本研究以乾濕式相轉換法(dry-wet phase inversion method)由PVP(polyvinylpyrrolidone) /γ-丁內酯(gamma-Butyrolactone)/聚醚碸與Tween 20/碳酸丙烯酯(propylene carbonate)/聚乳酸兩系統製備多孔型薄膜，前者依PVP及PES之添加量不同，探討其對薄膜之物性與過濾效能之影響，所製得薄膜呈非對稱結構，表面為皮層，內部為手指狀巨孔，隨著PVP添加量增加，上、下表面孔洞逐漸變大，使純水通量提升，當添加至15 wt%時，結構轉變形成雙連續互穿結構；改變PES添加量時，薄膜表面孔洞尺寸變小，上表面變得緊實，使純水通量逐漸下降，薄膜之孔隙度約為60~81%，上表面的接觸角薄膜的抗張強度皆隨著PVP的添加逐漸下降，這是由於上、下表面孔洞變大所致，然而當固定PVP添加量時，抗張強度會隨著PES添加量增加，呈上升趨勢。PVP在薄膜的殘留量乃由NMR分析得知，結果顯示，殘留量佔膜重0.1~6.4 %而PVP的移除率約為73~99.8 %。在純水通量測試中發現隨著PVP的添加通量呈上升趨勢，當PVP添加至15 wt%時，其通量最高可達約1000 LMH。將薄膜進行BSA過濾時，發現BSA之移除率最高可達96%，過濾通量為51 LMH，利用PEG量測薄膜之截留分子量，發現其截留分子量約為137~454 kDa，此現象與純水通量及孔洞大小相互呼應。
後者依Tween 20之添加量及製膜液冷卻時間的不同，探討其對薄膜之物性與孔洞結構之影響，所製得薄膜之冷卻時間維持在10分鐘時，隨著Tween 20添加量增加，上、下面孔洞逐漸變大，截面結構由倒V趨勢轉為上下均一的孔洞，接著再轉為正V趨勢，最後轉變形成雙連續互穿結構，薄膜之孔隙度約為49~55%，抗張強度會隨著Tween 20添加量增加，呈下降趨勢；再添加5 wt% Tween 20而改變製膜液冷卻時間時，薄膜表面孔洞尺寸無太大變化，當冷卻時間達15分鐘時，胞孔縮小並開始產生相互連通之雙連續互穿結構，薄膜之孔隙度約為53~68 %。

In this research, we used the dry-wet phase inversion method to prepare porous membranes from the polyvinylpyrrolidone (PVP) / γ-butyrolactone (GBL) / polyethersulfone  (PES) and  the Tween 20 / propylene carbonate / poly(lactic acid) system to prepare porous membrane. According to the amount of added different PVP and PES content, we can be divided into 6 series: P16, P16K5, P16K10, P16K15, P13K10, P20K10. All membranes show the asymmetric structure with a dense surface (skin) and porous cross section composed of finger-liked macrovoids. With the increase of added PVP, the pores on the top and bottom surfaces increase, resulting in an increase of the pure flux. When increase of added 15 wt% PVP, the structure transform into bi-continuous porous. Changing the amount of added PES, the surface pore size of the membrane is found to decrease, resulting in a decrease of the pure flux. The porosity of membrane is about 60-81%, and the contact angle of the top surface gradually decreases with the addition of PVP. The tensile strength decrease with the increase of added amount of PVP, which is attributed to the larger pores of the top and bottom surfaces. However, when the added PVP is fixed, the tensile strength increases with the addition of PES. The amount of PVP resided in the membrane has been determined by NMR analysis. The results show that about 73-99.8 % of the PVP is removed during the membrane formation process and the residual amount only accounts for 0.1~6.4 % of the membrane weight. As to the pure water flux increase with the PVP content, when increase of added 15 wt% PVP, the flux are up to 1000 LMH. The BSA filtration experiments show that the rejection ratio of the membrane are up to 96% and permeation flux of BSA solution are 51 LMH. PEG is used to determine the molecular weight cut-off (MWCO) of the membranes. For PES membranes, the MWCO is about 137-454 kDa, these results are consistent with the pure water flux and the pore size.
The latter is based on the addition of different Tween 20 and different cooling time. All membranes show the asymmetric structure. With the increase of added Tween 20, the pores on the top and bottom surfaces increase, and the structure changes from the inverted V and then turns to the positive V trend and finally transform into bi-continuous porous. The porosity of membrane is about 49-55%, and the tensile strength decrease with the increase of added amount of Tween 20. With the increase of cooling time, the pores on the top and bottom surfaces is not much different. When increase of cooling time on 15 min, the cross section pores shrink and transform into bi-continuous porous. The porosity of membrane is about 53-68 %.

目錄
致謝 I
論文提要內容 Ⅱ
Abstract Ⅳ
目錄 VI
圖目錄 VIII
表目錄 X
第一章 序論 1
1.1 前言和研究目的 1
第二章 製備雙連續互穿結構之聚醚碸薄膜及其在超過濾之應用 3
2.1 前言 3
2.2 實驗 8
2.2.1 實驗藥品 8
2.2.2 浸置沉澱法製備聚醚碸薄膜 10
2.2.3 PES薄膜之物性測試分析 11
2.2.4 純水通量、截留分子量及抗垢測試 14
2.3 結果與討論 25 
2.3.1 PES薄膜之製備與物性分析 25
2.3.2 PES薄膜BSA抗垢能力測試 50
2.3.3 PES薄膜截留分子量測試 52
2.4 結論 55
2.5 參考文獻 56
附錄A PMI測試 65
附錄B AFM測試 73
附錄C 拉力測試 74
第三章 製備雙連續互穿結構之聚乳酸薄膜及其在微過濾之應用 77
3.1 前言 77
3.2 實驗 80
3.2.1 實驗藥品 80
3.2.2 浸置沉澱法製備聚乳酸薄膜 82
3.2.3 PLA薄膜之物性測試分析 83
3.3 結果與討論 85
3.3.1 PLA薄膜之製備與物性分析 85
3.4 結論 100
3.5 參考文獻 101

圖目錄
圖2-1 製備PES薄膜之流程 10
圖2-2 CFP之壓差與孔徑之關係 14
圖2-3 以HPLC測試分子量為26 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 16
圖2-4 以HPLC測試分子量為43 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 17
圖2-5 以HPLC測試分子量為50 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 18
圖2-6 以HPLC測試分子量為100 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 19
圖2-7 以HPLC測試分子量為150 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 20
圖2-8 以HPLC測試分子量為230 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 21
圖2-9 以HPLC測試分子量為500 kDa之PEG Standard所獲得之(a)折現率變化圖及(b)檢量線 22
圖2-10 不同濃度牛血清白蛋白(BSA)之UV吸收度檢量線 24
圖2-11 PES薄膜上表面之SEM影像圖 29
圖2-12 PES薄膜截面之SEM影像圖 30
圖2-13 PES薄膜截面巨孔之SEM放大影像圖 31
圖2-14 PES薄膜截面之SEM放大影像圖 32
圖2-15 不同比例組成之PES薄膜下表面SEM影像圖 33
圖2-16 (a)聚醚碸PES與 (b)聚乙烯吡咯烷酮PVP之H-NMR光譜圖 37
圖2-17 PES薄膜之H-NMR光譜圖 40
圖2-18 PES薄膜之FTIR-ATR光譜圖 45
圖2-19 製膜液中PVP含量對薄膜厚度及拉伸強度作圖 47
圖2-20 製膜液中PES含量對薄膜厚度及拉伸強度作圖 47
圖2-21 PES薄膜之薄膜純水通量 49
圖2-22 PES薄膜過濾BSA之通量隨時間變化圖 52
圖2-23 PES薄膜之截留率與水通量對PEG分子量作圖 54
圖A-1 P16K5薄膜之氣體流量對壓力作圖 65
圖A-2 P16K5薄膜之累積氣體流量對孔徑作圖 65
圖A-3 P16K5薄膜之孔徑分佈圖 66
圖A-4 P16K5薄膜之孔徑分佈對平均孔徑作圖 66
圖A-5 P16K10薄膜之氣體流量對壓力作圖 67
圖A-6 P16K10薄膜之累積氣體流量對孔徑作圖 67
圖A-7 P16K10薄膜之孔徑分佈圖 68
圖A-8 P16K10薄膜之孔徑分佈對平均孔徑作圖 68
圖A-9 P16K15薄膜之氣體流量對壓力作圖 69
圖A-10 P16K15薄膜之累積氣體流量對孔徑作圖 69
圖A-11 P16K15薄膜之孔徑分佈圖 70
圖A-12 P16K15薄膜之孔徑分佈對平均孔徑作圖 70
圖A-13 P13K10薄膜之氣體流量對壓力作圖 71
圖A-14 P13K10薄膜之累積氣體流量對孔徑作圖 71
圖A-15 P13K10薄膜之孔徑分佈圖 72
圖A-16 P13K10薄膜之孔徑分佈對平均孔徑作圖 72
圖B-1 PES薄膜之粗糙度分析 73
圖C-1 PES薄膜之拉伸強度分析 76
圖3-1 製備PLA薄膜之流程 82
圖3-2 PLA薄膜上表面之SEM影像圖 89
圖3-3 PLA薄膜截面之SEM影像圖 90
圖3-4 PLA薄膜截面之SEM放大影像圖 91
圖3-5 PLA薄膜下表面之SEM影像圖 92
圖3-6 不同冷卻時間之PLA薄膜上表面之SEM影像圖 94
圖3-7 不同冷卻時間之PLA薄膜截面之SEM影像圖 95
圖3-8 不同冷卻時間之PLA薄膜截面之SEM放大影像圖 96
圖3-9 不同冷卻時間之PLA薄膜下表面之SEM影像圖 97

表目錄
表2-1 製備PES薄膜之製膜液組成 11
表2-2 PES薄膜之厚度、接觸角、孔隙度、孔洞尺寸及製膜液黏度 27
表2-3 由H-NMR計算所得PVP之殘留率及移除率 36
表2-4 PES薄膜之FTIR/ATR上下表面分析 42
表2-5 PES薄膜之抗張強度與伸長率 46
表2-6 PES薄膜之純水通量 (L/m2h) 49
表2-7 Guerout–Elford–Ferry 方程式計算所得之薄膜表面平均孔徑dma 50
表2-8 PES薄膜BSA過濾之回復率及截留率 51
表2-9 PES薄膜過濾BSA阻力 51
表2-10 各系列薄膜之截留分子量及計算之表面孔洞大小 (nm) 53
表3-1 製備PLA薄膜之製膜液組成 83
表3-2 PLA薄膜之厚度、接觸角、孔隙度、孔洞尺寸及製膜液黏度 86
表3-3 不同冷卻時間系列薄膜之厚度、接觸角、孔隙度、孔洞尺寸 87
表3-4 PLA薄膜之抗張強度與伸長率 99
表3-5 不同冷卻時間之PLA薄膜抗張強度與伸長率 99

第二章
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