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研究生： 施正倫
Shih, Cheng-Lun
論文名稱： 高選擇性隔膜結構的設計與三維列印
Design and 3D Printing of High-Selectivity Semipermeable Membrane Structures
指導教授： 蘇育全
Su, Yu-Chuan
口試委員: 陳宗麟
陳紹文
學位類別： 碩士
Master
系所名稱： 原子科學院 - 工程與系統科學系
Department of Engineering and System Science
論文出版年： 2024
畢業學年度： 113
語文別： 中文
論文頁數： 113
中文關鍵詞： 高選擇性 、隔膜 、三維列印
外文關鍵詞： High-Selectivity, Semipermeable, Membrane
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    • 傳統噴塗法製造的商用防水透氣膜，其滲透反射係數通常較低且製造時間較長，
    本研究運用三維光聚合固化列印技術製造具有較高滲透反射係數的隔膜結構，相比
    傳統噴塗法可更快速成形和降低成本。該隔膜在光聚合固化後為凝膠結構(PEG
    GEL)，固體部分為高分子結構，液體部分為聚氧化乙烯（PEG）和聚丙二醇
    （PPG），通過增加高分子結構中官能基環氧乙烷(EO)的比例和更改凝膠(GEL)中
    液體：聚氧化乙烯（PEG）和聚丙二醇（PPG）彼此之間的比例，在光聚合固化後
    微結構將受到這些比例的影響從而改變其滲透率和選擇性。本研究採用實驗室自組
    光機，使用 405nm波長光源使高分子材料光聚合固化，製作出僅一立方公分的裝置。
    為提升純水滲透速率，重點聚焦於隔膜的化學組成與多孔微結構。透過調整官能基
    環氧乙烷(EO)在高分子材料中所佔比例進而影響隔膜的透水性能，結果顯示，不同
    官能基環氧乙烷(EO)比例可造成 20%的滲透反射係數差異。當配方中液體(PEG 和
    PPG)的比例在 45%至 60%之間時，相較於商用防水透氣膜滲透反射係數提升 1.6 倍，
    滲透反射係數可達 0.26以上；超過 60%時，滲透反射係數下降，顯示當液體含量過
    多會造成相分離導致微結構孔徑過大。反之，當固體材料比例高於 55%時，高分子
    密度增加導致水穿透隔膜速率下降。最後，透過三維列印技術設計並製造了多種腔
    體結構，其中鰭片型腔體透過設計柵欄方式降低腔體厚度並設計鰭片結構增加表面
    積，顯著提升了整體透水速率與運輸效率，經過設計後的總透水表面積為
    356.88mm²，相較於相同體積下的正立方體，表面積提升 13%，透水速率達
    0.08mm³/s，整體運輸速率提升 20%。

    The commercial waterproof breathable membranes manufactured using traditional spray coating methods typically have a lower permeation reflection coefficient and require longer production times. This study employs three-dimensional photopolymerization curing printing technology to produce membrane structures with a higher permeation reflection coefficient, allowing for faster formation and reduced costs compared to traditional spray methods. After photopolymerization curing, the membrane forms a gel structure (PEG GEL), with the solid part consisting of a polymer structure and the liquid part comprising polyethylene glycol (PEG) and polypropylene glycol (PPG). By increasing the proportion of the functional group ethylene oxide (EO) in the polymer structure and adjusting the ratio of liquid PEG to PPG in the gel, the microstructure after photopolymerization curing will be affected by these proportions, thereby altering its permeability and selectivity.
    This study utilized a self-assembled laboratory optical machine with a 405 nm light source to photopolymerize and cure polymer materials, creating a device as small as one cubic centimeter. To enhance the pure water permeation rate, the focus was on the chemical composition and porous microstructure of the membrane. By adjusting the proportion of the functional group EO in the polymer materials, the membrane's water permeation performance was influenced. Results showed that different EO ratios caused up to a 20% difference in the permeation reflection coefficient. When the liquid (PEG and PPG) ratio in the formula ranged between 45% and 60%, the permeation reflection coefficient increased by 1.6 times compared to commercial waterproof breathable membranes, reaching a coefficient of over 0.26. However, when the liquid content exceeded 60%, the permeation reflection coefficient decreased, indicating that excessive liquid content led to phase separation, resulting in overly large microstructural pore sizes. Conversely, when the solid material ratio exceeded 55%, the increased polymer density caused the water permeation rate through the membrane to decrease.

    摘要 1 Abstract 2 致謝 3 目錄 4 表目錄 8 圖目錄 9 符號目錄 14 第一章、緒論 15 1.1 前言 15 1.2 滲透式驅動裝置 16 1.2.1 水勢能 16 1.2.2 滲透作用原理 17 1.2.3 半透膜 19 1.2.4 半透膜的應用 19 1.3 三維列印 21 1.3.1 三維列印技術介紹 21 1.3.2 光固化三維列印 22 1.3.3 研究動機與目的 24 第二章、文獻回顧 26 2.1 半透膜 26 2.2 光固化樹脂半透膜 27 2.3 薄膜之相分離結構 28 2.3.1 薄膜之非溶劑誘導相分離 28 2.3.2 非擴散誘導相分離 31 2.4 薄膜微結構製備之參數 33 2.4.1 非光固化相(溶劑)種類 33 2.4.2 非光固化相(溶劑)濃度 34 2.4.3 UV強度 35 2.4.4 厚度 36 2.5 多孔聚合物 38 第三章、實驗原理與設計 42 3.1 實驗機台介紹 42 3.1.1 上拉式DLP機台介紹 42 3.1.2 上拉式DLP製造流程 44 3.1.3 其他實驗設備與儀器 45 3.2 實驗材料介紹 46 3.2.1 隔膜單體材料 48 3.2.2 隔膜溶劑材料 54 3.2.3 洗滌材料 55 3.3 測試裝置製造流程 56 3.3.1 容器腔體 56 3.3.2 隔膜支架結構 59 3.3.3 密封墊片 62 3.4 測試裝置整合 63 3.4.1 隔膜與支架之整合 63 3.4.2 隔膜組與容器腔體接合製程 65 3.4.3 滴入高濃溶液 65 3.4.4 塑膠軟管測試之整合 66 3.5 測試機制建立 67 3.5.1 隔膜本身滲透率量測 67 3.5.2 膜阻力K值計算 69 3.5.3 滲透反射係數σ值計算 70 第四章、研究結果與分析 72 4.1 隔膜厚度影響 72 4.2 曝光對隔膜影響 73 4.2.1 曝光強度對隔膜影響 73 4.2.2 曝光劑量對隔膜影響 75 4.3 BPA(30EO)DA、PEG(600)DA、PEGMEA比較 76 4.4 非光固化相比較 78 4.4.1 溶劑PEG200和H2O比較 78 4.4.2 PPG對隔膜結構影響 79 4.5 滲透反射係數σ計算 80 4.5.1 商用透水膜之滲透反射係數σ 81 4.5.2 不同材料之σ 83 4.5.3 類神經網絡計算 84 4.5.4 R1配方之滲透反射係數σ 84 4.5.5 M1配方之滲透反射係數σ 89 4.5.6 S1配方之滲透反射係數σ 92 4.5.7 極限壓力測試 95 4.5.8 微結構對σ影響 96 4.6 疊層技術製造腔體 98 4.6.1 一體成型之腔體 98 4.6.2 四面型腔體 99 4.6.3 九面型腔體 100 4.6.4 鰭片型腔體 101 第五章、結論 102 5.1 隔膜微結構之相分離 102 5.2 隔膜的化學結構 102 5.3 隔膜的分子結構 103 5.4 三維機械結構 106 附錄 107 附錄1 配方R數據 107 附錄2 配方M數據 108 附錄3 配方S 數據 109 參考文獻 110

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