本論文以奈米碳管(Multi-wall Carbon nanotubes, CNTs)、奈米石墨烯片(Graphene nanosheets, GNS)、環氧樹脂(Epoxy, EPO)交聯聚氧代氮代苯并環己烷(polybenzoxazine, PBZ)及碳纖維積層板為研究主體，旨在探討奈米高分子複合材料的化學性質、物理性質及機械性質相輔相成的重要性，且藉由材料疊層結構、製程設計及化學改質/ 合成的方法來滿足某些物理性質的需求、並以物理性質研究來延續複合材料的應用性與實用性。研究內容將分為四個主題：
I. 奈米補強填充材的製備方法與鑑定：
在以往的文獻中指出，因應終端應用進而改變奈米碳材的表面特性，並導入高分子複合材料中，材料各項性質也將隨之改變，本研究製備二種不同維度的奈米碳材，分別為奈米碳管及石墨烯，並將其進行表面改質；藉由X-ray diffraction analysis, XRD、X-ray photoelectron spectra ,XPS、Raman spectroscopy…等的量測結果，均顯示成功製備奈米石墨烯片及奈米銀線，並成功將二種不同維度之奈米碳材接枝上MDI的官能基，以利後續奈米複合材料分散性的研究。
II. 應用奈米複合材料製程設計改善奈米填充材分散性之研究：
應用製程工序的改善，以提升奈米碳材對於高分子基材的分散性，並提出一種高性能熱固性高分子複合材料的製程設計方法，結果顯示，應用縮短基材固化時間而提升高黏度時間的特性，抵抗奈米碳材因凡得瓦力互相吸引堆疊，提高奈米複合材料整體的分散性及均質性，並同時添加化學改質後的奈米碳材，有效提升各項綜合機械性能。
III. 奈米複合材料之分散性對於薄膜各項性質之影響：
藉由製程工法定讞最佳的製備程序，成功製備出無缺陷之高分子奈米複合材料之薄膜試片，由於薄膜的高縱橫比及透光的特性，能清楚的在巨觀的狀態下，觀察奈米碳材在高分子基材中整體分散性的優劣，並以應力指標及誤差範圍佐以證明分散性對機械強度及實驗再現性的影響。
IV. 應用不同維度之協同效應改善奈米複合材料之機械性質研究：
實驗結果指出，改質後的奈米碳管及石墨烯混和摻入纖維積層板中，存在著協同效應，相較於添加單一奈米碳材，更能有效補強積層板的性能，在拉伸、彎曲、層間剪切及扭轉疲勞各項性質均有顯著的補強效果，奈米碳材能提升纖維和基材之間的黏著力，致使減少或延緩脫鍵及脫層的情形，讓負載能夠順利傳遞至纖維，使強度及壽命提升。

Herein, the significance of chemical, physical, and mechanical synergies in a variety of nano-polymer composites were investigated. The composites included multi-wall carbon nanotubes (CNTs), graphene nanosheets (GNS), epoxy (EPO) resin cross-linked polybenzoxazine (PBZ), and carbon fiber laminates. In these nano-polymer composites, physical requirements were achieved using laminated structures, process design, and chemical modification/synthesis. The physical properties of the prepared materials were subsequently examined in further detail to extend the applicability and usability of the composite materials. The contents of this study can be divided into four major themes:
I. Preparation and characterization of reinforcing nano-fillers
Previously, it has been demonstrated that changes in the surface characteristics of a nanocarbon material incorporated into a polymer composite for a particular end-use application often alters other composite properties. Herein, we prepared two nanocarbon materials with different dimensionalities (carbon nanotubes and graphene), and subsequently modified their surfaces. The X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), and Raman spectroscopic analyses indicated that nanographene sheets and silver nanowires were successfully prepared. These nano-carbon materials were successfully grafted onto the functional groups of MDI, which facilitated the subsequent study of nanocomposite dispersion.
II. Improving nanocarbon materials dispersibility by optimizing nanocomposite process design
The dispersibility of nano-carbon materials in polymer substrates was enhanced by optimizing the related synthetic processes. Furthermore, a process for producing high-performance thermosetting polymer composites was proposed. Application of the proposed method shortened the substrate curing time, improved the characteristics of the high-viscosity period, prevented nanocarbon stacking due to Van der Waals forces, and enhanced the overall dispersibility and homogeneity of the resulting nanocomposite material. Moreover, addition of the chemically modified nanocarbon materials effectively improved all mechanical properties of the nanocomposite.
III. The effect of nanocomposite dispersibility on film properties
A defect-free nanocomposite polymer film was successfully produced using the optimized preparation procedure obtained via process engineering. Because of the high aspect ratio and transmissivity of the film, the nanocarbon dispersibility in the polymer substrate was clearly observed under macroscopic conditions. The dispersibility effects on the mechanical strength and experimental reproducibility of the composite were subsequently examined via stress index and margin of error analyses.
IV. Enhancing the mechanical properties of the nanocomposites by exploiting synergies between nanocarbon materials with different dimensionalities
The experimental results suggested a synergistic effect between the modified carbon nanotubes and graphene after mixing into the fiber laminate. Compared to the addition of a single nanocarbon material, the addition of both nanocarbon materials more effectively improved the performance of the laminate. Significant improvements were obtained in terms of tensile strength, flexural strength, interlaminar shear strength, and torsional fatigue. The addition of nanocarbon materials also improved the adhesion between the fiber and substrate, thereby reducing or delaying debonding and delamination of the material. This allowed loads to be smoothly transferred to the fibers, greatly increasing the strength and endurance of the composite material.

目錄

第一章 緒論 1
1-1 因能源及環保需求而發展的複合材料 1
1-1-1 全球風力機發展背景 1
1-1-2 高環境親和性之高分子複合材料 4
1-2 高分子複合材料 5
1-2-1 複合材料簡介 5
1-2-2 高分子基材簡介 7
1-3 研究動機及方法 8
第二章 文獻回顧 15
2-1 環氧樹脂 15
2-1-1 環氧樹脂的性質與應用 16
2-1-2 環氧樹脂的硬化機制 16
2-2 奈米填充材料 18
2-3 奈米碳管 20
2-4 石墨烯 22
2-5 碳纖維補強複合材料 22
2-6 奈米碳材於複合材料之機械與疲勞性質 23
2-6-1 奈米碳材於高分子基材中之分散性 23
2-6-2 奈米碳材補強奈米複合材料之機械性質 24
2-6-3 奈米補強材於碳纖維積層板之機械性質探討 27
2-7 溫濕效應對複合材料之影響 28
2-8 複合材料疲勞性質 30
2-8-1 材料破壞模式 30
2-8-2 應變能量釋放率 31
2-8-3 複合材料之破壞機制 32
2-8-4 應力(S)與疲勞週次(Nf)曲線(S-N curve) 33
2-9 奈米銀線 34
2-9-1 奈米銀線的製備 34
2-9-2 奈米銀線於高分子複合材料之應用 36
第三章 實驗方法 37
3-1 實驗材料 37
3-1-1 高分子基材與溶劑 37
3-1-2 奈米填充材料及纖維布 38
3-1-3 實驗試劑 39
3-2 實驗設備與量測儀器 41
3-2-1 實驗設備 41
3-2-2 量測儀器 43
3-3 奈米材料製備流程 47
3-3-1 表面改質奈米碳管之製備 47
3-3-2 奈米石墨烯片之製備 48
3-3-3 表面改質石墨烯之製備 48
3-3-4 奈米銀線之合成 49
3-4 實驗量測方法 50
3-4-1 奈米銀線鑑定 50
3-4-2 石墨烯及奈米碳管鑑定 51
3-4-3 奈米複合材料薄膜電性質及熱性質量測 52
3-4-4 奈米複合材料之機械性質量測 52
3-4-5 碳纖維積層板複合材料機械性質 54
第四章 奈米碳材及奈米銀線鑑定 56
4-1 石墨烯鑑定 56
4-1-1 X射線繞射圖譜分析 56
4-1-2 X射線光電子能譜分析 57
4-1-3 拉曼光譜分析 58
4-1-4 穿透式電子顯微鏡分析 60
4-1-5 熱重損失分析 60
4-2 改質奈米碳管鑑定 61
4-2-1 拉曼光譜分析 61
4-2-2 霍式紅外線光譜分析 61
4-2-3 高解析電子能譜儀分析 62
4-2-4 熱重損失分析 63
4-3 奈米銀線鑑定 64
4-3-1 電子顯微鏡型態分析 64
4-3-2 紫外光/可見光譜儀(UV/Vis Spectroscopy)分析 65
4-3-3 X射線繞射結晶結構分析 65
第五章 奈米複合材料及碳纖維積層板製程 66
5-1 高分子奈米複合材料製程 66
5-1-1 Polybenzoxazine/ Epoxy共聚物複合材料製備 66
5-1-2 奈米碳材暨共聚物複合材料製備 67
5-2 碳纖維積層板複合材料製備 70
第六章 石墨烯/奈米碳管/奈米銀線 奈米複合材料之分散性對於薄膜各項性質之影響 73
6-1 機械性質 74
6-2 熱機械性質 75
6-3 電性質 77
第七章 石墨烯/奈米碳管/奈米銀線複合材料之各項性質 81
7-1 機械性質 81
7-1-1 拉伸性質 81
7-1-2 彎曲性質 83
7-2 熱動態機械性質 84
第八章 石墨烯/ 奈米碳管/ 碳纖維 積層板之機械性質 86
8-1 機械性質 86
8-1-1 拉伸性質 86
8-1-2 彎曲性質 87
8-1-3 衝擊性質 89
8-1-4 扭轉性質 89
8-1-5 層間剪應力量測 90
8-2 動態扭轉疲勞機械性質 91
第九章 結論與未來研究方向 94
9-1 結論 94
9-2 未來研究方向 96
參考文獻 98
附表 108
附圖 120

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