以溶膠-凝膠法製備聚醯亞胺/奈米級陶瓷混成膜及電性之研究

Electrical Property of Polyimide/Ceramic Hybrid Films Prepared via Sol-Gel Process

陳世信(Shin-Shih Chen)

指導教授 ： 王玉瑞

國立臺北科技大學/工程學院/材料及資源工程系所/碩士(2005年)

摘要

本研究使用有機單體二苯甲酮四羧酸二酐(BTDA) 和二胺基二苯基醚(ODA)先合成聚醯胺酸，再分別製造以四乙氧基矽烷(TEOS)和乙醇所製成之二氧化矽前驅物及四乙氧基鈦鹽(TET)並添加乙醯丙酮作為螯合劑所製成之二氧化鈦前驅物，並採用溶膠-凝膠法以原位(in-situ)合成的方式分別以聚醯胺酸均勻混合以產生水解、縮合反應可以得到聚醯胺酸/奈米二氧化矽和聚醯胺酸/奈米二氧化鈦混合溶液，其中不額外添加水來對金屬烷氧化合物產生水解反應，而是應用聚醯亞酸中的羧酸基與金屬烷氧化合物進行交換反應，產生副產物乙醇，乙醇再與羧酸基酯化反應產生副產物水，再與金屬烷氧化物產生水解/縮合反應。最後階段升溫的方式加熱使其脫水環化，形成聚醯亞胺/奈米二氧化矽混成膜和聚醯亞胺/奈米二氧化鈦混成膜。
研究中主要是探討利用聚醯亞胺與添加兩種不同成分與不同重量百分比的奈米級陶瓷粉體對微觀結構、組成成份、介電性質、絕緣性和熱性質之影響。結果顯示二氧化矽與二氧化鈦粒子均勻的分佈在聚醯亞胺基材內部，粒徑大小都在50~100nm以內，而有機相與無機相之間並沒有相分離現象產生，紅外光譜分析可檢測出除了聚醯亞胺的官能基外，還有二氧化矽與二氧化鈦特性峰生成。當奈米級陶瓷粉體添加量增加，介電常數及熱傳導係數有上升之趨勢，表面電阻會隨著二氧化矽與二氧化鈦粒子添加量增加，而有下降的趨勢。而混成膜之熱重損失測試不會因添加奈米粒子在聚醯亞胺內，而使熱重損失溫度提升。

關鍵字

聚醯亞胺 ； 溶膠-凝膠法 ； 奈米混成材料 ； 金屬烷氧化合物

並列摘要

In this thesis, polyimide/SiO2 hybrid film and polyimide/SiO2 hybrid films were prepared by an nonaqueous sol-gel process. 4, 4-diaminodiphenyl ether (ODA) and 3,3’,4,4’-Benzophenone tetracarboxylic dianhydride (BTDA) were employed to synthesize the polyamic acid. Tetraethoxysilane and ethanol were used as the precursor of silica，titanium ethoxide and acetylacetone were used as the precursor of titania. Acetylacetone was used to reduce the reaction rate and gelation. The hybrid films were obtained by the hydrolysis-polycondensation reaction of tetraethoxysilane and titanium ethoxide in polyamic acid, followd by thermal imidization process.
The cross-sectional SEM images of hybrid films indicate that the particle size increases with the increasing TiO2 or SiO2 content. SEM reveals a uniform dispersion of spherical shaped particles throughout the hybrid films. The mentioned peaks are the characteristic absorption of imide group shown in the FTIR spectra of the entire PI film, PI/TiO2 hybrid and PI/SiO2 films. Besides, the introduction of the SiO2 and TiO2 lead to a broad and strong absorption band in the range of 1100 cm-1and 400 to 850 cm-1, respectively. The study of electrical and thermal properties of the hybrid films indicated the dielectric constant and thermal conductivity increased with the increasing SiO2 and TiO2 content. The decomposition temperature and water adsorption rate of the hybrid films decrease with increasing SiO2 and TiO2content.

並列關鍵字

Polyimide ； non-hydrolytic Sol-gel method ； Hybrid material ； Metal alkoxides

參考文獻

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