol bath at 5℃.............41
Fig.2-21 DSC themograms of EVOH membranes precipitated from different casting thickness at 5℃baths...................44
Fig.2-22 XRD of EVOH membranes precipitated from different casting thickness at 5℃baths.............................45
Fig.2-23 Deconvolation of XRD patterns of EVOH membranes precipitated from different casting thickness at 5℃baths ..........................................................46
Fig.3-1 (a)Schematic representation of reusable bath composition for the ternary system.(b)The relative position of dope composition and gelation lines and L-L mixing line ..........................................................57
Fig.3-2 Phase separation behavior of PVDF/TEP/WATER system ..........................................................60
Fig.3-3 Phase diagram of the PVDF/TEP/WATER system........64
Fig.3-4 Total cross sectional morphologies of the PVDF membranes precipitated from different baths...............67
Fig.3-5 Cross sectional morphology of the PVDF membranes precipitated from different baths.........................68
Fig.3-6 Morphology of the cross section near the top surface of the PVDF membrane precipitated from different baths....69
Fig.3-7 High magnification of the cross section near the top surface of the PVDF membrane precipitated from water baths ..........................................................70
Fig.3-8 Top surface morphology of the PVDF membranes precipitated from different baths.........................71
Fig.3-9 Bottom surface morphology of the PVDF membranes precipitated from different baths.........................73
Fig.3-10 Water flux of PVDF membranes precipitated from different baths...........................................77
Fig.3-11 DSC themograms of PVDF membranes precipitated from different baths...........................................79
Fig.3-12 XRD diffractograms of PVDF membranes precipitated from different baths......................................81
Fig.3-13 Blue dextran filtration of PVDF membranes precipitated from reusable baths..........................83
Fig.3-14 Blue dextran concentration v.s. wavelength curve ..........................................................84
Fig.3-15 Concentration of blue dextran....................85
Fig.3-16 Total cross sectional morphologies of the PVDF membranes precipitated from reusable baths................88
Fig.3-17 Cross sectional morphology of the PVDF membranes precipitated from reusable baths..........................89
Fig.3-18 Morphology of the cross section near the top surface of the PVDF membrane precipitated from reusable baths.....................................................90
Fig.3-19 Top surface morphology of the PVDF membranes precipitated from reusable baths..........................91
Fig 3-20 Bottom surface morphology of the PVDF membranes precipitated from reusable baths..........................92
Fig.3-21 Water flux of PVDF membranes precipitated from different casting thickness at reusable baths.............95
Fig.3-22 DSC themograms of PVDF membranes precipitated from from different casting thickness at reusable baths........97
Fig.3-23 XRD diffractograms of PVDF membranes precipitated from different casting thickness at reusable baths........98

表目錄
Table 1-1 薄膜的最新技術以及它們的應用 2
Table 1-2 商業合成薄膜之結構、材料以及其分離機制 2
Table 2-1 Porosity of membranes precipitated from different temperature baths 25
Table 2-2 Image J analysis of membranes precipitated from different temperature baths 26
Table 2-3 Wettability and water flux of membranes precipitated from different temperature baths 29
Table 2-4 30
Table 2-5 Tensile strengths of membranes precipitated from different temperature baths 31
Table 2-6 Themal properties and crystallinity of EVOH membranes 33
Table 2-7 Curve fitting of membranes precipitated from different temperature baths 35
Table 2-8 Porosities of the membranes precipitated from different casting thickness at 5℃baths 42
Table 2-9 Image J analysis of membranes precipitated from different casting thickness at 5℃baths 42
Table 2-10 Tensile strengths of membranes precipitated from different casting thickness at 5℃baths 43
Table 2-11 Themal properties and crystallinity of EVOH membranes 44
Table 2-12 Curve fitting of membranes precipitated from different casting thickness at 5℃baths 46
Table 3-1 Dope composition of the PVDF/TEP/WATER system phase diagram 59
Table 3-2 Porosity of membranes precipitated from different baths 75
Table 3-3 Tensile strengths of membranes precipitated from different baths 76
Table 3-4 Contact angle of membranes precipitated from different baths 78
Table 3-5 Themal properties and crystallinity of PVDF membranes 79
Table 3-6 Crystal type of PVDF 80
Table 3-7 Crystallinity of PVDF membranes determined by XRD 81
Table 3-8 Rejection and filtration of PVDF membranes precipitated from 60wt% TEP and reusable baths 84
Table 3-9 Porosity of membranes precipitated from from different casting thickness at reusable baths 93
Table 3-10 Tensile strengths of membranes precipitated from from different casting thickness at reusable baths 94
Table 3-11 Contact angle of membranes precipitated from from different casting thickness at reusable baths 96
Table 3-12 Themal properties and crystallinity of PVDF membranes 97
Table 3-13 Crystallinity of PVDF membranes determined by XRD 98
Table 3-14 Rejection and filtration of PVDF membranes precipitated from different casting thickness at reusable baths 99
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