臺灣博碩士論文加值系統

本研究在製膜液中導入自行合成之奈米二氧化鈦(titania, TiO2)溶膠及聚乙烯吡咯烷酮(PVP)兩種添加劑，藉由前者之親水性改善PES薄膜易結垢之缺失，及後者之造孔功能，使孔隙交穿連通，製備出PES/TiO2複合薄膜(俗稱mixed matrix membrane, MMM)，依PVP添加量不同，將薄膜分為P0、P1.5以及P5三系列，每系列薄膜中各含不同濃度TiO2。TiO2是採用溶膠-凝膠法合成，其粒徑大小約為2-3 nm，並且為了讓TiO2能充分分散在製膜液中，不論調配製膜液或合成TiO2皆以二甲基乙醯胺(DMAc)作為溶劑；所製得薄膜皆呈現非對稱結構，表面為皮層，內部則由手指狀巨孔及不規則大型巨孔所構成，隨著PVP添加量增加，上下表面孔洞逐漸變大，使得純水通量隨之增加，而不規則大型孔洞逐漸轉化為手指狀巨孔；改變TiO2添加量時，會使得薄膜表孔洞尺吋呈先增後降趨勢，使得純水通量亦呈相同趨勢，薄膜之孔隙度約為80~88%，上表面接觸角則會隨著TiO2的添加而逐漸下降，抗張強度隨著PVP添加量提高，逐漸下降，這是由於上下表面孔洞變大所造成，然而當固定PVP添加量時，抗張強度則會隨著TiO2的添加，呈先增後降趨勢。PVP在薄膜的殘留量是由NMR分析取得，結果顯示約90% PVP於成膜過程中已被移除，殘留量僅佔膜重1~2%。熱性質方面，由TGA與DSC分析可知隨著TiO2的添加，薄膜熱穩定性隨之提升，最大裂解溫度可提升約5C，玻璃轉換溫度約提升10C。將薄膜進行BSA過濾時，發現P0及P1.5系列之移除率皆可達99%，而P5只有約93%，至於純水通量及回復率則隨著TiO2的添加呈現先增後降趨勢，原因是TiO2可提高表面親水性，進而減少BSA和薄膜表面的疏水性吸附，但過量添加會導致TiO2團聚而降低其效能。利用PEG測試薄膜之截留分子量，發現P0系列約為270~350 kDa、P1.5系列約為325~510 kDa、P5系列約為450~850 kDa，此現象與純水通量以及孔洞大小數據互相呼應。

In this research, we introduce TiO2 sol (synthesized via the sol-gel procedure) and polyvinylpyrrolidone (PVP) into the casting dope for polyethersulfone (PES)/TiO2 composite membrane formation. The former additive is used to enhance the hydrophilicity, whereas the latter functions as a pore former to engender pore-pore interconnection. Prepared membranes (termed mixed matrix membrane, MMM) can be divided into 3 series: P0, P1.5 and P5, according to the amount of added PVP. Each series consists of several membranes with TiO2 contents. To disperse TiO2 finely (on the scale of 2-3 nm) in the casting dope, the sol-gel process incorporates DMAc as the solvent, same as that used for preparation of the casting dopes. All membranes show the asymmetric structure with a dense surface (skin) and a porous cross section composed of finger-liked macrovoids and large irregular macrovoids. With the increase of added PVP, the pores on the top and bottom surfaces increase, resulting in an increase of the pure water flux, while the irregular large macrovoids gradually transform into finger-liked macrovoids. Changing the amount of added TiO2, the surface pore size of the membrane is found to increase first and then decrease; the pure water flux follows the same trend. The porosity of the membrane is about 80-88%, and the contact angle of the top surface gradually decreases with the addition of TiO2. The tensile strength decreases 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 first and then decreases with the addition of TiO2. The amount of PVP resided in the membrane has been determined by NMR analysis. The results show that about 90% of the PVP is removed during the membrane formation process and the residual amount only accounts for 1-2% of the membrane weight. Thermal properties based on TGA and DSC analysis show that the thermal stability of the membrane increases with the TiO2 content: an increase of 5C on the maximum thermal degradation temperature and 10C of the glass transition temperature. The BSA filtration experiments show that the rejection ratio of the P0 and P1.5 series are both 99% and yet it is only about 93% for the P5 series. As to the pure water flux and the recovery ratio, both increase first and then decrease with the TiO2 content. The reason is that TiO2 can increase the hydrophilicity of the membrane surface and thus reduces the hydrophobic adsorption of BSA on the surface. However, excessive amount of TiO2 can cause agglomeration of TiO2, which in turn lead to decrease of its antifouling efficiency. PEG is used to determine the molecular weight cut-off (MWCO) of the membranes. For the P0 series, the MWCO is about 270-350 kDa, for the P1.5 series, it is about 325-510 kDa, and for the P5 series, it is about 450-850 kDa. These results are consistent with the pure water flux and the pore size data.

目錄
致謝 I
論文提要內容 Ⅱ
Abstract IV
目錄 VI
圖目錄 VIII
表目錄 XI
一 序論 1
1.1 前言 1
1.2 奈米TiO2溶膠的合成 3
1.3 PES/TiO2有機無機複合薄膜 5
1.4 PES/無機粒子複合薄膜文獻回顧 7
1.5 UF與薄膜結垢 8
二 實驗 10
2.1 實驗藥品 10
2.2 實驗步驟 12
2.2.1 奈米二氧化鈦粒子之合成 12
2.2.2 浸漬沉澱法製備PES/TiO2複合薄膜 15
2.2.3 TiO2溶膠及薄膜之物性分析 17
2.2.4 純水通量、超過濾、截留分子量及抗垢測試 21
三 結果與討論 29
3.1 奈米二氧化鈦溶膠的合成與結構鑑定 29
3.1.1 奈米二氧化鈦粒徑分析與鑑定 29
3.1.2 傅氏紅外線吸收光譜(FTIR)之鑑定與分析 31
3.2 PES/TiO2複合薄膜之製備與物性分析 34
3.2.1 SEM structure & EDS 34
3.2.2 PES/TiO2複合薄膜之製備與物性分析 51
3.2.3 成孔劑PVP的殘留 55
3.2.4 薄膜拉伸測試 61
3.2.5 添加TiO2奈米粒子對PES薄膜熱性質的影響 65
3.2.6 純水通量測試 72
3.3 薄膜BSA抗垢能力檢測 77
3.4 薄膜截留分子量測試 89
四 結論 93
五 參考文獻 95
附錄A SEM 104
附錄B PMI測試 110

圖目錄
圖1-1 恆溫浸漬沉澱法與三成份相圖關係 6
圖1-2 成膜路徑及溶劑-非溶劑擴散路徑圖 7
圖2-1 合成奈米二氧化鈦之實驗流程 12
圖2-2 不同重量百分濃度的DMAc-C4H9OH溶液折射率檢量線 14
圖2-3 製備PES/TiO2薄膜之流程 15
圖2-4 以HPLC測試分子量5萬PEG Standard 22
圖2-5 以HPLC測試分子量11萬PEG Standard 23
圖2-6 以HPLC測試分子量27萬PEG Standard 24
圖2-7 以HPLC測試分子量53萬PEG Standard 25
圖2-8 以HPLC測試分子量100萬PEG Standard 26
圖2-9 不同濃度牛血清白蛋白(BSA)之UV吸收度檢量線 28
圖3-1 溶膠中奈米二氧化鈦粒子大小隨反應時間變化圖 30
圖3-2 溶膠中奈米二氧化鈦之粒徑分佈 30
圖3-3 TBOT/DMAc溶液之FTIR圖譜 31
圖3-4 TBOT+DMAc水解縮合及減壓濃縮前後FTIR圖譜 32
圖3-5 未添加PVP之薄膜上表面SEM影像圖 37
圖3-6 未添加PVP之薄膜下表面SEM影像圖 38
圖3-7 未添加PVP之薄膜截面SEM影像圖 39
圖3-8 未添加PVP之薄膜截面EDS元素分析圖 40
圖3-9 添加1.5wt% PVP之薄膜上表面SEM影像圖 42
圖3-10 添加1.5 wt% PVP之薄膜下表面SEM影像圖 43
圖3-11 添加1.5 wt% PVP之薄膜截面SEM影像圖 44
圖3-12 添加1.5 wt%之PVP薄膜截面EDS元素分析圖 45
圖3-13 添加5 wt% PVP之薄膜上表面SEM影像圖 47
圖3-14 添加5 wt% PVP之薄膜下表面SEM影像圖 48
圖3-15 添加5 wt% PVP之薄膜截面SEM影像圖 49
圖3-16 添加5 wt%之PVP薄膜截面EDS元素分析圖 50
圖3-17 聚醚碸PES (a)與聚乙烯吡咯烷酮PVP (b)之H-NMR光譜圖 56
圖3-18 P1.5系列薄膜之H-NMR光譜圖(a) P1.5T0, (b) P1.5T4, (c) P1.5T8. 58
圖3-19 P5系列薄膜之H-NMR光譜圖 (a) P5T0, (b) P5T4, (c) P5T8 60
圖3-20 不同比例PVP之薄膜厚度對TiO2含量作圖 63
圖3-21 不同比例PVP之薄膜拉伸強度對TiO2含量作圖 64
圖3-22 不同比例PVP之薄膜斷裂伸長率對TiO2含量作圖 64
圖3-23 P0系列薄膜之熱重分析圖 66
圖3-24 PVP K-30之熱重分析圖 67
圖3-25 P1.5系列薄膜之熱重分析圖 68
圖3-26 P5系列薄膜之熱重分析圖 69
圖3-27 P5系列薄膜之DSC熱分析掃描圖，DSC一次升溫圖，升溫速率為10C/min 71
圖3-28 P0系列薄膜之薄膜純水通量 73
圖3-29 P1.5系列薄膜之薄膜純水通量 74
圖3 30 P5系列薄膜之薄膜純水通量 75
圖3-31 BSA過濾示意圖 (a) 適量TiO2 , (b) 過量TiO2 80
圖3-32 未添加PVP之薄膜BSA過濾通量隨時間變化圖 87
圖3-33 添加1.5 wt% PVP之薄膜BSA過濾通量隨時間變化圖 88
圖3-34 添加5 wt% PVP之薄膜BSA過濾通量隨時間變化圖 88
圖3-35 各系列薄膜之截留分子量與水通量對PEG分子量作圖 92
圖A-1 P0系列之薄膜截面SEM放大影像圖 104
圖A-2 P1.5系列之薄膜截面SEM放大影像圖 105
圖A-3 P5系列之薄膜截面SEM放大影像圖 106
圖A-4 未添加PVP之薄膜上表面EDS元素分析圖 107
圖A-5 添加1.5 wt%之PVP薄膜上表面EDS元素分析圖 108
圖A-6 添加5 wt%之PVP薄膜上表面EDS元素分析圖 109
圖B-1 P1.5T0薄膜之氣體流量對壓力作圖 110
圖B-2 P1.5T0薄膜之累積氣體流量對孔徑作圖 110
圖B-3 P1.5T0薄膜之孔徑分佈圖 111
圖B-4 P1.5T0薄膜之孔徑分佈對平均孔徑作圖 111
圖B-5 P1.5T2薄膜之氣體流量對壓力作圖 112
圖B-6 P1.5T2薄膜之累積氣體流量對孔徑作圖 112
圖B-7 P1.5T2薄膜之孔徑分佈圖 113
圖B-8 P1.5T2薄膜之孔徑分佈對平均孔徑作圖 113
圖B-9 P1.5T4薄膜之氣體流量對壓力作圖 114
圖B-10 P1.5T4薄膜之累積氣體流量對孔徑作圖 114
圖B-11 P1.5T4薄膜之孔徑分佈圖 115
圖B-12 P1.5T4薄膜之孔徑分佈對平均孔徑作圖 115
圖B-13 P1.5T6薄膜之氣體流量對壓力作圖 116
圖B-14 P1.5T6薄膜之累積氣體流量對孔徑作圖 116
圖B-15 P1.5T6薄膜之孔徑分佈圖 117
圖B-16 P1.5T6薄膜之孔徑分佈對平均孔徑作圖 117
圖B-17 P1.5T8薄膜之氣體流量對壓力作圖 118
圖B-18 P1.5T8薄膜之累積氣體流量對孔徑作圖 118
圖B-19 P1.5T8薄膜之孔徑分佈圖 119
圖B-20 P1.5T8薄膜之孔徑分佈對平均孔徑作圖 119

表目錄
表2-1 合成奈米二氧化鈦之反應物莫耳組成 12
表2-2 減壓濃縮前後奈米二氧化鈦溶膠之莫耳組成 13
表2-3 製備PES/TiO2複合薄膜之製膜液組成 16
表3-1 TBOT及DMAc其FTIR吸收峰位置 32
表3-2 由Image J分析SEM圖量測pore size (nm) 34
表3-3 P0系列薄膜之厚度、接觸角、孔隙度、孔洞尺寸及製膜液黏度…52
表3-4 P1.5系列薄膜厚度、接觸角、孔隙度、孔洞尺寸及製膜液黏度 53
表3-5 P5系列薄膜厚度、孔隙度、孔洞尺寸及製膜液黏度 54
表3-6 PVP在PES/TiO2複合薄膜中由NMR計算殘留率和萃取率 55
表3-7 P0系列薄膜之抗張強度與伸長率 62
表3-8 P1.5系列薄膜之抗張強度與伸長率 62
表3-9 P5系列薄膜之抗張強度與伸長率 63
表3-10 P0系列薄膜之熱重分析數據 66
表3-11 P1.5系列薄膜之熱重分析數據 69
表3-12 P5系列薄膜之熱重分析及玻璃轉移溫度數據 70
表3-13 P0系列薄膜之純水通量(L/m2h) 73
表3-14 P1.5系列薄膜之薄膜純水通量(L/m2h) 74
表3-15 P5系列薄膜之薄膜純水通量(L/m2h) 75
表3-16 Guerout–Elford–Ferry equation計算薄膜表面平均孔徑dm (m) 76
表3-17 P0系列薄膜BSA過濾之回復率及移除率 81
表3-18 P1.5系列薄膜BSA過濾之回復率及移除率 82
表3-19 P5系列薄膜BSA過濾之回復率及移除率 83
表3-20 P0系列薄膜BSA過濾阻力 84
表3-21 P1.5系列薄膜BSA過濾阻力 85
表3-22 P5系列薄膜BSA過濾阻力 86
表3-23 各系列薄膜截留率線與R = 90% 線交點之PEG截留分子量 (kDa) 90
表3-24 各系列薄膜截留分子量計算表面孔洞大小 (nm) 90

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