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研究生: 王存德
Wang, Tsun-Te
論文名稱: 聚(N-乙烯甲醯胺)奈米纖維之製備及纖維內分子位向性之研究
Preparation of Poly(N-vinylformamide) Nanofibers and Study of Molecular Orientation in the Fibers
指導教授: 侯聖澍
Hou, Sheng-Shu
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2010
畢業學年度: 98
語文別: 中文
論文頁數: 105
中文關鍵詞: 聚(N-乙烯甲醯胺)分子位向性順向性纖維偏光鏡
外文關鍵詞: Poly(N-vinylformamide), molecular orientation, aligned nanofiber, polarized FTIR
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  • 本研究中以自由基水相聚合法製備出高分子聚(N-乙烯甲醯胺),為無毒性、生物可相容性且易親水性之高分子,可被應用於生醫領域。電紡絲中PNVF/H2O系統容易使纖維互相溶解在一起,而PNVF/H2O/EtOH系統則改善溶液性質,利用OM及SEM研究溶液性質與操作參數對纖維型態與平均直徑的影響,並觀察到在電壓變因中可製備出97 ± 21 nm之纖維,在流速變因中發現隨流速增快其纖維平均直徑有一極限值存在,而工作距離變因下得知距離拉愈遠其纖維平均直徑有下降的趨勢。
    此外,藉由電場誘導製備出平行排列的順向性纖維,利用polarized FTIR對等方性及順向性纖維作分析,以及程式PeakFit對圖譜中C=O與N-H之吸收峰進行波峰拆解,研究光偏振方向與纖維拉伸軸向之間夾角分別為 0o及90o時與分子位向性的關係,並且發現誘導電場促使纖維內分子鏈沿著拉伸軸向而排列,造成C-N於90o下trans-對cis-之波鋒積分面積比值為5.55;而且,於0o時幾乎所有的官能基之波峰強度皆大於90o下的值;並且在結果中得知0o時hydrogen C=O對free C=O之波峰積分面積比值為7.76,而hydrogen N-H對free N-H之波峰積分面積比值於0o及90o分別為5.16及5.28。

    In the present study, we have synthesized poly(N-vinylformamide) via free radical polymerization in aqueous phase. The polymer is a non-toxic, biocompatible, and hydrophilic for applying in biomedical field. In electrospinning, the PNVF/H2O system leads to form junctions due to solvent easily. For preventing the results, the PNVF/H2O/EtOH system was prepared for improving the solution parameters. The factors that affect the fiber morphology and average diameter such as the solution parameters and the processing conditions have been investigated. In the effect of voltage, we found the fiber average diameter is 97 ± 21 nm at 15 kV. There’s a limit for diameter as increased flowrate. The average diameter of fibers reduced as the distance increasing.
    Besides, the aligned nanofibers were prepared by electric field inducing, and we study the isotropic nanofibers and the aligned nanofibers through polarized FTIR. We also deconvolve the peaks of C=O and N-H by using PeakFit. We study the relationship between the molecular orientation and the angles such as 0o and 90o which are between the polarization vector of infrared radiation and the draw direction of fibers. The chains in fibers orientate along the draw direction of fibers have been investigated, and this results to the peak area ratio of C-N trans- to C-N cis- at 90o is 5.55. Moreover, the peak intensities of almost functional groups at 0o are larger than that at 90o. Finally, we discover the peak area ratio of hydrogen-bonded C=O to free C=O at 0o is 7.76, and the ratios of hydrogen-bonded N-H to free N-H at 0o and 90o are 5.16 and 5.28.

    中文摘要 I 英文摘要 II 誌謝 III 總目錄 IV 表目錄 VII 圖目錄 IX 第一章、緒論 1 1-1 奈米科技與奈米纖維 1 1-2 研究動機與目的 3 第二章、文獻回顧 5 2-1 奈米纖維 5 2-2 製備奈米纖維之方法 6 2-2.1 拉移法 (Drawing) 8 2-2.2 模板合成法 (Template synthesis) 9 2-2.3 相分離法 (Phase separation) 10 2-2.4 自組裝法 (Self-assembly) 11 2-2.5 電紡絲 (Electrospinning) 11 2-3 電紡絲原理 12 2-4 影響電紡絲之因素 13 2-4.1 溶液性質 13 2-4.1.1 分子量與溶液黏度 13 2-4.1.2 溶液表面張力 14 2-4.1.3 溶液導電度 16 2-4.1.4 溶劑介電效應 18 2-4.2 操作參數 19 2-4.2.1 施加電壓 19 2-4.2.2 溶液流速 22 2-4.2.3 針頭與收集板間的距離 23 第三章、實驗部份 25 3-1 實驗藥品與儀器設備 25 3-1.1 實驗藥品 25 3-1.2 實驗器材 25 3-1.2.1 非分析用儀器 25 3-1.2.2 分析用儀器 26 3-1.2.3 電紡絲實驗用儀器 27 3-2 實驗製備方法與步驟 28 3-2.1 實驗藥品之純化 28 3-2.1.1 NVF單體純化與減壓蒸餾 28 3-2.1.2 AIBA的純化 28 3-2.2 聚(N-乙烯甲醯胺)之合成與純化 28 3-2.3 PNVF粉末的製備 29 3-2.4 電紡絲實驗用溶液之配製 29 3-2.4.1 配製以水為溶劑之溶液 (PNVF/H2O) 29 3-2.4.2 配製以水與乙醇為混合溶劑之溶液 (PNVF/H2O/EtOH) 29 3-2.5 電紡絲實驗 29 3-2.5.1 等方性纖維之製備 30 3-2.5.2 順向性纖維之製備 30 第四章、結果與討論 31 4-1 PNVF高分子之性質鑑定 31 4-1.1 PNVF組成結構之鑑定 31 4-1.2 PNVF分子量之鑑定 31 4-2 PNVF/H2O系統對各參數的探討 32 4-2.1 溶液黏度 32 4-2.2 溶液表面張力 34 4-2.3 溶液導電度 36 4-2.4 施加電壓 36 4-2.5 溶液流速 38 4-2.6 工作距離 39 4-3 PNVF/H2O/EtOH系統對各參數的探討 41 4-3.1 選擇乙醇作為共同溶劑之原因 41 4-3.2 各H2O/EtOH比例對操作參數與纖維型態的影響 44 4-3.3 各H2O/EtOH比例對纖維平均直徑的影響 50 4-3.3.1 施加電壓 50 4-3.3.2 溶液流速 59 4-3.3.3 工作距離 65 4-4 對電紡纖維內分子位向性之探討 72 4-4.1 PNVF之粉末型態與纖維型態之比較 72 4-4.2 等方性纖維之polarized FTIR分析 74 4-4.3 順向性纖維之polarized FTIR分析 77 4-4.4 拆解峰之分析 (deconvolution) 79 4-4.5 trans-與cis-結構於PNVF各型態中之分析 91 4-4.6 各官能基於纖維型態中分子位向性之討論 94 第五章、結論 99 第六章、參考文獻 101 自述 105

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