臺灣博碩士論文加值系統

　　近年來，電子元件的散熱問題在3C產業中引起相當大的重視，在高分子材料中，液晶環氧樹脂已經獲得相當大的關注，因為其優異性能，如高機械性質、高耐熱性及低熱膨脹係數等特性，但其導熱係數仍然受到限制；因此本研究主要製備導熱複合材料來改善材料的導熱率並探討其熱性質。
　　研究分成兩部分：第一部分合成酮基團液晶環氧樹脂 (LCE)，並利用FTIR、1H-NMR及MS鑑定其結構。利用DSC及POM分析LCE的液晶相範圍及液晶型態。由DSC顯示LCE的液晶相範圍為升溫過程在125oC~135oC之間；利用POM在液晶相範圍可觀察到馬爾他十字 (Maltese Cross)之液晶相，其結果與DSC曲線相符合。使用硬化劑DDM及DDS以DSC來探討LCE之硬化反應，結果顯示DDM系統之起始硬化速率比DDS系統快；在硬化過程中，利用POM觀察DDM系統有雙折射現象而DDS系統卻沒有；利用DSC在非恆溫條件下探討其硬化動力學，並使用Kissinger和Ozawa法來計算活化能 (Ea)，其結果顯示DDS系統高於DDM系統。第二部分是將自行合成的LCE做為基材，添加不同比例之奈米碳管 (CNT)做為填充材料，經熱硬化來製備LCE/CNT複合材料。利用SEM觀察複合材料之形態，以TGA、TMA及Hot-disk探討複合材料之熱性質。由SEM結果顯示，隨著CNT含量增加，且均勻的分散於LCE中；由TMA結果顯示，其玻璃轉移溫度 (Tg)隨著CNT添加量增加而增加，而熱膨脹係數 (CTE)則會隨之下降。TGA及Hot-disk結果顯示，其熱穩定性、焦碳殘餘率及熱傳導係數都隨著導熱填充材料的增加而增加，其熱穩定性可達到400oC。

　　In recent years, heat dissipation of electronic component problems caused considerable attention in the 3C industry. In polymer materials, liquid crystalline epoxy resin is in the limelight because of many peculiar properties such as excellent mechanical, high heat resistance and low coefficients of thermal expansion, but its thermal conductivity is still restricted. Therefore, the purpose of this research, we will focus on the preparation of thermal conductive composite to improve the thermal conductivity and research its thermal properties.
This research is mainly divided into two parts: First, the liquid crystalline epoxy resin with Ketone mesogen (LCE) was synthesized and its chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H-NMR) and mass spectroscopy (MS). The liquid crystal mesophase range and liquid crystal phase were characterized by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The DSC result showed that the liquid crystal mesophase range of LCE is at 125oC~135oC on heating process. The liquid crystal phase of Maltese cross was observed during liquid crystal mesophase range by POM, the result was consistent with the DSC curve. The curing reaction of LCE was monitored that using diaminodiphenylmethane (DDM) and diaminodiphenylsulfone (DDS) as curing agent by DSC. The results showed that the curing reaction of DDM system proceeded faster than DDS system in the initial stage of the curing reaction. Birefringence with DDM system was observed during curing processes by POM, but the DDS system didn’t. The cured kinetic studies by DSC non-isothermal conditions and the activation energy (Ea) are calculated according to the models of Kissinger and Ozawa. The results showed that the Ea of DDS system was higher than DDM system. In the second part, we use the composites of LCE with different ratios of carbon nanotube to prepare LCE/CNT composites. The morphology of LCE/CNT composites was characterized by field emission scanning electron microscopy (SEM), and the thermal properties of LCE/CNT composites were characterized by thermal gravimetric analysis (TGA), thermal mechanical analyzer (TMA) and Hot-disk. The SEM results showed that more CNT was added, the better dispersion was in the LCE. The TMA results showed that the glass transition temperature (Tg) was increased and the coefficient of thermal expansion (CTE) of LCE/CNT composites was decreased significantly with the addition of CNT. TGA and Hot-disk results showed that the thermal stability, char yield and thermal conductivity were increased by filler contents, and its thermal stability stand up to 400oC.

目錄
中文摘要 i
Abstract iii
誌謝 v
目錄 vi
Scheme viii
表目錄 ix
圖目錄 x
第一章 緒論 1
1-1 前言 1
1-2 導熱複合材料之現況及發展 2
1-3 研究目的 3
第二章 文獻回顧 4
2-1 液晶簡介 4
2-1-1 液晶起源 5
2-1-2 液晶的種類 7
2-1-3 液晶分子的結構 13
2-2 環氧樹脂簡介 14
2-3 硬化劑簡介 15
2-4 液晶環氧樹脂簡介 19
2-5 液晶高分子簡介 20
2-6 導熱複合材料 39
2-6-1 熱傳導理論 39
2-6-2 導熱機制 39
2-6-3 複合材料 40
2-6-4 奈米碳管 41
2-6-5 導熱高分子複合材料 42
第三章 實驗 45
3-1 實驗流程圖 45
3-2 材料與藥品 46
3-3 實驗裝置圖 47
3-4 儀器設備 50
3-5 實驗步驟 52
3-5-1 p-glycidyloxybenzaldehyde (ER)之合成 52
3-5-2 Liquid crystalline epoxy resin (LCE)之合成 53
3-5-3 奈米碳管之酸化改質 55
3-5-4 LCE/CNT複合材料之製備及熱硬化 56
3-6 結構鑑定與物性測試 57
第四章 結果與討論 60
4-1 LCE之合成鑑定 60
4-2 奈米碳管之表面改質鑑定 63
4-3 液晶形態之探討 65
4-3-1 DSC液晶相範圍探討 65
4-3-2 POM液晶相觀察 66
4-4 熱硬化之探討 68
4-5 硬化動力學參數探討 71
4-6 LCE/DDM及LCE/DDS之熱性質探討 78
4-7 LCE/CNT複合材料之探討 80
4-7-1 SEM形態觀察 80
4-7-2 LCE/CNT複合材料之液晶相觀察 82
4-7-3 Hot-Disk熱傳導係數分析 84
4-7-4 TGA熱穩定性分析 86
4-7-5 TMA熱機械性質分析 88
第五章 結論 90
參考文獻 92

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