臺灣博碩士論文加值系統

本研究採用溶膠-凝膠法製備Novolac Penolic Resin/SiO2有機/無機混成奈米複合材料，並探討其在物性與化性之間所造成的影響及差別。
本研究利用偶合劑改善有機相與無機相之相分離情形。其中的共價鍵結係由偶合劑和樹脂反應所形成，可由FT-IR鑑定出其結構。由29Si Solid-state NMR所鑑定出矽氧烷所形成之無機網狀交聯的幾何結構主要皆為四取代(Q4)及三取代(T3)居多(其各取代之定義為氧烷基完全水解縮合變成Si－O－Si的結構之數目)。在形態學之研究係利用SEM所觀察到改質過後之系統的無機粒子為100nm以下。經由穿透度的測試，其材料可呈現接近純酚醛樹脂的透明性。
經由TGA、DMA的測試分析，混成複合材料在熱性質方面有明顯的改善，而在機械性質、燃燒性質及透光度測試等方面也都有顯著的不同，其中以改質過後的有機/無機混成奈米複合材料性質為最佳。5wt%的熱重損失溫度由281℃提昇至350℃左右，玻璃轉化溫度由202℃提高到了230℃，表現出優異的熱穩定性。另外，在機械性質方面，其抗折強度測試約提昇了6~30%左右、抗折模數也增加至100%。在L.O.I.的測試中發現此奈米複合材料其L.O.I.值為37，已達耐燃材料標準；在U.L. 94耐燃性質測試結果顯示材料為94V-0的等級，顯示此奈米複合材料具有極佳的耐燃性質。

The preparation of the phenolic resin/silica hybrid organic-inorganic nanocomposite is via sol-gel process. The coupling agent was used to improve the interface between organic and inorganic phase. Effects of nanocomposite structure on the physical and chemical properties were discussed.
The reaction of coupling agent and resin forms covalent bonds. The structure of the covalent bonds was identified by Fourier-transform infrared (FT-IR) spectroscope. The silica network was characterized by solid-state 29Si nuclear magnetic resonance (29Si solid-state NMR). Results revealed that Q4 (tetra-substituted siloxane bond) and T3 (tri-substituted siloxane bond) are the major microstructures. The size of silica particle in the phenolic resin was characterized by scanning electron microscope (SEM). The particle size of inorganic silica in the modified-system is less than 100 nm. The hybrid nanocomposites exhibits excellent transparence.
Thermal properties and mechanical properties show significant difference between the conventional composite and nanocomposite. The modified hybrid composite exhibits promising thermal properties. The 5% weight loss temperature increased from 281℃ to 350℃. The flexural strength increased by 6~30%. The L.O.I. of the nanocomposite can reach 35 and the U.L. value is 94V-0. Hence, the materials possess excellent flame-retardant properties.

第一章、緒論………………………………………………………………1
第二章、理論基礎與文獻回顧……………………………………………4
2-1 酚醛樹脂之製備與特性………....………………………………...4
2-1-1 Novolac type 酚醛樹脂之製備與特性……………………4
2-1-2 Resole type 酚醛樹脂之製備與特性……………………...8
2-1-3 酚醛樹脂之性質……………………..……………..……..10
2-2 溶膠-凝膠法……..……..……..…………………………………..12
2-2-1 溶膠-凝膠技術之簡介…………...………...……………..12
2-2-2 反應機構與影響反應的因素…………………………..…16
2-2-3 溶膠-凝膠技術之歷史發展及應用………………..……..20
2-3 有機/無機混成材料………………………………………………24
2-3-1 有機/無機混成材料之簡介…………..…………………..24
2-3-2 有機/無機混成材料之特性與實例…………………....…28
2-4 熱裂解動力學理論基礎………………………………………….31
2-5 相關研究文獻……………………………………..……………...37
2-4-1 以溶膠-凝膠製備有機/無機混成材料之相關研究……...37
2-4-2 以溶膠-凝膠製備Phenolic Resin/SiO2之有機/無機混成材料之相關研究…………………………………………….50
第三章、研究目的與內容………………………………………………...54
3-1 研究目的…………………………………………………………54
3-2 研究內容…………………………………………………………56
第四章、實驗方法………………………………………………………...58
4-1 實驗藥品………………………………………………………….58
4-2 實驗儀器設備…………………………………………………….60
4-3 實驗流程………………………………………………………….52
4-4 實驗步驟………………………………………………………….63
4-4-1 改質酚醛基材之前趨物製備…………………………….63
4-4-2 酚醛樹脂/二氧化矽之有機/無機混成材料之製備……...64
4-5 測試方法………………………………………………………….69
第五章、研究成果與討論………………………………………………73
5-1 FT-IR結構鑑定…………………………………………………...73
5-2 29Si Solid NMR結構鑑定…………………………………………77
5-3 奈米複合材料微結構之形態學研究…………………………….86
5-4 熱性質分析……………………………………………………….94
5-4-1 TGA………………………………………………………..94
5-4-2 裂解動力學分析………………………………………….99
5-4-3 DMA……………………………………………………...108
5-5 燃燒性質分析…………………………………………………....112
5-5-1 L.O.I.測試………………………………………………...112
5-5-2 U.L.測試………………………………………………….113
5-6 機械性質分析……………………………………………………115
5-6-1 抗折強度與抗折模數測試結果分析…………………...115
5-7透光率測試…………..…………………………………………...120
第六章、研究結論…………………………………………………….…124
第七章、參考文獻…………………………………………………….…127

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