本研究係採用改質紅麻植物纖維添加入聚乳酸基材中，另外再添加多壁奈米碳管熔融混摻後，對複合材料整體性能的探討與研究。其中纖維先經兩種不同矽烷偶合劑(3‐glycidoxypropyltrimethoxysilane, 代號OX)與(vinyltriethoxy silane, 代號Vi)改質，結果顯示以OX改質之效果較佳，在添加30wt%之OX改質紅麻纖維與1wt%奈米碳管時，複合材料之拉伸強度最佳，提升了84%；而添加40wt%改質紅麻纖與1wt%奈米碳管時，複合材料之耐衝擊強度最佳，提升了156%，熱變形溫度也提升122%。從XRPD、DSC分析與等溫結晶動力學之探討得知，紅麻纖維與奈米碳管的添加能改變聚乳酸的結晶型態與增快其結晶速率。SEM分析可以觀察到經由偶合劑改質可使紅麻纖維與聚乳酸間相容性提升。電性質分析中，含30wt% OX改質紅麻纖維與1wt%奈米碳管之複合材料，其表面電阻為3.47x109 Ω，可達到抗靜電等級。結果顯示，聚乳酸添加改質紅麻植物纖維與多壁奈米碳管，能增進聚乳酸之熱性質、機械性質、電性質，使複合材料應用範圍更廣泛，並對環境較為友善。

In this study, the chemically modified kenaf fibers (KF), and an acid-treated multi-walled carbon nanotubes (MWCNTs) were added into polylactic acid (PLA) matrix. Moreover, the fibers were pre‐treated by two kinds of coupling agent (3-glycidoxypropyltr-imethoxysilane, code: OX, and vinyltriethoxy silane, code: Vi). The results showed that the reinforcing effects of OX modified fibers were better than those of Vi modified ones. The tensile strength of PLA was increased about 84% when 30wt% of OX modified KF and 1wt% of MWCNTs were added. The impact strength and heat deflection temperature were increased about 156 and 122%, respectively, when the composite reinforced with 40wt% of OX modified KF and 1wt% of MWCNTs. The analysis of XRPD, DSC and isothermal crystallization kinetics showed that the crystalline behavior of PLA can be changed and accelerated with the addition of modified KF and MWCNT. SEM analysis showed that the compatibility between PLA and KF was improved after coupling agent modification. The results of electrical properties test showed that the surface resistivity of the composite containing 30wt% of OX modified KF and 1wt% of MWCNTs was 3.47x109 Ω, which can reach the anti-static purpose. These results show that the thermal, mechanical and electrical properties of PLA can be improved by the addition of modified KF and MWCNTs. Moreover, this type of reinforced PLA would be more environmental friendly than the artificial additive-reinforced one.

目錄
摘要.............................I
Abstract........................II
誌謝............................ III
表目錄...........................IX
圖目錄.......................... XI
第一章 緒論....................................1
1-1前言.......................................1
1-2 生物可分解塑膠介紹.........................5
1-2-1 生物可分解塑膠合成方式....................5
1-2-2生物可分解性能標準.........................7
1-3聚乳酸之簡介................................10
1-3-1聚乳酸的介紹與特性.........................10
1-3-2聚乳酸之製造合成...........................11
1-4天然纖維之簡介...............................15
1-4-1植物纖維介紹與特性..........................15
1-4-2植物纖維性質比較............................18
1-4-3 紅麻植物纖維簡介...........................19
1-5奈米碳管之簡介................................21
1-5-1碳的同素異形體..............................21
1-5-2奈米碳管的發現與結構........................22
1-5-3 奈米碳管性質..............................25
1-5-4奈米碳管的合成..............................27
1-5-5奈米碳管的改質..............................29
1-6矽烷偶合劑之簡介..............................30
1-7生質複合材料..................................32
第二章 文獻回顧及研究動機.........................35
2-1複合材料.....................................35
2-2天然纖維/非生物降解性高分子複合材料.............36
2-3天然纖維/生物降解性高分子複合材料...............42
2-4奈米碳管/生物降解性聚合物複合材料...............50
2-5 Avrami 方程式................................56
2-6研究動機.....................................59
第三章 實驗內容..................................61
3-1實驗藥品......................................61
3-2儀器設備......................................63
3-3儀器測試方法及條件.............................65
3-4實驗概述......................................71
3-5實驗流程......................................72
3-5-1紅麻纖維表面改質.............................72
3-5-2多壁奈米碳管表面改質..........................74
3-5-3多壁奈米碳管/植物纖維/聚乳酸複合材料的製作與分析 ...75
第四章結果與討論......................................79
4‐1傅立葉轉換紅外光譜儀(FT-IR)分析.....................79
4‐1‐1未處理紅麻纖維與改質紅麻纖維的FT‐IR分析.............79
4-2 機械性質分析.........................................80
4-2-1萬能材料試驗機-拉伸強度測試(未熱處理(NO Annealing)複合材料)...........80
4-2-2 耐衝擊試驗機測試(未熱處理(NO Annealing)複合材料).................84
4-2-3 複合材料拉伸強度與耐衝擊強度測試(未熱處理(NO Annealing)複合材料).............87
4-2-4動態機械分析儀(DMA)測試.............................88
4-2-5萬能材料試驗機-拉伸強度測試(未熱處理(NO Annealing)與熱處理(Annealing)複合材料).....92
4-2-6耐衝擊試驗機測試(未熱處理(NO Annealing)與熱處理(Annealing)複合材料)...............94
4-3熱性質分析...............................96
4-3-1熱變形溫度測試(HDT)(未熱處理(NO Annealing)與熱處理(Annealing)複合材料)............96
4-3-2微差掃描式熱分析儀(DSC)分析.................99
4-3-3等溫結晶動力學研究..........................103
4-4結構分析.....................................105
4-4-1 X-光粉末繞射儀(XRPD)分析...................105
4-5微觀結構分析..................................107
4-5-1掃描式電子顯微鏡(SEM)分析....................107
4-6電性質分析....................................110
4-6-1導電高阻計分析...............................110
4-7生物可分解性分析..............................114
第五章 結論......................................117
第六章 參考文獻...................................121
附錄..............................................126

表目錄
表1-1 全球海洋塑膠碎片比例[1].......................4
表1-2各項生物可分解高分子合成法與產品[7].............6
表1-3各種不同生物分解之標準化測試方式[3].............8
表1-4生物可分解塑膠的檢測、標準與認證[13].............9
表1-5植物纖維化學組成[23]..........................17
表1-6人造纖維與天然植物的機械性質比較[23]............19
表1-7碳的同素異形體的結構及物性參數[27]..............22
表1-8聚合物性質與價格[42]............................33
表1-9 合成纖維與植物纖維性質與價格[42].................34
表2-1含30wt%修飾亞麻纖維/聚丙烯基材和玻璃纖維/聚丙烯複合材料拉伸性質。[43]......38
表2-2天然纖維/熱塑性聚合物經不同官能基矽烷偶合劑處理後，不添加起始劑下的拉伸性質改善幅度(%)[40].39
表2-3環氧樹脂及環氧樹脂複合材料儲存模數(Eʹ)[44]............42
表2-4環氧樹脂及環氧樹脂複合材料損失模數(Eʹʹ)[44]............42
表2-5 多壁奈米碳管/PLA複合材料損失模數峰最大值 (MPa)[16].....54
表2-6多壁奈米碳管/PLA複合材料表面電阻率[16]..................54
表2-7聚乳酸、複合材料(PLLA/ZnCC、PLLA/ZnCit、PLLA/talc) ，135°C下等溫結晶動力參數[53].....59
表3-1各物質之代號說明............71
表3-2各成分比例及配方............72
表4-1未經熱處理複合材料之拉伸強度數據表............83
表4-2未經熱處理複合材料之耐衝擊強度數據............86
表4-3未熱處理複合材料之DMA儲存模數數據.............90
表4-4未經熱處理複合材料之DMA損失模數Eʹʹ與溫度關係數據..........91
表4-5熱處理與未熱處理複合材料之拉伸強度數據....................93
表4-6熱處理與未熱處理複合材料之耐衝擊強度數據..................95
表4-7複合材料熱處理與未熱處理之熱變形溫度數據..................98
表4-8複合材料之DSC分析數據 ..................................101
表4-9複合材料在72℃下等溫結晶動力學參數.......................105
表4-10複合材料PC1F 30、PF30 UN與PLA XRPD分析數據.............106
表4-11 PLA與複合材料PC1F 30、PF30 UN導電高阻計測定數據........112
表4-12複合材料之生物可分解性測試數據(%).......................115

圖目錄
圖1-1 黑背信天翁雛鳥，庫雷環礁島，2002[2].....................3
圖1-2 2006到2013年布侖特原油交易價格範圍[5]...................4
圖1-3不同樣品在土壤中掩埋時間的外觀變化[11]....................7
圖1-4乳酸的立體異構物結構....................................11
圖1-5丙交酯的雙環異構物結構..................................11
圖1-6聚乳酸製造概述[21].....................................13
圖1-7聚乳酸不同旋光性結構....................................14
圖1-8天然纖維分類[23].......................................15
圖1-9天然植物纖維的纖維素化學結構[23].........................16
圖1-10天然植物纖維細胞壁概念圖[23]............................17
圖1-11紅麻植物[23]..........................................20
圖1-12奈米碳管的HRTEM圖。(a)5層石墨層，外徑為6.7nm；(b)2層石墨層，外徑為5.5nm；(c)7層石墨層，內徑為2.2nm，外徑為6.5nm[28~29]...............................23
圖1-13 底部成長單壁奈米碳管TEM圖[29]..........................24
圖1-14 奈米碳管捲曲手性矢量二維平面示意圖[30]....................24
圖1-15單壁奈米碳管電腦計算生成圖:(a) (11,11) 扶手型(armchair)，(b) (18,0)鋸齒型(zigzag)，(c) (14,7) 螺旋型(helix)。[29].....................................25
圖1-16 Stone-Wales形變示意圖[32].................................26
圖1-17 奈米碳管的成長機制[34].....................................27
圖1-18化學氣相沉積合成單壁奈米碳管合成法[35].........................28
圖1-19 (a)熱化學氣相沉積法(b)微波電漿化學氣相沉積法之裝置圖[16].........29
圖1-20含3wt%多壁奈米碳管/聚乳酸複合材料斷裂面SEM圖[37]................30
圖1-21矽烷偶合劑化學結構通式........................................31
圖1-22矽烷偶合劑與植物纖維相互作用水解過程[40]........................31
圖1-23生質複合材料生命週期[23]......................................32
圖1-24 BMW 5 Series天然植物複合材料的應用[41].......................33
圖2-1表面修飾亞麻/聚丙烯複合材料對拉伸、模數性質的影響[43].............37
圖2-2 矽烷偶合劑(γ-aminopropyl triethoxy silane, APS)處理天然纖維與PVC基材之間酸鹼反應機制[40]...........................................................38
圖2-3 矽烷偶合劑(vinyltriethoxy silane, VTS)接枝聚乙烯反應機制[40]................40
圖2-4(a)纖維與偶合劑和(b)修飾纖維與環氧樹脂之間的化學反應[44].......................41
圖2-5 FT-IR光譜(a) RSF (b) MRSF 吸附PBA重量W(%)=7.98 (C) RSF (b) MRSF 吸附PBA重量W(%)=132.9 (d) PBA (e) BA[45].............................................43
圖2-6 SEM掃描圖 (a) RSF (b) MRSF 吸附PBA重量W(%)=7.98 (C) MRSF 吸附PBA重量W(%)=132.9[45].44
圖2-7 PBA吸附重量比例對拉伸性質的影響 (a) 拉伸強度(MPa) 和 (b) 斷裂延伸率 (%)[45]...........44
圖2-8疏棉處理製備生質複合材料程序[46]............................................45
圖2-9不同纖維、矽烷偶合劑含量生質複合材料之抗彎強度測試[46]........................46
圖2-10不同纖維、矽烷偶合劑含量生質複合材料之熱變形溫度(HDT)測試[46].................46
圖2-11 SEM掃描圖(a)未處理纖維 (b)矽烷偶合劑處理亞麻纖維 (c)鹼處理與矽烷偶合劑處理後纖維[47]...47
圖2-12 發生化學偶合界面區域 (1a) (1b)聚乳酸與纖維凡得瓦力和氫鍵相互作用力 (2)聚乳酸與修飾纖維間之化學接枝反應[47].........................................47
圖2-13 亞麻/聚乳酸複合材料之拉伸承受力與延伸率測試[47].......................48
圖2-14聚乳酸和聚乳酸/苧麻纖維複合材料DSC加熱曲線 (a) C-PLA (b) O-PLA (c) C-PLA10 (d) O-PLA10[48]..................................................49
圖2-15 POM (a) C-PLA10 (b) O-PLA10，在136°C下恆溫40分鐘[48]..............50
圖2-16不同CNTs、PLA添加量在PCC複合材料中之拉伸性質測試[49]...................51
圖2-17 90PCC/10PLA/1.5CNT複合材料斷裂面經丙酮/乙醇 (1:1 ) 混合液除去部分PCC的SEM圖[49]....51
圖2-18 90PCC/10PLA/CNT複合材料導電率測試[49]................................52
圖2-19複合材料 TEM圖(a) PC 1.5% (b) PC-18 1.5% (c) PC-18T 1.5%[16]..........53
圖2-20最初40分鐘1D WAXD圖 (a) PLLA (b) PLLA/0.05wt % CNTs (c) PLLA/0.05wt % GNSs [50]...55
圖2-21聚乳酸、複合材料(PLLA/ZnCC、PLLA/ZnCit、PLLA/talc)135°C恆溫下DSC放熱結晶曲線[53]....57
圖2-22 135°C恆溫條件下，聚乳酸、複合材料(PLLA/ZnCC、PLLA/ZnCit、PLLA/talc)之(a) 轉化曲線 (b) Avrami圖[53]..................................58
圖3-1紅麻纖維表面改質流程圖.......................73
圖3-2紅麻纖維鹼及酸中和處理反應機制................73
圖3-3紅麻纖維矽烷偶合劑處理(OX)的反應機制..........73
圖3-4紅麻纖維矽烷偶合劑處理(Vi)的反應機制...........74
圖3-5多壁奈米碳管酸處理反應機制....................74
圖3-6多壁奈米碳管酸處理流程圖.......................75
圖3-7多壁奈米碳管/植物纖維/聚乳酸複合材料混合示意圖.......76
圖3-8多壁奈米碳管/植物纖維/聚乳酸複合材料製作分析圖..........77
圖3-9改質紅麻纖維(OX)與聚乳酸之可能反應機制.................77
圖3-10改質紅麻纖維(Vi)與聚乳酸之可能反應機制 ................78
圖4-1未處理紅麻纖維與化學處理紅麻纖維FT‐IR分析圖.............80
圖4-2未經熱處理複合材料之拉伸強度柱狀圖......................83
圖4-3未經熱處理複合材料之耐衝擊強度柱狀圖.....................86
圖4-4未經熱處理複合材料之拉伸強度與耐衝擊強度比較圖.............87
圖4-5未熱處理複合材料之DMA儲存模數Eʹ分析圖與溫度關係圖..........90
圖4-6未熱處理複合材料之DMA損失模數Eʹʹ與溫度關係圖...............91
圖4-7熱處理與未熱處理複合材料之拉伸強度比較柱狀圖................93
圖4-8熱處理與未熱處理複合材料之耐衝擊強度比較柱狀圖...............95
圖4-9複合材料熱處理與未熱處理之熱變形溫度分析圖...................98
圖4-10複合材料之DSC二次升溫分析圖..............................100
圖4-11熱處理與未熱處理複合材料PC1F10 OX之DSC第一次升溫分析圖.......102
圖4-12複合材料在72℃下DSC之等溫結晶放熱曲線圖......................103
圖4-13 複合材料之不同時間下與相對結晶度關係圖......................104
圖4-14 複合材料之log(-ln(1- Xt))與log t 關係Avrami圖.............105
圖4-15 PLA與複合材料PC1F 30、PF30 UN之 XRPD分析..................107
圖4-16複合材料經耐衝擊測試後之斷裂表面SEM圖 (a) PC1F30 OX (b) PC1F40 OX (c) PF30 UN......109
圖4-17 PLA與複合材料PC1F 30、PF30 UN簡單抗靜電測試圖(a) PLA (b) PF30 UN (c) PC1F30 OX............................113
圖4-18複合材料之生物可分解性測試分析圖...........................115
圖4-19複合材料之生物可分解性試片照片.............................116

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