臺灣博碩士論文加值系統

本研究首先經由有機胺dodecylamine(DOA)及4-phenoxyaniline (POA)和鈉蒙特納石(Na+-mentmorillonite)進行離子交換反應，製成膨潤化的有機黏土(organ clay)。再利用二酸酐(dianhydride)單體和二胺(diamine)單體，製成聚醯胺酸/clay薄膜，最後將聚醯胺酸/clay薄膜在高溫(300℃)環化以形成聚亞醯胺/clay薄膜。經由X-ray繞射分析顯示，DOA-clay和POA-clay添加至5%時，呈脫層型分散，當添加量超過7%時，黏土開始出現聚集或插層分散。TEM分析也顯示添加3%及5% 黏土時，呈奈米分散，但添加7%黏土時，開始呈現聚集的情形。熱機械分析(TMA)指出，聚亞醯胺/clay奈米複合材料的熱膨脹係數隨clay添加量的增加而降低，添加7% DOA-clay時，聚亞醯胺的熱膨脹係數可以降低32%，而添加7% POA-clay時，聚亞醯胺的熱膨脹係數可降低18%，此外，其玻璃轉移溫度則隨clay添加量的增加而上升，添加5% clay時可達到最大值。由熱重量分析(TGA)可以看出添加有機黏土，可以增加聚亞醯胺的熱裂解溫度，添加5% clay時可達到最大值。由聚亞醯胺/clay薄膜試片的機械性質分析可以看出，有機黏土可以增加聚亞醯胺的彈性模數，添加7% DOA-clay的聚亞醯胺其彈性模數增加168%，而添加7% POA clay之聚亞醯胺，其彈性模數增加51%，顯示有機黏土有很好的補強效果，但其伸長率則隨黏土添加量的增加而降低。由介電常數分析顯示，黏土對聚亞醯胺介電常數影響不大，僅略為增加其介電常數。由吸水性實驗可看出添加黏土可降低聚亞醯胺的吸水率，添加5% clay時吸水率可達到最低值。從可見度分析可以看出，添加黏土會降低聚亞醯胺的可見度，但由熱安定性較好的POA-clay所製成的聚亞醯胺/clay薄膜，具有較佳的透光率。另外，由尺寸安定性實驗中可以瞭解，添加黏土可降低聚亞醯胺經熱處理後的尺寸變化。

Polyimide(PI)/clay nanocomposites have been prepared from a PI precursor－poly(amic acid) (PAA) and two different organoclays. The PI precursor was made by a polycondensation reaction between 4,4’-oxydianiline (ODA) and Pyromellitic dianhydride (PMDA). The organoclays were formed by a cation exchange reaction between a Na+-montorillonite clay and an ammonium salt of dodecylamine(DOA) or 4-phenoxyaniline (POA). Both X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses showed that the organoclay was dispersed in PI matrix in a nanosacle. The in-plane coefficient of thermal expansion (CTE) of PI/clay film was decreased with the increasing amounts of organoclay. The CTE of PI/clay film which contained 7 wt % DOA-clay was decreased 32% compared to the pure film and the PI/clay film contained 7 wt % POA-clay was decreased 18% . Both of the glass transition temperatures (Tgs) and the thermal decomposition temperatures of PI/clay films increased with increasing amounts of organoclay. The tensile moduli of PI/clay films were increasing with the increasing amounts of organoclay. The tensile modulus of PI/clay film which contained 7 wt % DOA-clay was increased 168% compared to the pure PI film and the PI/clay film contained 7 wt % POA-clay was increased 51%. The dielectric constants of PI/clay films were slightly increased with the increasing amounts of organoclay. The water absorption of PI/clay film was decreased with the increasing amounts of organoclay. From UV-visible spectra, the PI/POA-clay film showed a batter transparency than the PI/DOA-clay film which could be due to the fact that the POA has a higher thermal stability than DOA. The size stability of PI/clay films after heat treatment was batter than the pure PI film.

摘要..................................................Ⅰ
Abstract .............................................Ⅲ
誌謝..................................................Ⅴ
目錄..................................................Ⅵ
表目錄................................................Ⅹ
圖目錄................................................XI
第一章 緒論............................................1
1-1 前言...............................................1
1-2 研究動機與目的.....................................2
1-3 研究架構...........................................3
第二章 文獻回顧........................................5
2-1 引言...............................................5
2-2 黏土之介紹.........................................7
2-3 聚亞醯胺之介紹....................................10
2-4 黏土/高分子奈米複合材料之介紹.....................14
2-4-1 黏土/高分子奈米複合材料之製備方法...............14
2-4-2 黏土/高分子奈米複合材料之型態...................15
2-4-3 奈米高分子複合材料之特性........................16
2-4-4 奈米高分子複合材料之應用........................17
第三章 實驗方法與步驟.................................22
3-1 實驗材料..........................................22
3-2 實驗儀器..........................................23
3-3 實驗步驟..........................................24
3-3-1 黏土改質........................................24
3-3-2 聚醯胺酸/黏土複合高分子前驅物之合成.............25
3-3-3 聚亞醯胺/黏土奈米複合材料薄膜之製備.............26
3-4 性質測試與分析....................................27
3-4-1聚醯胺酸固有黏度測定.............................27
3-4-2紅外線光譜儀分析(FT-IR)..........................27
3-4-3聚亞醯胺/黏土奈米複合材料之型態分析..............28
3-4-3-1 X-ray繞射分析(XRD)............................28
3-4-3-2 穿透式電子顯微鏡觀察(TEM).....................28
3-4-4熱性質分析.......................................29
3-4-4-1 熱重損失分析(TGA).............................29
3-4-4-2 熱機械分析(TMA)...............................29
3-4-5 可見度測試......................................29
3-4-6 薄膜機械性質分析................................30
3-4-7 尺寸安定性實驗..................................30
3-4-8 吸水性實驗......................................30
3-4-9 介電常數值量測..................................31
第四章 結果與討論.....................................36
4-1 聚醯胺酸及聚亞醯胺之分析..........................36
4-1-1 聚醯胺酸固有黏度測定............................36
4-1-2 傅立葉紅外線光譜之分析..........................36
4-2 有機黏土之分析....................................37
4-2-1 傅立葉紅外線光譜分析............................37
4-2-2 X光繞射分析.....................................37
4-2-3 熱重損失分析....................................39
4-3 聚亞醯胺/黏土奈米複合材料之分析...................40
4-3-1 X光繞射分析.....................................40
4-3-2 穿透式電子顯微鏡之分析..........................41
4-3-3 熱膨脹係數之分析................................42
4-3-4 玻璃轉移溫度之分析..............................43
4-3-5 熱重損失分析....................................44
4-3-6 機械性質分析....................................46
4-3-7 介電常數分析....................................47
4-3-8 吸水性實驗......................................48
4-3-9 可見度分析......................................49
4-3-10尺寸安定性實驗..................................49
第五章 結論...........................................88
參考文獻..............................................91
自述..................................................95
表目錄
表(一) 黏土/聚亞醯胺薄膜之熱膨脹係數..................51
表(二) 黏土/聚亞醯胺薄膜之玻璃轉移溫度................52
表(三) 黏土/聚亞醯胺薄膜之熱裂解溫度..................53
表(四) 黏土/聚亞醯胺薄膜之熱裂解溫度..................54
表(五) 黏土/聚亞醯胺薄膜之機械性質....................55
表(六) 黏土/聚亞醯胺薄膜之介電常數....................56
表(七) 黏土/聚亞醯胺薄膜之吸水率......................57
表(八) 黏土/聚亞醯胺薄膜之透光度......................58
表(九) 黏土/聚亞醯胺薄膜之尺寸安定性..................59
圖目錄
圖2-1 層狀矽酸鹽礦物基本結構單元......................20
圖2-2 黏土/高分子複合材料之分散型態示意圖.............21
圖3-1 實驗步驟流程圖..................................32
圖3-2 黏土改質之流程圖................................33
圖3-3 合成聚亞醯胺/黏土奈米複合材料之流程圖...........34
圖3-4 膨脹型探針及拉伸型探針之示意圖..................35
圖4-1 聚醯胺酸之FTIR 光譜圖...........................60
圖4-2 聚亞醯胺之FTIR 光譜圖...........................61
圖4-3 DOA 改質劑、DOA-Clay、未改質黏土之FTIR 光譜圖...62
圖4-4 POA 改質劑、POA-Clay、未改質黏土之FTIR 光譜圖...63
圖4-5 未改質黏土、DOA-Clay、DOA-Clay 經300℃熱處理、
POA-Clay、POA-Clay 經300℃熱處理後之XRD分析圖.........64
圖4-6 改質劑DOA、POA之熱重損失曲線(in N2) ............65
圖4-7 改質劑DOA、POA之熱重損失曲線(in Air) ...........66
圖4-8 未改質黏土與DOA- Clay、POA-Clay 之熱重損失曲線(in N2)
......................................................67
圖4-9 未改質黏土與DOA- Clay、POA-Clay 之熱重損失曲線(in Air)
......................................................68
圖4-10 不同含量DOA-Clay/聚醯胺酸薄膜之XRD分析圖.......69
圖4-11 不同含量DOA-Clay/聚亞醯胺薄膜之XRD分析圖.......70
圖4-12 不同含量POA-Clay/聚醯胺酸薄膜之XRD分析圖.......71
圖4-13 不同含量POA-Clay/聚亞醯胺薄膜之XRD分析圖.......72
圖4-14 3wt% DOA-Clay/聚亞醯胺薄膜之TEM 圖.............73
圖4-15 3wt% POA-Clay/聚亞醯胺薄膜之TEM 圖.............74
圖4-16 5wt% DOA-Clay/聚亞醯胺薄膜之TEM 圖.............75
圖4-17 5wt% POA-Clay/聚亞醯胺薄膜之TEM 圖.............76
圖4-18 7wt% DOA-Clay/聚亞醯胺薄膜之TEM 圖.............77
圖4-19 7wt% POA-Clay/聚亞醯胺薄膜之TEM 圖.............78
圖4-20 不同含量DOA-Clay/聚亞醯胺薄膜之熱重損失曲線(in N2)
......................................................79
圖4-21 不同含量POA- Clay/聚亞醯胺薄膜之熱重損失曲線(in N2)
......................................................80
圖4-22 不同含量DOA- Clay/聚亞醯胺薄膜之熱重損失曲線(in Air)
......................................................81
圖4-23 不同含量POA- Clay/聚亞醯胺薄膜之熱重損失曲線(in Air)
......................................................82
圖4-24 不同含量DOA-Clay/聚亞醯胺薄膜之UV 光譜分析.....83
圖4-25 不同含量DOA-Clay/聚亞醯胺薄膜之UV 光譜分析.....84
圖4-26 3wt%黏土含量之聚亞醯胺薄膜照片.................85
圖4-27 5wt%黏土含量之聚亞醯胺薄膜照片.................86
圖4-28 7wt%黏土含量之聚亞醯胺薄膜照片.................87

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