本研究旨在綠色意識的環保概念下製備綠色環保型官能基化石墨烯奈米片之難燃材料，並摻入環氧樹脂製備成複合材料。
主要將含矽烷耦合劑(Vinyl-triethoxysilane, VTES)利用自由基反應接枝於石墨烯奈米片表面，之後再將環氧樹脂(Epoxy)基材經矽烷耦合劑(IPTS, 3-Isocyanatoproply-triethoxysilane)接枝改質，接著進行溶膠凝膠反應，形成緻密性的網絡結構，製備官能基化環氧樹脂/石墨奈米片複合材料。藉由高解析電子能譜儀(XPS)利用粗掃圖與細掃圖與FT-IR以及Raman來判定材料的結構鑑定；掃描式(SEM)與穿透式電子顯微鏡(TEM)的形態學來判定材料的型態表徵，觀察石墨奈米片等級與形成複合材料後的燃燒反應；熱重量分析儀(TGA)量測複合材料至高溫後所呈現的重量損失曲線分布，並且透過LOI來觀察複合材料之熱性質與難燃性質。可以發現TGA結果顯示VTES-GNSs隨著含量的增加，使得焦炭殘餘率從13.8wt%(Pure Epoxy)增加到26.2wt%(Epoxy/m-GNSs 10wt%)，有效提升90%，顯示含矽烷改質接枝於石墨烯奈米片有效熱穩定性質。在LOI進行難燃測試，結果顯示從21(Pure Epoxy)增加到27(Epoxy/m-GNSs 10wt%)，顯示改質過後有效提升難燃性質。

In this study, eco-type flame retardant containing functionalized graphene nanosheets was prepared. It was incorporated into epoxy to produce composites.
The coupling agent containing silicon was grafted onto the surface of graphene nanosheets, epoxy was also modified by coupling agent. The functionalized graphene nanosheets were added to the modified epoxy to improve thermal stability through the sol-gel reaction to form functionalized Epoxy/GNSs composites.
VTES-GNSs was characterized by XPS, FT-IR, Raman spectrum to determine structure of the material identification. SEM and TEM were utilized to observe the morphology of GNSs. The thermal stability and flammability of Epoxy/m-GNSs composites were also analyzed by TGA and LOI. Results indicated the char yield increased from 13.8wt% (pure Epoxy) to 26.2wt% (Epoxy/m-GNSs 10wt%), showing an 90% of enhancement. The LOI values from 21 (pure Epoxy) to 27 (Epoxy/m-GNSs 10wt%) achieve flame retardant Level.

摘 要……………………………………………………………………………………………………………………………………I
Abstract………………………………………………………………………………………………………………………II
謝 誌………………………………………………………………………………………………………………………………III
目 錄…………………………………………………………………………………………………………………………………VI
圖目錄…………………………………………………………………………………………………………………………………IX
表目錄……………………………………………………………………………………………………………………………XIII

第一章緒論……………………………………………………………………………………………………………………………1
1-1前言…………………………………………………………………………………………………………………………………1
第二章理論基礎與文獻回顧………………………………………………………………………………………………3
2-1燃燒理論…………………………………………………………………………………………………………………………3
2-1-1燃燒的機制………………………………………………………………………………………………………………3
2-1-2燃燒產生的危害………………………………………………………………………………………………………5
2-1-3高分子的燃燒理論與過程………………………………………………………………………………………9
2-2綠化產品法規概論………………………………………………………………………………………………………12
2-3 難燃劑(Flame retardant)……………………………………………………………………………15
2-3-1難燃劑之概述…………………………………………………………………………………………………………15
2-3-2難燃劑之難燃作用與種類介紹……………………………………………………………………………17
2-4環氧樹脂(Epoxy resin)………………………………………………………………………………………21
2-4-1環氧樹脂發展之概述及應用領域…………………………………………………………………………21
2-4-2環氧樹脂之反應特性………………………………………………………………………………………………21
2-4-3環氧樹脂之種類………………………………………………………………………………………………………24
2-5溶膠凝膠法(sol-gel method)…………………………………………………………………………25
2-5-1溶膠凝膠法之概述…………………………………………………………………………………………………25
2-5-2溶膠凝膠法反應過程……………………………………………………………………………………………28
2-6石墨烯奈米片(Graphene nanosheets, GNSs)………………………………………29
2-6-1 石墨烯奈米片之結構原理與特性概要介紹……………………………………………………29
2-6-2石墨烯奈米片應用在高分子基材之複合材料相關文獻…………………………………32
2-6-3石墨烯奈米片與難燃劑之相關文獻……………………………………………………………………50
第三章研究目的與內容………………………………………………………………………………………………………56
3-1研究目的…………………………………………………………………………………………………………………………56
3-2研究內容…………………………………………………………………………………………………………………………57
第四章實驗方法與步驟………………………………………………………………………………………………………58
4-1實驗藥品…………………………………………………………………………………………………………………………58
4-2實驗儀器…………………………………………………………………………………………………………………………60
4-3實驗流程圖……………………………………………………………………………………………………………………62
4-4實驗步驟…………………………………………………………………………………………………………………………63
4-4-1環氧樹脂/含矽官能基化石墨烯奈米片複合材料之製備(Epoxy/m-GNSs composites)………………………………………………………………………………………………………………………63
4-4-1-1含矽官能基化石墨烯奈米片之合成(VTES-GNSs)……………………………………63
4-4-1-2 環氧樹脂/含矽官能基化石墨烯奈米片之合成(Epoxy/m-GNSs)……64
第五章結果與討論…………………………………………………………………………………………………………………66
5-1 VTES-GNSs鑑定分析………………………………………………………………………………………………66
5-1-1 高解析電子能譜(High resolution X-ray Photoelectron Spectrometer, HR-XPS)……………………………………………………………………………………………66
5-1-2穿透式電子顯微鏡(Transmission Electron Microscopy, TEM) ……………………………………………………………………………………………………………………………………………………69
5-1-3掃描式電子顯微鏡 ( Scanning Electron Microscope, SEM)…70
5-1-4 拉曼光譜( Raman spectrm)………………………………………………………………………73
5-2 IPTS-Epoxy鑑定分析……………………………………………………………………………………………75
5-2-1傅立葉轉換紅外線光譜(fourier transform infrared spectroscopy, FT-IR)……………………………………………………………………………………………75
5-3 Epoxy/m-GNSs複材鑑定分析……………………………………………………………………………76
5-3-1 熱重量分析(Thermgravimetric Analysis, TGA)………………………76
5-3-2積分程序分解溫度(Integral procedure decomposition temperature, IPDT)…………………………………………………………………………………………………79
5-3-3理論值與實驗值………………………………………………………………………………………………………80
5-3-4TG△……………………………………………………………………………………………………………………………81
5-3-5裂解動力學分析………………………………………………………………………………………………………83
5-3-6極限需氧濃度指數(Limited Oxyen Index, LOI)……………………………90
5-3-7 動態機械性質分析(Dynamic Mechanical Analyzer, DMA)……91
5-3-8固態核磁共振光譜儀(Solid state Nuclear Magnetic Resonance spectroscopy, Solid-state 29Si-NMR)………………………………………………………93
5-4焦炭分析(Char analysis)…………………………………………………………………………………95
5-4-1掃描式電子顯微鏡( Scanning Electron Microscope, SEM)……95
5-4-2 能量散射光譜儀(Energy Dispersive Spectrometer, EDS)……98
第六章結論……………………………………………………………………………………………………………………………100
第七章參考文獻……………………………………………………………………………………………………………………103

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