臺灣博碩士論文加值系統

本篇碩士論文內容主要分為兩個部分，第一部分為電活性環氧樹脂的製備、鑑定及防蝕性能探討; 第二部分則是機械強度可調之彈性矽化物氣凝膠之合成、鑑定與物性探討。
第一部分的研究以電化學法探討具有電活性環氧樹脂/石墨烯複合塗料在冷軋鋼的防腐蝕應用上。 首先，使用氧化偶合法製備側鏈電活性-二胺單體，並利用傅利葉轉換紅外光譜儀、液相層析質譜儀及核磁共振儀進行電活性單體結構鑑定。 此外，使用紫外-可見光光譜儀及循環伏安儀確認其氧化還原特性。
將電活性二胺單體與環氧樹脂前驅物進行開環熱聚合反應來合成電活性環氧樹脂塗料，並同時合成電活性環氧樹脂塗料加入1 wt-% 石墨烯來合成電活性複合塗料。 藉由一系列電化學量測方式及氣體穿透分析可知，電活性複合塗料對冷軋鋼具有最好的防腐蝕能力。 其原因可分為兩部分： (1) 藉由加入還原氧化石墨烯提升防蝕塗料之電催化效果，使鈍性金屬氧化層(Fe2O3及Fe3O4)快速升成。 (2) 電活性環氧樹脂內的苯胺五聚體與還原氧化石墨烯之間形成分子間作用力增加還原氧化石墨烯在高分子內的分散能力，有效提升塗層氣體(特別是氧氣)的阻隔特性。
接下來，第二部分是機械強度可調之彈性矽化物氣凝膠之研究，首先以乙烯基三甲氧基矽烷與2,2''-（亞乙二氧基）二乙硫醇經紫外光照射合成所需之前驅物，並以溶膠-凝膠法製備出未改質與利用甲基三甲氧基矽烷進行改質之彈性氣凝膠。 合成出之前驅物以傅利葉轉換紅外光譜與核磁共振儀鑑定其結構，再將合成之彈性氣凝膠藉由固態核磁共振儀確認其化學結構。 合成出之彈性氣凝膠，利用掃描式電子顯微鏡與比表面積及孔隙度分析儀 (BET) 來進行彈性氣凝膠的孔洞性質鑑定，得知經改質後之彈性氣凝膠孔洞分佈密度較高，且具有較高的比表面積及較多的孔隙率。 彈性氣凝膠亦進行接觸角測試，得到隨著甲基三甲氧基矽烷增加，其疏水特性也逐漸提升。 同時，彈性氣凝膠對熱傳導係數進行應用上之分析，由分析結果獲得當甲基三甲氧基矽烷比例提升時，其熱傳導係數亦會提升。
此外，利用硬度計與動態機械熱分析儀進行彈性氣凝膠之機械強度測試，當甲基三甲氧基矽烷添加量為0 wt%、1 wt% 與10 wt% 時，由硬度計測得的值則為27、35與67逐漸提升。接著，動態機械熱分析獲得的數值為壓縮量11.44 %、10.89 % 與 7.65 % 逐漸降低。最後，從上述結果得知: 改質後之彈性氣凝膠可藉由甲基三甲氧基矽烷添加的多寡對其結構之機械強度進行調整。

This thesis is mainly divided into two parts. The first part discusses the preparation, characterization and anticorrosion application of electroactive epoxy resin/reduced graphene oxide (rGO). The second part discusses the preparation and characterization and physical property studies of flexible aerogels with tunable mechanical strength.
In the part 1, first of all, side-chain electroactive diamine monomer (DAAP) was synthesized by oxidative coupling reactions, followed by characterized through Fourier transform infrared (FT-IR) spectroscopy, liquid chromatography mass spectrometry (LC-MS) and nuclear magnetic resonance (NMR) spectroscopy. Moreover, the redox capability of as-prepared monomer was investigated by UV-vis spectroscopy and cyclic voltammetry (CV).
An electroactive epoxy resin coating was prepared by reacting as-synthesized electroactive monomer and epoxy pre-polymer through performing the thermal epoxide-ring polymerization reactions. The corresponding composite containing 1 wt% of rGO was also prepared for comparative studies. Subsequently, the corrosion protection of as-prepared all coating materials upon cold rolled steel (CRS) electrode was evaluated by a series of electrochemical corrosion measurements in saline condition. It should be noted that CRS coated with composite containing 1 wt% of rGO was found to exhibit best anticorrosion performance based on the studies of Tafel plots and impedance spectroscopy. Gas permeability analysis (GPA) of all as-prepared membranes showed that the composite containing 1 wt% of rGO coating exhibited the best oxygen gas barrier property. The possible reason for the enhancement of composite coating in anticorrosion as compared to that of neat epoxy resin can be drawn into two conclusions: (1) incorporation of 1 wt-% of rGO into electroactive epoxy may enhance the electro-catalytic effect of electroactive epoxy to promote the formation of densely passive oxide layer (Fe2O3 and Fe3O4). (2) The formation of π-π interaction between the aniline pentamer of electroactive epoxy coating and rGO led to the better dispersion capability of rGO in polymer coating matrix, implied the higher oxygen gas barrier property of composite coating as compared to that of neat polymer coating.
In the part 2, the research target focused on the preparation and characterization and physical property studies of flexible aerogels with tunable mechanical strength. First, the synthesis of precursor began with a click reaction of vinyltrimethoxynonane (VTMS) and 2,2''- (ethylenedioxy) diethanethiol (EDDET). Subsequently, the acid-catalyzed and base-catalyzed sol-gel reactions were used to turn precursor into generally flexible aerogel. Subsequently, MTMS was used as modifier to fine-tune the mechanical strength of flexible aerogels. The precursor was identified by FT-IR and NMR spectroscopy, and the chemical structures of synthesized flexible aerogel were confirmed by 13C- and 29Si- solid-state nuclear magnetic resonance spectroscopy (SSNMR).
The porous structure and surface area of synthetic flexible aerogels were identified by nitrogen adsorption – desorption. Surface morphological image and surface wettability of as-prepared flexible aerogels was observed by scanning electron microscope (SEM) and contact angle, respectively. Thermal conductivity measurement of as-prepared flexible aerogel was determined by Hot Disk TechMax H5DR with sensor design No. 5501.
It should be noted that, as the MTMS increased, the flexible aerogel have higher specific surface area and porosity. Moreover, increase of hydrophobic properties and thermal conductivity was also accompanied with the increase of MTMS loading. In addition, the mechanical strength of the flexible aerogel was measured using a durometer and dynamic mechanical thermal analysis (DMA). When the loading of methyltrimethoxydecane was 0 wt%, 1 wt% and 10 wt%, the corresponding hardness agent was increased from 27 to 35 and 67. On the other hand, the compressibility values obtained by dynamic mechanical thermal analysis were gradually reduced from 11.44 % to 10.89 % and 7.65 %. From the analysis results, flexible aerogel was able to fine-tune the mechanical strength with the addition of MTMS.

目錄
中文摘要 I
Abstract III
謝誌 VI
目錄 VII
圖目錄 XII
表目錄 XVI
第一章 1
第一節 緒論 1
1.1.1 導電高分子簡介 1
1.1.1.1 歷史發展之回顧 2
1.1.1.2 共軛高分子的導電理論 4
1.1.1.3 導電高分子聚合方式 5
1.1.1.4 具電活性聚苯胺之簡介 7
1.1.2 苯胺寡聚體簡介 10
1.1.2.1 歷史發展之回顧 10
1.1.2.2 苯胺寡聚體之電活性特性 11
1.1.3 環氧樹脂簡介 13
1.1.3.1 環氧樹脂的固化劑與開環反應機制 13
1.1.3.2 環氧樹脂的種類 15
1.1.3.3 環氧樹脂官能基含量表示法 16
1.1.3.4 環氧樹脂的功能與應用 17
1.1.4 石墨簡介 21
1.1.4.1 石墨烯簡介 21
1.1.4.2 石墨烯之特性 24
1.1.4.3 石墨烯之製備 26
1.1.4.4 石墨烯之應用 30
1.1.5 防腐蝕簡介 33
1.1.5.1 腐蝕簡介 33
1.1.5.2 金屬氧化腐蝕 33
1.1.5.3 常見的金屬防蝕方法 35
1.1.6 研究動機 37
第二節 實驗藥品、儀器與步驟 39
1.2.1 實驗藥品與儀器 39
1.2.1.1 實驗藥品 39
1.2.1.2 實驗儀器與測試條件 43
1.2.2 製備電活性單體 50
1.2.2.1 苯胺五聚體 (AP) 之合成 50
1.2.2.2 苯胺五聚體-二氟苯單體 (DFAP) 之合成 50
1.2.2.3 側鏈電活性-二胺單體 (DAAP) 之合成 51
1.2.3 製備環氧樹脂及其複合材料 53
1.2.3.1 非電活性環氧樹脂 (NEET) 53
1.2.3.2 電活性環氧樹脂 (EET) 53
1.2.3.3 電活性環氧樹脂/氧化石墨烯複材 (GOEET) 54
1.2.3.4 電活性環氧樹脂/還原氧化石墨烯複材 (rGOEET) 54
第三節 結果與討論 55
1.3.1 電活性單體之合成鑑定 55
1.3.1.1 電活性單體之傅利葉轉換紅外光譜鑑定 (FT-IR) 55
1.3.1.2 電活性單體之液相層析質譜儀鑑定 (LC-MS) 57
1.3.1.3 電活性單體之核磁共振光譜鑑定 (NMR) 58
1.3.1.4 電活性單體之氧化還原性 60
1.3.2 環氧樹脂及其複合材料之合成鑑定 64
1.3.2.1 環氧樹脂薄膜之合成鑑定 64
1.3.2.2 利用UV-vis鑑定電活性單體與rGO之摻和 65
1.3.2.3 利用Raman光譜鑑定電活性單體與rGO之摻和 66
1.3.3 石墨烯在電活性環氧樹脂中之分散性 68
1.3.3.1 使用靜置法進行分散性比較 68
1.3.3.2 穿透式電子顯微鏡(TEM) 70
1.3.4 電活性測試 72
1.3.4.1 循環伏特安培儀 (CV) 72
1.3.5 防腐蝕測試 74
1.3.5.1 塔伏試驗檢測 (Tafel) 74
1.3.5.2 電化學阻抗光譜測試 (EIS) 76
1.3.5.3 電活性複合材料產生鈍性氧化層之鑑定 81
1.3.6 氣體阻隔性 84
1.3.6.1 氣體穿透分析儀 (GPA) 84
第四節 結論 86
第五節 參考文獻 88
第二章 96
第一節 緒論 96
2.1.1 溶膠-凝膠原理簡介 96
2.1.1.1 歷史發展之回顧 97
2.1.1.2 溶膠-凝膠法之原理 101
2.1.1.3 溶膠-凝膠法之影響因子 104
2.1.2 氣凝膠簡介 107
2.1.2.1 氣凝膠之種類 107
2.1.2.2 氣凝膠之製備 113
2.1.2.3 氣凝膠之應用 118
2.1.3 研究動機 120
第二節 實驗藥品、儀器與步驟 122
2.2.1 實驗藥品與儀器 122
2.2.1.1 實驗藥品 122
2.2.1.2 實驗儀器與測試條件 124
2.2.2 彈性氣凝膠之製備 130
2.2.2.1 彈性氣凝膠之合成 130
2.2.2.2 彈性氣凝膠之改質 130
第三節 結果與討論 132
2.3.1 彈性氣凝膠之鑑定 132
2.3.1.1 傅利葉轉換紅外光譜鑑定 (FT-IR) 132
2.3.1.2 核磁共振光譜儀 (NMR) 133
2.3.1.3 固態核磁共振光譜鑑定 (SSNMR) 135
2.3.2 彈性氣凝膠之結構與孔洞鑑定 138
2.3.2.1 掃描式電子顯微鏡 (SEM) 138
2.3.2.2 孔洞及表面分析儀 (BET) 139
2.3.3 彈性氣凝膠之親疏水性質鑑定 142
2.3.3.1接觸角 (Contact angle) 142
2.3.4 彈性氣凝膠之機械性質鑑定 144
2.3.4.1 材料硬度測試 (Hardness) 144
2.3.4.2 動態機械熱分析 (DMA) 145
2.3.4.3 壓縮性測試 (Compression set) 147
2.3.5 彈性氣凝膠之熱傳導性質鑑定 149
第四節 結論及未來展望 151
第五節 參考文獻 153
圖目錄
圖1-1-1 目前常見的高分子 3
圖1-1-2 Bipolaron 與 Polaron 之能帶示意圖[6] 5
圖1-1-3 苯胺八聚體之不同氧化程度示意圖[12] 7
圖1-1-4 聚苯胺摻雜及氧化還原型態[14] 8
圗1-1-5 導電高分子的應用 9
圖1-1-6 雙端胺基封端苯胺三聚體之合成[26] 11
圖1-1-7 電活性聚醯胺 11
圖1-1-8 側鏈含電活性苯胺寡聚體之聚甲基丙烯酸甲酯 12
圖1-1-9 環氧樹脂與胺類的固化反應機構 15
圖1-1-10 電子效應示意圖 15
圖1-1-11 DGEBA之化學結構及基本功能性 18
圖1-1-12 石墨烯示意圖[52] 22
圖1-1-13 石墨烯及其衍生物之示意圖[57] 23
圖1-1-14 Hummers Method的氧化石墨烯製程示意圖[70] 28
圗1-1-15 本實驗所研究之目標 38
圖1-2-1 工作電極裝置示意圖 47
圖1-2-2 電化學反應槽示意圖 47
圖1-2-3 氣體穿透分析儀之Membrane cell示意圖 49
圖1-2-4 苯胺五聚體 (AP) 之結構圖 50
圖1-2-5 苯胺五聚體-二氟苯單體(DFAP)之結構圖 51
圖1-2-6 側鏈電活性-二胺單體 (DAAP) 之結構圖 52
圖1-2-7 電活性環氧樹脂之結構圖 53
圖1-3-1 電活性單體之紅外線光譜圖 (a) AP (b) DFAP (c) DAAP 56
圖1-3-2 電活性單體之液相層析質譜圖 57
圖1-3-3 電活性單體之核磁共振光譜圖 (a) AP (b) DFAP (c) DAAP 60
圖1-3-4 苯胺五聚體氧化還原流程 61
圖1-3-5 電活性單體之氧化還原 UV-vis 62
圖1-3-6 電活性單體之氧化還原CV 63
圖1-3-7 紅外線光譜圖 (a)液態 NEET (b)固態 NEET 65
圖1-3-8 紫外-紅外光吸收 (a)DAAP (b)DAAP+rGO 66
圖1-3-9 電活性單體與rGO之相互作用力拉曼光譜 (a) rGO (b) DAAP (c) DAAP+rGO 67
圖1-3-10 GO與rGO溶於DMAc中靜置沉降情況 (a) GO (b) rGO 69
圗1-3-11 電活性複合材料溶於DMAc中靜置沉降情況 (a) 添加GO (b) 添加rGO 69
圖1-3-12 GO與rGO分散在電活性環氧樹脂的TEM圖 (A) 倍率x50K下GO的分散 (B) 倍率x200K下GO的分散 (C) 倍率x50K下rGO的分散 (D) 倍率x200K下rGO的分散 71
圖1-3-14 非電活性與電活性複合材料之CV比較 (a) NEET (b) EET (c) GOEET (d) rGOEET 73
圖1-3-15 塔伏曲線分析(a) Bare (b) NEET (c) EET (d) GOEET (e) rGOEET 76
圖1-3-16 電壓與電流在交流電情況下的變化示意圖 77
圖1-3-17 複數平面上之阻抗圖形 77
圖1-3-18 電極的等效電路圖 78
圖1-3-19 Nyquist plot半圓圖形 79
圖1-3-20 Nyquist plot (a) Bare (b) NEET (c) EET (d) GOEET (e) rGOEET 80
圖1-3-21 Bode plot (a) Bare (b) NEET (c) EET (d) GOEET (e) rGOEET 81
圖1-3-22 鈍性氧化層反應機制[90] 82
圖1-3-23 文獻中由Raman光譜測得之鈍性氧化層光譜圖[101] 83
圖1-3-24為鈍性氧化層之Raman光譜鑑定 (a)CRS (b) coating EET (c) coating rGOEET 83
圗1-3-13 氧氣對不同薄膜之穿透特性 85
圗1-4-1 電活性環氧樹脂與rGO之關係 87
圖2-1-1 溶膠-凝膠法製備過程示意圖[6] 98
圖2-1-2 凝膠網狀構造結合之型式 101
圖2-1-3 TEOS單體反應成三維網狀交聯結構[22] 102
圖2-1-4 溶膠-凝膠在不同酸鹼環境下反應生成的顆粒大小[26] 106
圖2-1-5 不同pH值條件下合成二氧化矽氣凝膠示意圖[29] 108
圖2-1-6 美國科學家於2011年製造出鎳構成之氣凝膠[30] 111
圖2-1-7 全碳氣凝膠[31] 112
圖2-1-8 全碳氣凝膠之微觀結構[31] 112
圖2-1-9 溶膠-凝膠法製作氣凝膠流程說明圖 113
圖2-1-10 二氧化矽氣凝膠親疏水結構示意圖 114
圖2-2-1 DMA測試示意圖 126
圖2-2-2 邵氏硬度計示意圖[45] 126
圖2-2-3 熱傳導係數之量測裝置與Sensor樣式 128
圖2-2-4 ASTM D695規格之Compression set載具 129
圖2-2-5 乾燥前之白色塊狀氣凝膠 131
圖2-2-6 乾燥後之彈性氣凝膠 131
圖2-3-1 反應物單體與前驅物之FT-IR圖譜 133
圖2-3-2 文獻中 VTES, EDDET 和 Precursor 之1H NMR圖譜[50] 134
圖2-3-3 本實驗VTMS, EDDET和Precursor之1H NMR圖譜 134
圖2-3-3 固態核磁共振矽譜之結構 135
圖2-3-4 文獻中Precursor之固態核磁共振圖譜 (a) 13C NMR (b) 29Si NMR[50] 136
圖2-3-5 彈性氣凝膠之13C固態核磁共振圖譜 137
圖2-3-6 彈性氣凝膠之29Si固態核磁共振圖譜 137
圖2-3-7 彈性氣凝膠之SEM圖 (A) FAG (B) FAG-M05 (C) FAG-M1 (D) FAG-M5 (E) FAG-M10 (F) FAG-T10 139
圖2-3-8 彈性氣凝膠之吸脫附曲線 141
圖2-3-9 彈性氣凝膠之孔洞大小分佈 141
圖2-3-10 彈性氣凝膠之接觸角 143
圖2-3-11 彈性氣凝膠之DMA分析 146
圖2-3-12 彈性氣凝膠之Compression set鑑定 148
表目錄
表1-1-1 環氧樹脂種類與代號 16
表1-3-1 電活性單體之特徵官能基對照表 56
表1-3-2 電活性環氧樹脂及其複合材料之防腐蝕能力 75
表1-3-3 氧氣對薄膜之穿透率數據彙整 84
表2-1-1 二氧化矽氣凝膠之特性[29] 109
表2-1-2為較常使用於超臨界乾燥之化合物 [36]。 115
表2-2-1 邵氏硬度對照表[48] 127
表2-3-1 反應單體及前驅物之特徵吸收峰彙整 132
表2-3-2 彈性氣凝膠之 BET 數據彙整 140
表2-3-2 彈性氣凝膠之密度與硬度測試 145
表2-3-3 彈性氣凝膠之 DMA 壓縮數據彙整 146
表2-3-4 彈性氣凝膠之Compression set數據彙整 147
表2-3-4 彈性氣凝膠的熱傳導係數整理 149
表2-3-13 彈性氣凝膠之熱傳導係數 150

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