臺灣博碩士論文加值系統

本研究目的在於克服聚醯亞胺(polyimide)與多壁奈米碳管的相容性，因此，以混酸(H2SO4: HNO3 =3:1,vol %)對多壁奈米碳管預先處理做酸化改質，藉由超音波震盪截斷奈米碳管管壁而在表面接上羧酸基，並且使用耦合劑(coupling agent)先與聚醯亞胺之前驅物PAA(Polyamic acid)反應，之後再將含羧酸基之奈米碳管導入以共價鍵結形成Alkoxysilane terminated amic acid/MWNT-COOH之複合材料，再配合旋轉塗佈及階段性熱熟化步驟得到聚醯亞胺-奈米碳管複合薄膜。本研究將奈米碳管導入基材的目的是為了提升聚醯亞胺的導電性與機械性質，並且比較添加未改質及混酸改質四小時與六小時的碳管於聚醯胺酸中的影響。研究中使用傅立葉轉換紅外光譜儀（FTIR）來鑑定其化學結構，熱重損失分析儀（TGA）探討材料的熱穩定性質，萬能試驗機(Universal Test Machine)及鉛筆硬度計(Hardness Pencil Test)觀察其機械性質，掃描式電子顯微鏡（SEM）與穿透式電子顯微鏡(TEM)來觀察材料的表面型態及奈米碳管於基材中的分散性，超絕緣儀(Super Megohmmeter)量測材料的電性。

In this research﹐MWNTs were modified by mix acid(H2SO4:HNO3=3:1,vol%) under sonication for pretreatment to overcome the compatibility between polyimide and carbon nanotubes. The MWNTs were grafted with carboxylic groups on the wall of the tubes. Besides, APrTEOS was introduced as coupling agent. With ethoxysilane group, it can react with precursor of polyimide(PAA), which then combined with modified carbon nantubes(carboxylic group) to form covalent bond. The PI/MWNTs composites were obtained by a spin coating and multi-step thermal curing process.
In this study, the MWNTs were introduced into the matrix in order to increase its electrical and mechanical properties. The effect on PI/MWNTs composite with MWNTs unmodified or acid modified in four or six hours were also discussed. The structure of prepared PI-MWNTs was characterized by Fourier transform infrared (FTIR) spectrometr. The thermal properties, mechanical properties of PI-MWNTs nanocomposite were analyzed by Thermogravimetric analysis (TGA), Universal Test Machine and Hardness Pencil Test. The morphology of PI-MWNTs was observed by scanning electron microscopy (SEM). The dispersion of MWNTs in matrix were observed by transmission electron microscopy(TEM). The electrical property of composite were obtained by Super Megohmmeter.

目錄
中文摘要.................................................i
英文摘要................................................ii
誌謝...................................................iii
目錄....................................................iv
表目錄...................................................v
圖目錄.................................................. vi
第一章 緒論.............................................1
1-1 前言............................................1
1-2 研究動機........................................2
第二章 文獻回顧.........................................3
2-1聚醯亞胺的發展簡介...............................3
2-1-1聚醯亞胺的特性..............................4
2-1-2聚醯亞胺的合成原理..........................5
2-1-3聚醯亞胺的種類..............................6
2-2奈米碳管的簡介..................................13
2-2-1 奈米碳管的構造與特性..................15
2-3 奈米碳管的改質.............................19
2-4 聚醯亞胺-奈米碳管複合材料的簡介與應用......23
第三章 實驗設備與步驟..............................24
3-1實驗藥品....................................24
3-2實驗儀器....................................26
3-3實驗流程....................................27
3-4實驗步驟....................................29
3-5分析試片的製備..............................32
第四章 結果與討論..................................35
4-1 FTIR光譜分析..............................35
4-2 熱重損失分析...............................40
4-3 剖面型態分析...............................44
4-4 機械性質分析...............................55
4-5 導電性質分析...............................61
第五章 結論.........................................65
參考文獻................................................66
表目錄
表 2-1 奈米碳管與其他材料之機械性質比較................18
表 4-1 聚醯胺酸、聚醯亞胺(及添加奈米碳管)、改質碳管的FT-IR特性官能基..............................................37
表 4-2 純PI及添加改質四小時碳管(3wt%~12wt%)膜材的熱裂解溫度......................................................43 表 4-3 PI╱MWNTs奈米複材的拉伸測試數據.................59
表 4-4 不同試片的鉛筆硬度測試...........................60
表 4-5 純PI及PI╱MWNTs奈米複材的電性量測數據............64
圖目錄
圖2-1 醯亞胺基圖示......................................4
圖2-2 聚醯亞胺的反應流程圖..............................5
圖2-3 典型的聚醯亞胺製備方法............................6
圖2-4 由聚異醯亞胺前軀物合成聚醯亞胺....................7
圖2-5 一階段合成反應圖..................................8
圖2-6 PMR15反應圖.......................................9
圖2-7 Kerimide 601反應圖...............................10
圖2-8 Thermid LR-600反應圖.............................10
圖 2-9 碳的同素異形體..................................14
圖2-10 單層奈米碳管結構圖示 (a)armchair(椅狀) (b)zigzag(鋸齒狀) (c)chiral(螺旋狀).................................15
圖2-11 石墨平面上的二個單位向量表示奈米碳管的結構參數圖.16
圖2-12 缺陷位置(Defect-group)官能基化反應圖.............20
圖2-13 共價管壁(Sidewall covalent)官能基化反應圖........22
圖 3-1 多壁奈米碳管的純化與改質流程圖...................27
圖 3-2 PI/奈米碳管薄膜的製備流程圖......................28
圖 3-3 聚醯亞胺(BPDA+p-PDA)的合成反應流程圖.............29
圖 3-4 聚醯亞胺-奈米碳管奈米複合膜的製備流程圖..........31
圖 4-1 FT-IR光譜圖 (a)未改質碳管Umcnt(b)酸化改質六小時碳管M6cnt(c)純聚醯亞胺Pure PI(d)添加改質碳管(3wt%)聚醯亞胺複材.......................................................38
圖 4-2 FT-IR光譜圖 (a)聚醯胺酸-耦合劑(alkoxysilane terminated amide acid,PAA-coupling agent)(b)添加改質碳管(3wt%)聚醯亞胺複材(c)改質六小時碳管......................38
圖 4-3 聚醯亞胺奈米碳管複材的FT-IR光譜圖(a)~(e)依序為純聚醯亞胺及添加未改質碳管(3wt%、6wt%、9wt%、12wy%)..........39
圖 4-4 聚醯亞胺奈米碳管複材的FT-IR光譜圖(a)~(e)依序為純聚醯亞胺及添加改質四小時碳管(3wt%、6wt%、9wt%、12wy%)......39
圖 4-5 純PI及添加未改質碳管(3wt%~12wt%)複材(PIUm03~PIUm12)的TGA曲線圖..............................................42
圖 4-6 純PI及添加改質四小時碳管(3wt%~12wt%)複材(PIM03~PIM12)在氮氣下的TGA曲線圖.........................42
圖 4-7 PI-MWNTs(3wt%)未改質碳管之SEM圖..................46
圖 4-8 PI-MWNTs(6wt%)未改質碳管之SEM圖..................46
圖 4-9 PI-MWNTs(9wt%)未改質碳管之SEM圖.................47
圖 4-10 PI-MWNTs(12wt%)未改質碳管之SEM圖...............47
圖 4-11 PI- mMWNTs(3wt%)改質4hr碳管之SEM圖..............48
圖 4-12 PI- mMWNTs(6wt%)改質4hr碳管之SEM圖..............48
圖 4-13 PI- mMWNTs(9wt%)改質4hr碳管之SEM圖..............49
圖 4-14 PI-mMWNTs(12wt%)改質4hr碳管之SEM圖.............49
圖 4–15 PI-MWNTs(9wt%)未改質碳管之TEM圖。(10K倍) .......50
圖 4–16 PI-MWNTs(9wt%)未改質碳管之TEM圖。(50K倍) .......50
圖 4-17 PI- mMWNTs(3wt%)改質4hr碳管之TEM圖。(10K倍).....51
圖 4-18 PI- mMWNTs(3wt%)改質4hr碳管之TEM圖。(50K倍).....51
圖 4-19 PI-mMWNTs(6 wt %)改質4hr碳管之TEM圖。(10K倍)....52
圖 4-20 PI-mMWNTs(6 wt %)改質4hr碳管之TEM圖。(50K倍)....52
圖 4-21 PI-mMWNTs(9 wt %)改質4hr碳管之TEM圖。(10K倍)....53
圖 4-22 PI-mMWNTs(9 wt%)改質4hr碳管之TEM圖。(50K倍).....53
圖 4-23 PI-mMWNTs(12 wt %)改質4hr碳管之TEM圖。(10K倍)...54
圖 4-24 PI-mMWNTs(12 wt%)改質4hr碳管之TEM圖。(50K倍)....54
圖 4-25 PI/MWNTs奈米複材的抗拉強度曲線圖................57
圖 4-26 PI/MWNTs奈米複材的楊氏係數曲線圖................57
圖 4-27 PI/MWNTs奈米複材的拉伸率曲線圖..................59
圖 4-28 純PI及PI/MWNTs複材的表面電阻圖示................63
圖 4-29 純PI及PI/MWNTs複材的體積電阻圖示................63

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