王大銘臺灣大學：化學工程學研究所李宛諭Lee, Wan-YuWan-YuLee2007-11-262018-06-282007-11-262018-06-282007http://ntur.lib.ntu.edu.tw//handle/246246/52278本研究主要工作是以非溶劑誘導相分離法製備高孔隙度膜面結構之探討，製程方法包括濕式法（Wet process）以及蒸氣誘導式法（VIPS process）。選用三種高應用性之材料分別為PEI ( polyetherimide)、PSf ( polysulfone )及CA ( cellulose acetae )；由於所使用之系統或製程中溶劑移除較慢，因此合併速度在薄膜孔洞控制方面極為重要，而本研究則透過添加物或改變溶劑來控制合併行為。 第一部份為濕式法，以乙醇為凝聚劑以避免緻密皮層產生；於PEI/NMP(N-Methyl-Pyrrolidone)系統，可得多孔膜面，孔隙度為30.8%；於PSf/NMP系統中，由於過度成長，膜面轉為緻密，因此透過添加物於鑄模液中，在黏度提升不高時（100cp以下），抑制孔洞合併，孔隙度為35.7%。在CA/NMP系統中，相分離過程表面高分子濃度大幅下降，因而相分離後高分子貧相與富相間的界面張力差異小，此外鑄膜液黏度高於1500cp，抑制孔洞合併，最終膜面孔隙度為46.5%。 第二部份為蒸氣誘導式相分離法，此部份控制不同的VIPS時間，使孔洞成長，再入水固定結構，而達到控制孔洞大小之目的。由於VIPS中溶劑移除較濕式法為慢，因此需設法抑制合併以製備多孔結構。在PEI/NMP系統中相較添加非溶劑GBL(γ-butyrolactone)於鑄膜液中，添加劑2P(2-Pyrrolidinone)較可有效提升黏度(約196cp以上)，此外於PSf系統以2P為溶劑，也可大幅提升黏度(約588cp)，因此抑制合併速度，利於製程上控制孔洞大小。在後續研究中結合VIPS程序再以乙醇為凝聚劑固定結構，最終膜面孔隙度可高達49.6%，且抑制巨型孔洞之生成，並有機會提升薄膜之應用性。The present work was to prepare polymer membranes with highly porous surface structure by non-solvent induced phase separation method, including wet process and vapor induced phase separation. Three highly applied materials, PEI, PSf and CA were chosen. In some systems or during the membrane preparation process, because the solvents were hard to be removed, the coarsening rate was important for controlling the pore size. Therefore the present work was to reduce the coarsening phenomena by additives or changing solvents in the casting solution. In first part, wet process method was used. Ethanol was chosen as coagulant to prevent the formation of dense surface. In PEI/NMP system, a porous surface with 30.8% porosity was obtained. In PSf/NMP system, because of further coarsening a denser surface was obtained. By adding non-solvent in the casting solution, while the viscosity was lower than 100cp, the coarsening phenomenon was reduced and a porous surface with 35.7% porosity was obtained. In CA/NMP system, during phase separation process the polymer concentration on the surface decreased, therefore the interfacial tension between two phases was smaller. Also the viscosity was higher than 1500 cp, as a result a slower coarsening rate and the porosity reached 46.5%. In second part, the vapor induce phase separation method was used. By controlling different VIPS time, the growth of polymer poor phase could be controlled. Then water was chosen as coagulant to solidify the structure to prepare membranes with different pore sizes. Because the solvents were harder to be removed compared the wet process, it would be necessary to reduce the coarsening rate and a micron porous surface membrane could be prepared. In PEI/NMP system, by adding non-solvent 2P, the viscosity increased efficiently ( about 196cp ) compared the casting solution by adding non-solvent GBL. Also in PSf system, 2P was chosen as solvent, the viscosity could increase efficiently ( about 588cp ). Therefore the coarsening rate was slower, and hence it was easier to control the membrane structure. Finally, the method combining the VIPS process and wet process with coagulant ethanol could obtain porous surface approaching 49.6% porosity, suppress the formation of macrovoids, and have chance to improve the application of membranes.致謝 I 摘要 III Abstract V 目錄 VII 圖目錄 IX 表目錄 XIII 縮寫符號說明 XV 第一章、緒論 1 1-1 、薄膜簡介 1 1-2 、成膜方式之介紹 2 1-2-1 、濕式相轉換法(Wet method ) 2 1-2-2 、蒸氣誘導式相分離法 ( Vapor induced phase separation method ) 3 1-2-3 、乾式製程（Dry method） 3 1-2-4 、乾/濕式製程(Dry/Wet method) 3 1-2-5 、熱誘導式相轉換法 (Thermally induced phase separation) 3 1-3 、基礎理論 4 1-3-1 、熱力學 4 1-3-1-1 、液-液相分離(liquid-liquid demixing) 4 1-3-1-2 、膠化（gelation） 5 1-3-1-3 、結晶（crystallization） 5 1-3-2 、動力學 6 1-3-2-1 、質傳動力學 6 1-3-2-2 、質傳動力學-成長及合併(coarsening)行為 8 1-4 、影響薄膜結構及孔洞控制之因素 11 1-5 、製備多孔薄膜及孔洞控制 12 1-6 、PEI、PSf、CA高分子之性質介紹 16 1-7 、研究動機 18 第二章、實驗 19 2-1 、實驗藥品 19 2-2 、實驗儀器 20 2-3 、實驗方法 21 2-3-1 、鑄膜液之配製 21 2-4 、薄膜之製備與觀察 21 2-4-1 、濕式法（wet process） 21 2-4-2 、蒸氣誘導式法（VIPS） 22 2-4-3 、薄膜結構之分析 22 2-4-4 、光學顯微鏡 22 2-4-5 、鑄膜液黏度的量測 23 2-4-6 、凝聚值（CVs）量測 23 第三章、結果與討論 25 3-1 、以乙醇為凝聚劑濕式成膜 26 3-1-1 、PEI多孔薄膜之製備 27 3-1-2 、PSf多孔薄膜之製備 33 3-1-3 、CA多孔薄膜之製備 39 3-2 、以蒸氣誘導式法製膜 47 3-2-1 、VIPS製備多孔PEI薄膜 – 黏度對合併速度之效應 47 3-2-2 、VIPS製備多孔PEI薄膜 – 濃度對合併速度之效應 57 3-2-3 、VIPS法製備多孔PSf薄膜 – 黏度對合併速度的效應 59 3-2-4 、後續濕式法凝聚劑使用乙醇槽之效應 64 第四章、結論 67 參考文獻 69 附錄…………………………………………………………………………………… 735941211 bytesapplication/pdfen-US高孔隙度非溶劑誘導相分離法聚醚醯亞胺聚碸醋酸纖維素合併速度high porositynon-solvent induced phase separation process methodpolyetherimidepolysulfonecellulose acetatecoarsening ratethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/52278/1/ntu-96-R94524022-1.pdf