臺灣博碩士論文加值系統

本研究目的在於比較與探討鳳梨葉纖維PLF及微纖絲化纖維素MFC於不同添加量下對於聚乳酸（PLA）機械性質與熱性質的影響。其中是藉由TEMPO氧化系統進行PLF纖維的微纖絲化反應，製備出所需的MFC，此外本研究也藉由溶膠-凝膠法以TEOS為前驅物進行纖維的表面改質，得到改質後的鳳梨葉纖維SGLF及微纖絲化纖維素SGC。將不同纖維與PLA進行熔融混摻，製備出一系列的綠色複合材料。實驗結果顯示，SGC添加5 wt%時其熱變形溫度（HDT）提升最為顯著，最高可以提升30.56%；機械性質方面，SGLF添加3 wt%提升較為顯著，分別在拉伸強度提升31.58%及耐衝擊強度提升20.98%。添加纖維素至複合材料中都有效提升其儲能模數與損失模數，表示纖維素的添加可以補強聚乳酸的剛性以及韌性。從SEM分析斷裂面可觀察到表面改質後纖維與PLA相容性提升並且無拔出現象，而MFC均勻分散於PLA中。透光性測試中可以得知複合材料中以添加1 wt% MFC透光性極佳。由以上結果總結得知，鳳梨葉纖維素及微纖絲化纖維素是可以有效補強聚乳酸的機械性質與熱性質，由於鳳梨葉纖維是鳳梨收成後的廢棄物，因此作為複合材料之補強劑，不僅可以降低工業上的成本，更能降低其廢棄量，及發揮再利用的價值。

The aim of this study is to compare the influence of mechanical and thermal properties of polylactic acid (PLA) reinforced with different cellulose such as pineapple leaf fiber (PLF) or microfibrillated cellulose (MFC). The MFC was obtained by the TEMPO-mediated oxidation of PLF. Moreover, surface modified pineapple leaf fiber (PLF) or microfibrillated cellulose (MFC) were prepared by modification of PLF or MFC through sol-gel reaction. Finally, a series of green composites were prepared by melt-blending. The results revealed that heat deflection temperature shows an increase of 30.56% with reinforced by 5 wt% of SGC. Besides, tensile strength was increased approximately 31.58% and impact strength was increased about 20.98% with reinforced by 3 wt% of SGLF. The storage and loss modulus of the composites can be enhanced by addition of cellulose effectively. These results showed that cellulose can reinforce the rigidity and toughness of PLA. The compatibility of fiber with PLA can be enhanced by surface modification of the fiber, which can be observed by SEM analysis. Furthermore, the MFC uniformly dispersed in PLA was also found in SEM analysis. In addition, the test of diaphaneity revealed that the composite reinforced by 1 wt% MFC has excellent transparency. These results showed that PLF and MFC can enhance mechanical and thermal properties of PLA. Pineapple leaf fibers are the waste after harvest, therefore it can reduce the costs of the composites. Moreover, the pineapple leaf fibers can be reduced and re-used as utilized as reinforcement in composites.

目錄

摘要 I
Abstract II
誌謝 III
目錄 IV
表目錄 VIII
圖目錄 X
第一章 緒論 1
1-1 前言 1
1-2 生物可分解塑膠之簡介 3
1-2.1 生物可分解塑膠性能評價及標準 5
1-3 聚乳酸之簡介 7
1-3.1 聚乳酸的製備方法 8
1-3.2 聚乳酸的特性 10
1-3.3 聚乳酸的應用 11
1-4 天然植物纖維之簡介 14
1-4.1 天然植物纖維的組成及特性 14
1-4.2 鳳梨纖維之簡介 15
1-5 微纖絲化纖維素之簡介 16
1-5.1 微纖絲化纖維素化學組成及特性 17
1-5.2 微纖絲化纖維素的發現 18
1-5.3 微纖絲化纖維素的製備[14] 19
1-6 溶膠-凝膠法（Sol-Gel）之簡介 25
1-6.1 影響溶膠-凝膠法反應之因素[44] 26
第二章 文獻回顧及研究動機 29
2-1 天然植物纖維補強聚乳酸 29
2-2 微纖絲化纖維素的製備 32
2-3 微纖絲化纖維素補強聚乳酸 35
2-4 溶膠-凝膠法改質纖維 39
2-5 研究動機 41
第三章 實驗內容 44
3-1 實驗藥品 44
3-2 儀器設備 47
3-3 儀器測試方法及條件 49
3-5 實驗流程 56
3-5.1 鳳梨葉纖維的處理 56
3-5.2 改良之TEMPO自由基氧化法製備微纖絲化鳳梨葉纖維 56
3-5.3 利用溶膠-凝膠法改質鳳梨葉纖維和微纖絲化鳳梨葉纖維 57
3-5.4 鳳梨葉纖維/聚乳酸複合材料之製備 59
第四章 結果與討論 61
4-1 鳳梨葉纖維與微纖絲化纖維處理 61
4-1.1 傅立葉轉換紅外線光譜（FT-IR）分析 61
4-1.2 固態核磁共振儀（NMR）圖譜分析 63
4-1.3 偏光顯微鏡（POM）分析 66
4-1.4 穿透式電子顯微鏡（TEM）分析 68
4-1.5 熱重量分析儀（TGA）測試 69
4-2 複合材料—熱性質分析 71
4-2.1 熱重量分析儀（TGA）測試 71
4-2.2 微差掃描式熱分析儀（DSC）測試 74
4-2.3 扭矩值分析 77
4-2.4 熱變形溫度測定儀（HDT）測試 79
4-3 複合材料—機械性質分析 81
4-3.1 拉伸強度測試 81
4-3.2 耐衝擊強度測試 83
4-3.3 動態機械性質測試 85
4-4 複合材料—形態分析 93
4-4.1 偏光顯微鏡（POM）分析—複合材料結晶型態分析 93
4-4.2 偏光顯微鏡（POM）分析—複合材料纖維分散分析 95
4-4.3 掃描式電子顯微鏡（SEM）分析 97
4-5 複合材料—透光性分析 99
第五章 結論 101
第六章 參考文獻 104


表目錄

表1-1 生質塑膠主要應用市場 4
表1-2 生物分解性能評價方法分類及特徵 5
表1-3 生物分解國際標準 6
表1-4 PLA薄膜/片材的應用 12
表1-5 PLA纖維在各個領域應用舉例 13
表1-6 常見植物纖維的化學組成 15
表1-7 鳳梨葉纖維化學成分表 16
表1-8 纖維素名稱定義 16
表2-1 天然植物纖維/聚乳酸複合材料之機械性質分析表 31
表2-2 非晶態和結晶態PLA/MFC之機械性質分析表 38
表2-3 常見植物纖維的化學組成 42
表3-1 各組成比例及代號 55
表4-1 鳳梨葉纖維素化學處理前後之TGA數據分析表 70
表4-2 聚乳酸與複合材料之TGA數據分析表 73
表4-3 聚乳酸與複合材料之DSC數據分析表 76
表4-4 聚乳酸與複合材料之扭矩值數據分析表 78
表4-5 聚乳酸與複合材料之HDT數據分析表 80
表4-6 聚乳酸與複合材料之拉伸強度數據分析表 82
表4-7 聚乳酸與複合材料之耐衝擊強度數據分析表 84
表4-8 聚乳酸與複合材料DMA之儲存模數數據分析表 88
表4-9 聚乳酸與複合材料DMA之損失模數數據分析表 90
表4-10 聚乳酸與複合材料DMA之tan δ 數據分析表 92


圖目錄

圖1-1 聚乳酸的化學結構式 8
圖1-2 聚乳酸的生物循環 8
圖1-3 乳酸的化學結構式，左為L-乳酸，右為D-乳酸 9
圖1-4 由乳酸聚合成聚乳酸的反應示意圖 10
圖1-5 PLA與其他熱塑性塑膠的Tg和Tm之比較 11
圖1-6 纖維素的化學結構和構造圖 17
圖1-7 纖維素的基本化學結構並顯示了纖維二醣的重複單體 17
圖1-8 最常用以生產微纖絲化纖維素的機械處理法：均質、微流、研磨 22
圖1-9 溶膠-凝膠法之反應流程 25
圖1-10 水性矽的聚合行為 26
圖1-11 TEOS/ H2O/Ethanol之間相容性之三相圖 28
圖2-1（a）竹纖維；（b）椰子纖維；（c）香根草纖維未處理與經處理後補強PLA複合材料之拉伸模數 30
圖2-2（a）竹纖維；（b）椰子纖維；（c）香根草纖維未處理與經處理後補強PLA複合材料之拉伸強度 30
圖2-3 TEMPO氧化所得纖維素之酸基和醛基含量分析 32
圖2-4 棉短絨（A）經由TEMPO氧化於（B）2 h，（C）4 h，（D）24 h的反應時間後所得纖維素之光學顯微照片 33
圖2-5 改良之TEMPO自由基氧化反應機制 34
圖2-6改良之TEMPO氧化製得纖維素之酸基含量及聚合度分析 34
圖2-7 不同添加劑對於應力應變曲線補強效果之分析 36
圖2-8 MFC含量（wt%）對於應力應變曲線補強效果之分析 36
圖2-9（a）純PLA（b）PLA/MFC 10 wt%複合材料之DSC分析 37
圖2-10 MFC含量（wt%）對於（a）非晶態（b）結晶態複合材料儲存模數之影響 38
圖2-11 二氧化矽（silica）、漂白紙漿（BP）及兩者混合（BP/silica）之TGA曲線圖 39
圖2-12 複合材料之SEM分析圖 40
圖2-13 不同TEOS濃度與反應時間對於機械性質的影響 40
圖3-1 鳳梨葉纖維的鹼處理及酸中和處理的反應流程圖 56
圖3-2 改良之TEMPO自由基氧化法反應流程圖 57
圖3-3 鳳梨葉纖維溶膠-凝膠法表面改質之反應流程圖 58
圖3-4 鳳梨葉纖維處理之流程圖 58
圖3-5 鳳梨纖維與微纖絲化鳳梨纖維/聚乳酸複合材料製備流程圖 59
圖3-6 鳳梨葉纖維與聚乳酸複合材料的化學鍵結示意圖 60
圖4-1 鳳梨葉纖維之FT-IR分析圖 62
圖4-2 微纖絲化鳳梨葉纖維之FT-IR分析圖 62
圖4-3 PLF之13C固態核磁共振圖譜 64
圖4-4 MFC之13C固態核磁共振圖譜 64
圖4-5 SGLF之29Si固態核磁共振圖譜 65
圖4-6 SGC之29Si固態核磁共振圖譜 65
圖4-7 鳳梨葉纖維經不同化學改質前後之表面形態（a）未處理（b）鹼處理（c）溶膠-凝膠法（d）TEMPO氧化處理 67
圖4-8 微纖絲化纖維素（MFC）之TEM圖 68
圖4-9 鳳梨葉纖維素化學處理前後之TGA分析圖 70
圖4-10 聚乳酸與1 wt%纖維素補強複合材料之TGA分析圖 72
圖4-11 聚乳酸與3 wt%纖維素補強複合材料之TGA分析圖 72
圖4-12 聚乳酸與5 wt%纖維素補強複合材料之TGA分析圖 73
圖4-13 聚乳酸與1 wt%纖維素補強複合材料之DSC分析圖 75
圖4-14 聚乳酸與3 wt%纖維素補強複合材料之DSC分析圖 75
圖4-15 聚乳酸與5 wt%纖維素補強複合材料之DSC分析圖 76
圖4-16 聚乳酸與複合材料之扭矩值分析圖 78
圖4-17 聚乳酸與複合材料之HDT分析圖 80
圖4-18 聚乳酸與複合材料之拉伸強度分析圖 82
圖4-19 聚乳酸與複合材料之耐衝擊強度分析圖 84
圖4-20 聚乳酸與1 wt%纖維素補強複合材料DMA之儲存模數分析圖 87
圖4-21 聚乳酸與3 wt%纖維素補強複合材料DMA之儲存模數分析圖 87
圖4-22 聚乳酸與5 wt%纖維素補強複合材料DMA之儲存模數分析圖 88
圖4-23 聚乳酸與1 wt%纖維素補強複合材料DMA之損失模數分析圖 89
圖4-24 聚乳酸與3 wt%纖維素補強複合材料DMA之損失模數分析圖 89
圖4-25 聚乳酸與5 wt%纖維素補強複合材料DMA之損失模數分析圖 90
圖4-26 聚乳酸與1 wt%纖維素補強複合材料DMA之tan δ分析圖 91
圖4-27 聚乳酸與3 wt%纖維素補強複合材料DMA之tan δ分析圖 91
圖4-28 聚乳酸與5 wt%纖維素補強複合材料DMA之tan δ分析圖 92
圖4-29 結晶型態之POM分析圖（a）PLA（b）PLF1（c）SGLF1（d）MFC1（e）SGC1 94
圖4-30 纖維分散分析圖（a）PLF3（b）PLF5（c）SGLF3（d）SGLF5（e）MFC5（f）SGC5 96
圖4-31 複合材料經耐衝擊測試後之斷裂表面SEM圖（a）PLF（b）SGLF（c）MFC（d）SGC 98
圖4-32 聚乳酸與複合材料之透光度分析 99
圖4-33 聚乳酸與複合材料薄膜之透光示意圖 100

1.楊斌，PLA聚乳酸環保塑膠，五南圖書出版股份有限公司，2010年。
2.Spence, Kelley Lynn, Processing and Properties of Microfibrillated Cellulose, North Carolina State University; 2011.
3.日本生物可分解塑膠研究會，圖解生物可分解塑膠，世貿出版有限公司，2006年。
4.王國雄，聚乳酸的發展與市場應用，尖端材料科技協會季刊，2012年。
5.蘇明德，能自動分解的塑膠—可降解塑膠，科技發展，2010年。
6.三迪時空，http://www.3dfocus.com.cn/news/show-344.html
7.L.-T. Lim, R. Auras, M. Rubino, Processing technologies for poly(lactic acid), Progress in Polymer Science, 33, 820-52 (2008).
8.O. Faruk, A. K. Bledzki, H.-P. Fink, M. Sain, Biocomposites reinforced with natural fibers: 2000-2010, Progress in Polymer Science, 37, 1552-96 (2012).
9.A. Samir, F. Alloin, and A. Dufresne, Review of Recent Research into Cellulosic Whiskers, Their Properties and Their Application in Nanocomposite Field, Biomacromolecules, 6, 612-26 (2005).
10.T.W. Frederick, W. Norman, Natural fibers plastics and composites. Kluwer Academic Publishers, New York; 2004.
11.嘉義農業試驗分所，http://www.caes.gov.tw
12.王紅、邢聲遠，菠蘿葉纖維的開發及應用，紡織學報，第三卷，52-4 (2010)。
13.林忠誠，微米化纖維纖維素（MFC）於熱塑性複合材料的應用，工業材料雜誌，2011年。
14.N. Lavoine, I. Desloges, A. Dufresne, J. Bras, Microfibrillated cellulose – Its barrier properties and applications in cellulosic materials: A review, Carbohydrate Polymers, 90, 735-64 (2012).
15.E Brännvall, Aspect on Strength Delivery and Higher Utilisation of Strength Potential of Soft Wood Kraft Pulp Fibres. Royal Institute of Technology: Stockholm, Sweden; 2007.
16.M.J. John, S. Thomas, Biofibres and biocomposites, Carbohydrate Polymers, 71, 343-64 (2008).
17.J. Lu, P. Askeland, and L. T. Drzal, Surface modification of microfibrillated cellulose for epoxy composite applications, Polymer, 49, 1285-96 (2008).
18.F. W. Herrick, R. L. Casebier, J. K. Hamilton, and K. R. Sandberg, Microfibrillated cellulose: Morphology and accessibility, in Presented at the Conference: 9. Cellulose conference, Syracuse, NY, USA, 37, 797-813 (1983).
19.A. F. Turbak, F. W. Snyder, and K. R. Sandberg, Micro-fibrillated cellulose and process for producing it, Patent n◦ CH 648071 (A5) (1985).
20.M. Pääkkö, M. Ankerfors, H. Kosonen, A. Nykänen, S. Aloha, M. Osterberg et al., Enzymatic Hydrolysis Combined with Mechanical Shearing and High-Pressure Homogenization for Nanoscale Cellulose Fibrils and Strong Gels, Biomacromolecules, 8, 1934-41 (2007).
21.E.V. Gert, V.I. Torgashov, O.V. Zubets, and F.N. Kaputskii, Preparation and properties of enterosorbents based on carboxylated microcrystalline cellulose, Cellulose, 12, 517-26 (2005).
22.T. Kitaoka, A. Isogai, and F. Onabe, Chemical modification of pulp fibers by TEMPO-mediated oxidation, Nordic Pulp & Paper Research Journal, 14, 279-84 (1999).
23.S. Montanari, M. Roumani, L. Heux, and M. R. Vignon, Topochemistry of Carboxylated Cellulose Nanocrystals Resulting from TEMPO-Mediated Oxidation, Macromolecules, 38, 1665-71 (2005).
24.T. Saito and A. Isogai, TEMPO-mediated oxidation of native cellulose. The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions, Biomacromolecules, 5, 1983-9 (2004).
25.T. Saito, Y. Nishiyama, J.-L. Putaux, M. Vignon, and A. Isogai, Homogeneous Suspensions of Individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose, Biomacromolecules, 7, 1687-91 (2006).
26.T. Saito, Y. Okita, T. T. Nge, J. Sugiyama, and A. Isogai, TEMPO-mediated oxidation of native cellulose: Microscopic analysis of fibrous fractions in the oxidized products. Carbohydrate Polymers, 65, 435-40 (2006).
27.T. Saigo and A. Isogai, Introduction of aldehyde groups on surfaces of native cellulose fibers by TEMPO-mediated oxidation, Colloids and Surfaces A, 289, 219-25 (2006).
28.M. Hirota, N. Tamura, T. Saito, and A. Isogai, Water dispersion of cellulose II nanocrystals prepared by TEMPO-mediated oxidation of mercerized cellulose at pH 4.8, Cellulose, 17, 279-88 (2009).
29.T. Saito, M. Hirota, N. Tamura, S. Kimura, H. Fukuzumi, L. Heux, et al., Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions, Biomacromolecules, 10, 1992-6 (2009).

30.A. Isogai, T. Saito, and H. Fukuzumi, TEMPO-oxidized cellulose nanofibers, Nanoscale, 3, 71 (2011).
31.T. Isogai, T. Saito, and A. Isogai, Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation, Cellulose, 18, 421-31 (2011).
32.C. Aulin, S. Aloha, P. Josefsson, T. Nishino, Y. Hirose, M. Österberg, et al., Nanoscale cellulose films with different crystallinities and mesostructures—Their surface properties and interaction with water, Langmuir, 25, 7675-85 (2009).
33.T. Taipale, M. Österberg, A. Nykänen, J. Ruokolainen, and J. Laine, Effect of microfibrillated cellulose and fines on the drainage of kraft pulp suspension and paper strength, Cellulose, 17, 1005-20 (2010).
34.A. N. Nakagaito and H. Yano, The effect of morphological changes from pulp fiber towards nano-scale fibrillated cellulose on the mechanical properties of high-strength plant fiber based composites. Applied Physics A, 78, 547-52 (2004).
35.S. Iwamoto, A. N. Nakagaito, and H. Yano, Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites, Applied Physics A, 89, 461–6 (2007).
36.A. Dufresne, J.-Y. Cavaille, and M. R. Vignon, Mechanical behavior of sheets prepared from sugar beet cellulose microfibrils, Journal of Applied Polymer Science, 64, 1185–94 (1997).
37.A. Bhatnagar, and M. Sain, Processing of cellulose nanofiber-reinforced composites, Journal of Reinforced Plastics and Composites, 24, 1259–68 (2005).
38.B. Wang, and M. Sain, Isolation of nanofibers from soybean source and their reinforcing capability on synthetic polymers, Composites Science and Technology, 67, 2521–7 (2007).
39.P. Tingaut, T. Zimmermann, and F. Lopez-Suevos, Synthesis and characterization of bionanocomposites with tunable properties from poly(lactic acid) and acetylated microfibrillated cellulose, Biomacromolecules, 11, 454-64 (2009).
40.G. Rodionova, M. Lenes, Ø. Eriksen, and Ø. Gregersen, Surface chemical modification of microfibrillated cellulose: Improvement of barrier properties for packaging applications, Celullose, 18, 127-34 (2010).
41.P. Stenstad, M. Andresen, B. S. Tanem, and P. Stenius, Chemical surface modifications of microfibrillated cellulose, Cellulose, 15, 35–45 (2007).
42.吳人潔，複合材料，新文京開發出版股份有限公司，2004年。

43.Jianye Wen and Garth L. Wilkes, Organic/Inorganic Hybric Network Materials by the Sol-Gel Approach, Chem. Mater., 8, 1667-81 (1996).
44.黃仁宏，溶膠-凝膠法改質植物纖維/聚乳酸複合材料之製備及其特性分析，碩士論文，朝陽科技大學應用化學系，2013年。
45.R. K. Iler, The Chemistry of Silica, John Wiley & Sons, 1979.
46.C. Jeffrey Brinker, George W. Scherer, Sol-gel science : the physics and chemistry of sol-gel processing, Academic Press, Inc.; 1990.
47.W. Sujaritjun, P. Uawongsuwan, W. Pivsa-Art, H. Hamada, Mechanical property of surface modified natural fiber reinforced PLA biocomposites, Energy Procedia, 34, 664-72 (2013).
48.Y.-F. Shih, W.-C. Chang, W.-C. Liu, C.-C. Lee, C.-S. Kuan, Y.-H. Yu, Pineapple leaf/recycled disposable chopstick hybrid fiber-reinforced biodegradable composites, Journal of the Taiwan Institute of Chemical Engineers, 45, 2039-46 (2014).
49.A. Iwatake, M. Nogi, H. Yano, Cellulose nanofiber-reinforced polylactic acid, Composites Science and Technology, 68, 2103-6 (2008).
50.L. Suryanegara, A. N. Nakagaito, H. Yano, The effect of crystallization of PLA on the thermal and mechanical properties of microfibrillated cellulose-reinforced PLA composites, Composites Science and Technology, 69, 1187-92 (2009).
51.S. Sequeira, D. V. Evtuguin, I. Portugal, A. P. Esculcas, Synthesis and characterization of cellulose/silica hybrids obtained by heteropoly acid catalyzed sol-gel process, Materials Science and Engineering C, 27, 172-9 (2007).
52.A. Ashori, S. Sheykhnazari, T. Tabarsa, A. Shakeri, M. Golalipour, Bacterial cellulose/silica nanocomposites : Preparation and characterization, Carbohydrate Polymers, 90, 413-8 (2012)
53.吳寶芬，鳳梨產業現況及展望，101年度行政院農委會農民學院鳳梨栽培管理訓練班講義。
54.E. Espino-Pérez, S. Domenek, N. Belgacem, C. Sillard, and J. Bras, Green Process for Chemical Functionalization of Nanocellulose with Carboxylic Acids, Biomacromolecules, 15, 4551-60 (2014).
55.L.A. Colnago, M. Martins, L. Forato, L. Mattoso, A solid state 13C high resolution NMR study of raw and chemically treated sisal fibers, Carbohydrate Polymers, 64, 127-33 (2006).
56.F. Uhlig, H. C. Marsmann, 29Si NMR Some Pratical Aspects, Gelest, Inc.

57.Y. Habibi and A. Dufresne, Highly Filled Bionanocomposites from Functionalized Polysaccharide Nanoctystals, Biomacromolecules, 9, 1974-80 (2008).
58.H. Almasi, B. Ghanbarzadeh, J. Dehghannya, A. A. Entezami, A. K. Asl, Novel nanocomposites based on fatty acid modified cellulose nanofibers/poly(lactid acid): Morphological and physical properties, Food Packaging and Shelf Life, 5, 21-31 (2015).
59.M. R. Badrossamy and G. Sun, A Study on Melt Grafting of N-Halamine Moieties onto Polyethylene and Their Antibacterial Activities, Macromolecules, 42, 1948-54 (2009).