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研究生: 李桓安
Huan-An Lee
論文名稱: 以電紡技術開發多功能性微孔陣列薄膜 的研究與應用
Development and application of functional microtube array membranes by the co-axial electrospinning technique.
指導教授: 林震煌
Lin, Cheng-Huang
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 99
中文關鍵詞: 同軸電紡微孔陣列孔雀綠
英文關鍵詞: co-axial electrospinning, MTA, Malachite green
論文種類: 學術論文
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  • 本研究利用同軸-電紡絲法 (co-axial electrospinning) 成功製造出各式功能性微管陣列薄膜 (microtube array membrane),分別應用於層析與光譜。實驗是以聚乳酸或聚碳酸酯的有機溶液,利用 7.5 kV 的高電壓作為驅動力,電噴灑射出多孔洞之中空纖維,並排於收集滾筒上形成微管陣列薄膜。中空纖維管壁的孔洞率可隨實驗條件而加以調控。內徑的大小約20µm,管壁薄約2 µm。
    本實驗發現微孔陣列薄膜具有絕佳的吸附特性,被吸附的有機氣體經快速加溫後而被脫附。配合氣相層析質譜法,可做為高效率且可多次重複使用的吸/脫附材料。以丙酮為例,每 1 mg 的聚乳酸纖維可吸/脫附約 0.15 mg 的丙酮。此外,電紡絲法容易將各種奈米等級的顆粒摻雜在纖維管壁內。
    並且探討不同還原法製成的奈米銀粒子,其中以鹽酸羥胺還原法配製奈米銀效果最佳,並成功將奈米銀溶液紡入微孔陣列薄膜之中。
    以偵測孔雀石綠溶液為例,只需將含有銀粒子的微孔陣列薄膜浸泡於待測樣品溶液中,不需任何額外的前處理步驟,即可直接在顯微鏡式拉曼光譜儀之下直接進行觀測。基於表面增強拉曼效應,可以非常清楚得到孔雀綠的拉曼光譜圖。再者,奈米銀以溶液形態存在時性質較不穩定,但電紡至薄膜纖維時,以固體顆粒的型式存在則可存放較長的時間。

    In this study, we manufacture functional microtube array membrane
    with co-axial electrospinning, were used in chromatography and
    spectroscopy. Experiments were made use of seven thousand five
    hundred volts to create a high voltage electric field as the driving force,
    shooting multi-hole hollow fiber via electrospray and fiber will be
    collected by collecting drum side by side to form microtube array
    membrane. Hollow fiber wall porosity can be regulated with the
    experimental parameters, and the diameter of membrane is about 20 μm,
    the wall thin 2 μm approximately.
    Microtube array membrane has excellent adsorption characteristics,
    the adsorbed organic gases can be quickly desorbed after heating.
    Combine with gas chromatography can be used as high efficiency and
    repeatedly absorption / desorption materials. For example, 1 mg
    polylactic acid fiber can adsorb / desorb about 0.15 mg acetone steam. In
    addition, the electrospinning method is very easy to mix a variety of
    nanoscale particles in the fiber wall.
    At last, we choose Malachite green as the target compound, via the
    microtube array membrane contain with nanosilver particle. We can get a
    very clear spectra of malachite green based on surface-enhanced Raman
    effect. Moreover, nanosilver particle exist in solid type can be stored
    much longer than liquid type.

    中文摘要 ..................................................................................................... I Abstract ...................................................................................................... II 目錄 ................................................................................................... III 圖目錄 ............................................................................................. VII 表目錄 .............................................................................................. IX 第一章 緒論............................................................................................... 1 1-1 研究目的 ..................................................................................... 1 1-2 高分子材料之簡介 ..................................................................... 2 1-2-1 聚乳酸纖維 (polylactic acid, PLA) ................................ 2 1-2-2 聚碳酸酯 (polycarbonate, PC) ....................................... 2 1-2-3 聚乙二醇 .......................................................................... 3 1-3 分析物簡介 ................................................................................. 4 1-3-1 揮發性有機物質 (volatile organic compounds) ............ 4 1-3-2 孔雀石綠 .......................................................................... 5 第二章 分析方法與原理 .......................................................................... 6 2-1 靜電紡絲 ..................................................................................... 6 2-1-1 靜電紡絲簡介 .................................................................. 6 2-1-2 靜電紡絲原理 .................................................................. 7 2-2 靜電紡絲之參數 ......................................................................... 9 2-2-1 高分子溶液: .................................................................. 9 2-2-2 儀器設備: .................................................................... 10 2-3 同軸電紡法 (co-axial electrospinning) .................................... 11 2-4 拉曼散射 ................................................................................... 12 2-4-1 拉曼散射歷史簡介 ........................................................ 12 2-4-2 拉曼散射原理介紹 ........................................................ 14 2-5 表面增強拉曼 ........................................................................... 19 2-5-1 表面增強拉曼歷史簡介 ................................................ 19 2-5-2 表面增強拉曼原理介紹 ................................................ 20 2-6 奈米粒子的特性 ....................................................................... 25 2-7 哨式氣相層析法 ....................................................................... 26 2-7-1 氣相層析法 .................................................................... 26 2-7-2 哨式偵測器感測原理 .................................................... 28 2-8 掃描式電子顯微鏡 (SEM) ...................................................... 30 第三章 儀器藥品與實驗方法 ................................................................ 31 3-1 靜電紡絲儀器 ........................................................................... 31 3-2 薄膜纖維製備 ........................................................................... 33 3-2-1 外管溶液 ........................................................................ 33 3-2-2 內管溶液 ........................................................................ 33 3-2-3 薄膜製作之條件參數 .................................................... 34 3-3 哨式氣相層析裝置 ................................................................... 36 3-3-1 氣相層析儀 .................................................................... 36 3-3-2 哨式偵測器 .................................................................... 37 3-4 高解析拉曼光譜分析儀 ........................................................... 39 3-5 奈米銀膠體溶液 ....................................................................... 40 3-5-1 玻璃容器的清洗 ............................................................ 40 3-5-2 酸液配製方式 ................................................................ 40 3-6 奈米銀還原法分類 ................................................................... 41 3-6-1 鹽酸羥胺還原法 (Leopold and Lendl) ........................ 41 3-6-2 檸檬酸鈉還原法 (Lee and Meisel) .............................. 42 3-6-3 硼氫化納還原法 (Creighton) ....................................... 43 3-7 儀器及周邊設備列表 ............................................................... 44 3-8 實驗藥品列表 ........................................................................... 49 第四章 結果與討論 ................................................................................ 51 4-1 靜電紡絲過程 ........................................................................... 51 4-2 薄膜型態觀察 ........................................................................... 53 4-3 有機氣體之吸脫附 ................................................................... 58 4-3-1 線上吸脫附裝置 ............................................................ 58 4-3-2 進樣體積與頻率變化量之檢量線................................ 61 4-3-3 穩定測試 ........................................................................ 62 4-3-4 系統清潔方法 ................................................................ 64 4-4 吸脫附效果比較 ....................................................................... 65 4-4-1 不同材質之比較 ............................................................ 65 4-4-2 不同孔洞率之比較 ........................................................ 68 4-5 奈米銀溶液配製結果 ............................................................... 70 4-6 不同奈米銀合成法之偵測極限比較 ....................................... 74 4-7 孔雀石綠之拉曼及表面增強拉曼光譜 ................................... 75 4-8 真實樣品檢測 ........................................................................... 78 第五章 結論............................................................................................. 80 學會發表 ................................................................................................... 81 論文發表 ................................................................................................... 82 參考文獻 ................................................................................................... 83 附件:期刊論文

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