摘要
本研究以合成與分析聚醯亞胺/二氧化矽薄膜為主要方向，利用二氧化矽經溶凝膠法可以在室溫水解聚合的特性，使聚醯亞胺反應與二氧化矽團成長能同時進行，最後再經熟化(curing)可以得到堅韌的聚醯亞胺/二氧化矽薄膜。
就改變溶凝膠參數而言，首先以FTIR來定性，聚醯亞胺的官能基都有出現，代表在合環過程中不受酸或鹼催化劑、乙醇與二氧化矽粒子所影響，二氧化矽與界面活性劑的官能基吸收峰則因為量太小而無法觀察到。薄膜的透明度則與二氧化矽含量成反比，在低的二氧化矽含量時(少於20%)，薄膜透明度不受pH值影響；在TGA的熱分析當中，添加TEOS對不含界面活性劑的系統熱穩定性提升了10~28℃，pH＝4時最低，而往兩邊遞增。含界面活性劑的系統則在pH＝2∼4之間熱穩定性最佳，而往兩側遞減。利用SEM觀察二氧化矽粒子變化與分佈情形，粒徑整體趨勢在pH＝4時有最大值，而往兩邊遞減。對整體而言，降低二氧化矽粒子的尺寸，使二氧化矽能更均勻分佈在聚醯亞胺之間，更有助於增進熱穩定性。而交流阻抗分析儀則測量各薄膜的介電常數變化，二氧化矽粒子與介電常數大小成正比；增加二氧化矽的量會增加二氧化矽粒子的大小與複合材料的介電常數。
添加界面活性劑(GOPTMS，γ-glycidyloxypropyltrimethoxy
-saline、APTES，3-amino-propyltriethoxysilane)，有助於降低二氧化矽的粒子大小，並使其均勻分佈在聚醯亞胺當中。GOPTMS可以讓二氧化矽的粒子均勻分散與降低粒子尺寸至100 nm左右，而APTES稍差，二氧化矽尺寸在150∼250 nm之間，在熱性質部分則是APTES較佳。

Abstract

A series of polyimide/silica hybrid composites have been synthesized by simultaneous polycondensation of the organic polyimide (PI) phase and the sol-gel reactions (hydrolysis and condensation) of the inorganic silica phase. Sol-gel parameters such as pH value, solvent, water/Si ratio, were systematically varied so that their effect on the microstructure of silica could be explored. Emphasis has been placed on the interactions between the organic and the inorganic phases by FTIR with the introduction of two coupling agents, i.e., g-glycidyloxypropyl- trimethoxysilane (GOPTMS) and 3-amino-propyltriethoxysilane (ATPES). Thermal and electrical properties of the hybrid composites were examined by TGA, DSC, and AC impedance and the morphology by SEM; these properties were correlated to their synthesis chemistry.
FTIR results indicate complete imidization of PI, not affected by the presence of the catalyst, solvent ethanol, and silica particles of the inorganic phase. The hybrid films with lower silica content give higher transparency. TGA results indicate ~ 25 ℃increase of decomposition temperature for the hybrid composites compared to the neat PI; it shows a minimum when pH = 4. The thermal stability of the APTES system is generally better than the GOPTMS system. SEM results indicate that maximum particle size is obtained for the system with pH = 4. AC impedance results indicate that dielectric constant increases with the silica particle size and the silica content. The coupling agents help to reduce the silica particle size (~ 100 nm for GOPTMS, ~ 200 nm for ATPES, and > 400 nm with no coupling agent) and to distribute evenly the silica particles in the PI matrix.

目錄
摘要……………………………………………………………………Ⅰ
Abstract ………………………………… . …………………….….. Ⅱ
目錄……………………………………………………………………Ⅲ
表目錄……………..……………………………………………….... Ⅳ
圖目錄…………………………………………………………...……. Ⅴ
第一章 簡介與文獻回顧
1.1簡介……………………………………………………………..1
1.2聚醯亞胺的合成………………………………………………..1
1.3溶凝膠法………………………………………………………..3
1.4聚醯亞胺/二氧化矽混成材料………………………………….9
1.5研究動機與目的………………………………………… ..….15
第二章 實驗
2.1 凝膠法合成聚醯亞胺與二氧化矽複合材料………………...18
2.2 儀器與分析步驟……..……………………………………….22
第三章 結果
3.1 聚醯亞胺/二氧化矽的合成……..……………………..…….25
3.2 聚醯亞胺/二氧化矽的IR性質……..……………....……….26
3.3 聚醯亞胺/二氧化矽熱性質………..…………………….…..26
3.4 聚醯亞胺/二氧化矽表面型態………..…….………………..40
3.5 聚醯亞胺/二氧化矽介電性質…………….…….….….…….53
第四章 討論
4.1溶凝膠參數對聚醯亞胺熱性質的影響………..………….….58
4.2 界面活性劑對聚醯亞胺/二氧化矽的影響…………..………60
4.3 不同酸鹼值對聚醯亞胺/二氧化矽系統的影響………..……61

第五章 結論與未來工作
5.1 結論………………………………………………………..….63
5.2 未來工作………………………………………..…...………..63
參考文獻……………………..………………………………………..65

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