以3-胺丙基三甲氧基矽與雙酚A型環氧樹脂(環氧當量818 g/eq)之環氧基反應，並以FT-IR證實已反應完全。改質後的環氧樹脂(EP-APTES)掺混四乙氧基矽烷或奈米級二氧化矽以行溶膠凝膠法反應。在此實驗中主要的探討差異分別掺混不同量的TEOS或者奈米級二氧化矽在酸性條件與鹼性條件下催化之差異。
　　在實驗中發現各項物理性質如膠含量、對水與乙醇吸收損失率、接觸角以及硬度方面都比原本的環氧樹脂性質有所提升。在熱性質方面則是使用熱重分析(TGA) 量測，而改質過後的EP-APTES材料其熱安定性與熱氧化性皆有提升。在微差掃描熱卡儀測試則是發現改質過後的環氧樹脂之Tg比原本的高出50℃左右。利用掃描式電子顯微鏡觀察材料的形態學方面，發現到改質後的環氧樹脂在酸性條件下催化的材料其二氧化矽聚集的現象比較少，而鹼性條件下催化有較嚴重的聚集現象。

Epoxy/silica nano-composite materials are prepared by silane-terminated epoxy resin with tetraethoxysilane (TEOS) and nano-silica via a sol-gel process, respectively. The silane-terminated epoxy resin (EP-APTES) is obtained from a ring opening reaction of an epoxy resin (e.g. its EEW is 818) with 3-aminopropyltriethoxysilane (APTES). 
The nano-composites are prepared by mixing EP-APTES with various dosages of TEOS and nano-silica (dispersed in methanol solution), respectively in 5, 10, or 20 phr. The epoxy/silica nano-composites formation are catalyzed in acidic (pH= 3) and basic (pH=10) conditions, respectively via a sol-gel process.
  The performance properties, such as gel content, pencil hardness, contact angle, thermal stabilities and etc. of these resulted epoxy/silica nano-composites are enhanced with increasing silica dosage. Silica nano-size distribution of nano-composites from acidic condition is far better than that of obtained from base catalytic condition, which are demonstrated by SEM observations.

中摘..................................................... I
英摘.................................................... II
圖表目錄................................................ VI
一、緒論................................................. 1
1-1　前言................................................ 1
1-2　研究動機............................................ 3
二、文獻回顧............................................. 4
2-1　有機/無機奈米複合材料............................... 4
2-2　溶膠-凝膠法 (Sol-Gel process) ...................... 7
2-3　溶膠-凝膠法之控制變因............................... 8
2-4　環氧樹脂簡介....................................... 12
2-5　環氧樹脂的應用..................................... 14
2-6　環氧化合物之反應性................................. 16
2-7　環氧樹脂之改質..................................... 18
三、實驗................................................ 19
3-1　藥品............................................... 19
3-2　儀器............................................... 20
3-3　Epoxy-APTES 合成步驟............................... 21
3-4　由溶膠凝膠法合成奈米複合材料薄膜................... 22
3-4-1　有機環氧樹脂／無機四乙氧基矽烷複合材料合成....... 22
3-4-2　有機環氧樹脂／無機奈米二氧化矽複合材料合成....... 22
3-4-3　樣品編號命名..................................... 24
3-5　環氧樹脂環氧當量測定法 (EEW: equivalent epoxy weight)
   　....................................................25
3-5-1　使用試劑......................................... 25
3-5-2　測定流程......................................... 25
3-6　物理性質測試....................................... 27
3-6-1　固含量測試 (Solid Content)....................... 27
3-6-2　膠含量測試 (Gel Content)......................... 27
3-6-3　吸水率 (Water-Uptake %) 與對水損失率 (Weight % Loss 
     　in Water)........................................ 28
3-6-4　95%乙醇溶液浸泡吸收率(Ethanol-Uptake %)與對乙醇損失
     　率(Weight  Loss in Ethanol %).................... 29
3-6-5　接觸角 (Contact Angle ).......................... 30
3-6-6　鉛筆硬度 (Pencil Hardness )...................... 30
3-7　熱性質測試......................................... 31
3-7-1　熱重分析　(Thermal Gravity Analysis, TGA )....... 31
3-7-2　微差掃描熱卡分析儀　(Differential Scanning 
     　Calorimeter, DSC )............................... 32
3-8　掃描式電子顯微鏡 (Scanning Electronic Microscopy, 
   　SEM ) ............................................. 32
3-9　FT-IR光譜測試...................................... 32
四、結果與討論.......................................... 33
4-1　Epoxy-ATPES的合成.................................. 33
4-2　Epoxy-ATPES的物理性質.............................. 36
4-2-1　膠含量........................................... 36
4-2-2　水與乙醇對薄膜的吸收損失率....................... 40
4-2-3　接觸角 (Contact Angle ).......................... 43
4-2-4　鉛筆硬度 (Pencil Hardness )...................... 44
4-3　熱重分析 (Thermal Gravity Analysis, TGA ).......... 45
4-3-1　熱安定性......................................... 45
4-3-2　熱氧化性......................................... 53
4-4　微差掃描熱卡儀測試
   　(Differential Scanning Calorimeter, DSC ).......... 60
4-5　掃描式電子顯微鏡 (Scanning Electronic Microscopy, 
   　SEM ).............................................. 64
五、結論................................................ 74
六、參考資料............................................ 76
作者簡歷................................................ 79
會議論文................................................ 80
圖 表 目 錄
Scheme 3-1 Epoxy-APTES 合成流程圖................................................ 21
Scheme 3-2 Epoxy-APTES 架橋示意圖................................................ 23
Figure 2-1 矽烷氧化合物之水解縮合反應.......................................... 8
Figure 2-2 矽酸鹽在a.酸性環境 b.鹼性環境下之凝膠結構............. 9
Figure 2-3 pH 值對反應中矽烷氧架橋結構之影響............................. 10
Figure 2-4 環氧樹脂基本結構式.......................................................... 13
Figure 2-5 環氧基反應示意圖.............................................................. 16
Figure 3-1 二氧化矽粒子示意圖........................................................... 22
Figure 3-2 接觸角測試示意圖.............................................................. 30
Figure 4-1 環氧樹脂 NPES-904 之FT-IR 光譜圖............................ 34
Figure 4-2 APTES 之FT-IR 光譜圖.................................................. 34
Figure 4-3 EP-APTES 之 FT-IR 光譜圖........................................... 35
Figure 4-4 二氧化矽聚集示意圖........................................................ 39
Figure 4-5 酸性條件下催化之EP-APTES/TEOS 薄膜之熱重分析圖(氮
氣條件).................................................................................. 49
Figure 4-6 酸性條件下催化之EP-APTES/TEOS 薄膜之重量損失微分
圖(氮氣條件)........................................................................ 49
Figure 4-7 酸性條件下催化之EP-APTES/nano-silica dispersion 薄膜之
熱重分析圖(氮氣條件)...................................................... 50
Figure 4-8 酸性條件下催化之EP-APTES/nano-silica dispersion 薄膜之
重量損失微分圖(氮氣條件).............................................. 50
Figure 4-9 鹼性條件下催化之EP-APTES/TEOS 薄膜之熱重分析圖(氮
氣條件)................................................................................. 51
Figure 4-10 鹼性條件下催化之EP-APTES/TEOS 薄膜之重量損失微
分圖(氮氣條件).................................................................. 51
Figure 4-11 鹼性條件下催化之EP-APTES/nano-silica dispersion 薄膜
之熱重分析圖(氮氣條件)................................................ 52
Figure 4-12 鹼性條件下催化之EP-APTES/nano-silica dispersion 薄膜
之重量損失微分圖(氮氣條件)........................................ 52
Figure 4-13 酸性條件下催化之EP-APTES/TEOS 薄膜之熱重分析圖
(空氣條件).......................................................................... 56
Figure 4-14 酸性條件下催化之EP-APTES/TEOS 薄膜之重量損失微分
圖(空氣條件)........................................................................ 56
Figure 4-15 酸性條件下催化之EP-APTES/nano-silica dispersion 薄膜
之熱重分析圖(空氣條件)................................................ 57
Figure 4-16 酸性條件下催化之EP-APTES/nano-silica dispersion 薄膜之
重量損失微分圖(空氣條件)................................................ 57
Figure 4-17 鹼性條件下催化之EP-APTES/TEOS 薄膜之熱重分析圖
(空氣條件)............................................................................ 58
Figure 4-18 鹼性條件下催化之EP-APTES/TEOS 薄膜之熱重分析圖
(空氣條件)............................................................................ 58
Figure 4-19 鹼性條件下催化之EP-APTES/nano-silica dispersion 薄膜
之熱重分析圖(空氣條件)................................................ 59
Figure 4-20 鹼性條件下催化之EP-APTES/nano-silica dispersion 薄膜
之重量損失微分圖(空氣條件)........................................ 59
Figure 4-21 以酸性催化EP-APTES/TEOS 薄膜之DSC 圖............... 62
Figure 4-22 以酸性催化EP-APTES/nano-silica 薄膜之DSC 圖....... 62
Figure 4-23 以鹼性催化EP-APTES/TEOS 薄膜之DSC 圖............... 63
Figure 4-24 以鹼性催化EP-APTES/nano-silica 薄膜之DSC 圖....... 63
Figure 4-25 以酸性催化EP-APTES 薄膜之SEM 圖.......................... 67
Figure 4-26 以酸性催化EP-APTES / 5 phr TEOS 薄膜之SEM 圖.. . 67
Figure 4-27 以酸性催化EP-APTES / 10 phr TEOS 薄膜之SEM 圖... 68
Figure 4-28 以酸性催化EP-APTES / 20 phr TEOS 薄膜之SEM 圖... 68
Figure 4-29 以酸性催化EP-APTES / 5 phr nano-silica dispersion 薄膜
之SEM圖.... 69
Figure 4-30 以酸性催化EP-APTES / 10 phr nano-silica dispersion 薄膜
之SEM圖.......................................................................... 69
Figure 4-31 以酸性催化EP-APTES / 20 phr nano-silica dispersion 薄膜
之SEM圖.......................................................................... 70
Figure 4-32 以鹼性催化EP-APTES 薄膜之SEM 圖.......................... 70
Figure 4-33 以鹼性催化EP-APTES / 5 phr TEOS 薄膜之SEM 圖.... 71
Figure 4-34 以鹼性催化EP-APTES / 10 phr TEOS 薄膜之SEM 圖.. 71
Figure 4-35 以鹼性催化EP-APTES / 20 phr TEOS 薄膜之SEM 圖.. 72
Figure 4-36 以鹼性催化EP-APTES / 5 phr nano-silica dispersion 薄膜
之SEM圖.......................................................................... 72
Figure 4-37 以鹼性催化EP-APTES / 10 phr nano-silica dispersion 薄膜
之SEM圖.......................................................................... 73
Figure 4-38 以鹼性催化EP-APTES / 20 phr nano-silica dispersion 薄膜
之SEM圖.......................................................................... 73
Table 3-1 樣品命名 .............................................................................. 24
Table 4-1 酸性條件下催化之EP-APTES/二氧化矽混成膠含量...... 39
Table 4-2 鹼性條件下催化之EP-APTES/二氧化矽混成膠含量...... 39
Table 4-3 酸性條件下催化EP-APTES/二氧化矽混成薄膜之乙醇與水
對薄膜的吸收損失率........................................................... 42
Table 4-4 鹼性條件下催化EP-APTES/二氧化矽混成薄膜之乙醇與水
對薄膜的吸收損失率........................................................... 42
Table 4-5 酸性條件下催化EP-APTES/二氧化矽混成薄膜之接觸角43
Table 4-6 鹼性條件下催化EP-APTES/二氧化矽混成薄膜之接觸角43
Table 4-7 EP-APTES/二氧化矽混成薄膜之鉛筆硬度.......................... 44
Table 4-8 EP-APTES/二氧化矽混成薄膜之熱重分析(氮氣條件)....... 48
Table 4-9 EP-APTES/二氧化矽混成薄膜之熱重分析(空氣條件)....... 55
Table 4-10 EP-APTES/二氧化矽混成薄膜之Tg 分析......................... 61

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