臺灣博碩士論文加值系統

本研究將奈米木質纖維經由冷凍乾燥技術，使奈米纖維有效的去除水分，過程中利用控制奈米纖維懸浮液的濃度來降低奈米纖維乾燥後之團聚現象，製備一系列之奈米纖維/聚乳酸複合材料。透過懸浮液處理，可降低奈米纖維之尺寸大小及增加比表面積，藉以提升奈米纖維與聚乳酸間的界面相容性及分散性，最後以熔融混煉的方式製備出複合材料。結果顯示，經過懸浮液處理後的奈米纖維可以提升與聚乳酸間的界面相容性，有效改善複合材料之機械性質與熱性質。由熱變形溫度分析，最高可提升49.05%；機械性質測試在奈米纖維添加0.5、1wt%時有較佳的性質，抗張強度最高提升29.74%，耐衝擊強度最高提升57.17%。從SEM分析可以觀察到奈米纖維與聚乳酸間緊密性良好，沒有明顯的孔洞產生，在斷裂面中的奈米纖維呈現截斷沒有被拔出的現象；從透光性測試中可以得知，當奈米纖維經過懸浮液處理，與聚乳酸製成薄膜能有效提升分散性進而提升薄膜的透光性。由以上結果顯示，添加了懸浮液處理的奈米纖維能提升聚乳酸之熱性質與機械性質，並且提高了複合材料之透明性。

In this study, the moisture of cellulose nanofibers from wood were effectively removed via freeze-dried technology. During this process, the agglomeration of nanofibers was reduced by controlling the concentration of nanofiber suspensions. Moreover, the dimension of the nanofibers will be reduced and the specific surface area will also be increased. Subsequently, the interfacial compatibility and dispersion between nanofibers and polymer matrix can be improved. Finally, a series of nanofibers/polylactic acid (PLA) composites are prepared by melt-blending. The results reveal that the interfacial compatibility between the PLA and nanofibers was improved after suspension treatment, so that the mechanical and thermal properties of the composites are elevated effectively. The heat deflection temperature test shows an increase of approximately 49.05% for PLA. In addition, the tensile and impact strengths increase around 29.74% and 57.47%, respectively when the composite material is reinforced with 0.5 and 1wt% content of suspension-treatment nanofibers. The better compatibility between nanofibers and PLA can be observed from SEM analysis that no hole is found and the nanofibers exhibit the phenomenon of truncating instead of pulling-out on the fracture surface. Moreover, the test of diaphaneity reveals that the transparency of the film can be effectively enhanced by the suspension treatment. The results show that the addition of the suspension-treatment nanofibers into PLA not only increases the mechanical and thermal properties of PLA, but also enhances the diaphaneity of the composite material

目錄
中文摘要 I
Abstract I
誌謝 III
目錄 IV
表目錄 VIII
圖目錄 VIII
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/可堆肥塑膠的測試與認定標準 4
1-3聚乳酸之簡介 7
1-3-1聚乳酸的單體及合成 8
1-3-3 聚乳酸的應用 10
1-4 奈米纖維素之簡介 13
1-4-1 奈米纖維素化學組成及特性 14
1-4-2 奈米纖維的發現 15
1-4-3 奈米纖維的製備 16
1-5 熱塑性奈米複合材料 21
第二章 文獻回顧及研究動機 26
2-1奈米纖維 26
2-2 奈米纖維補強高分子材料 30
2-3 研究動機 33
第三章 實驗內容 35
3-1 實驗藥品 35
3-2 儀器設備 37
3-3儀器測試方法及條件 40
3-4實驗概述 45
3-5實驗流程 47
3-5-1奈米纖維前處理 47
3-5-2奈米纖維補強聚乳酸複合材料 49
第四章 結果與討論 51
4-1 奈米纖維處理 51
4-1-1傅立葉轉換紅外線光譜儀測試(FT-IR) 51
4-1-2偏光顯微鏡測試(POM) 53
4-1-3掃描式電子顯微鏡測試(SEM) 56
4-1-4穿透式電子顯微鏡測試(TEM) 58
4-1-3熱重量分析儀測試(TGA) 60
4-2複合材料-熱性質分析 62
4-2-1熱重量分析儀測試(TGA) 62
4-2-2微差掃描式熱分析儀測試(DSC) 65
4-2-3 熱變形溫度測定儀測試(HDT) 70
4-3複合材料-機械性質分析 72
4-3-1萬能材料試驗機-抗張測試 72
4-3-2耐衝擊試驗機測試 74
4-3-3動態機械分析儀測試(DMA) 76
4-4複合材料-形態分析 81
4-4-1偏光顯微鏡測試(POM) 81
4-4-2掃描式電子顯微鏡測試(SEM) 84
4-5複合材料-生物可分解性分析 87
4-6透光性測試 89
第五章 結論 91
第六章 參考文獻 94

表目錄
表1-1生物分解國際標準 5
表1-2生質塑膠主要應用市場 12
表1-3纖維素名稱定義 14
表1-4各國家奈米材料研究情形 24
表3-1 奈米纖維代號 46
表3-2各組成比例及代號 46
表4-1奈米纖維裂解溫度、焦炭含量數據表 61
表4-2聚乳酸與奈米纖維複合材料TGA分析數據 64
表4-3奈米纖維複合材料的DSC分析數據 69
表4-4聚乳酸與複合材料HDT數據表 71
表4-5聚乳酸與奈米纖維複合材料之抗張強度數據表 73
表4-6聚乳酸與奈米纖維複合材料耐衝擊強度數據表 75
表4-7聚乳酸與奈米纖維複合材料DMA測試之儲存模數分析表 78
表4-8聚乳酸與奈米纖維複合材料DMA測試之損失模數分析表 79
表4-9乳酸與奈米纖維複合材料DMA測試之tanδ分析表 80
表4-10聚乳酸與複合材料生物可分解性重量損失率數據表 88
圖目錄
圖1-1直接聚合製備聚乳酸過程 9
圖1-2直接聚合製備聚乳酸過程 10
圖1-3全球生質塑膠市場趨勢 12
圖1-4纖維素的化學結構 15
圖1-5微纖纖維素製備方式及圖示 18
圖1-6 TEMPO-Mediated Oxidation作用機制 19
圖1-7微米化纖維纖維素於奈米複合材料應用說明 22
圖2-1纖維素酸水解示意圖 26
圖2-2木分層結構CNC及NFC 27
圖2-3不同機械處理奈米纖維SEM圖(A)微晶纖維素、(B)MFC均質化、(C)微流體、(D)研磨、(E)冷凍乾燥、(F)強力超音波 28
圖2-4奈米纖維不同懸浮液濃度SEM圖(e)1.0%、(f)0.5%、(g)0.1% 29
圖2-5纖維素含量對彎曲強度 30
圖2-6奈米晶鬚分散於PLA之TEM 31
圖2-7 MFC/PLA複合材料應力-應變圖 32
圖2-8 MFC/PLA複合材料楊氏模數 32
圖3-1 製備奈米纖維之流程圖 48
圖3-2製備奈米纖維複合材料之流程圖 50
圖4-1奈米纖維之FT-IR分析圖 52
圖4-2奈米纖維未經懸浮液處理之表面型態 54
圖4-3奈米纖維懸浮液處理濃度0.5wt%之表面型態 54
圖4-4奈米纖維懸浮液處理濃度0.5wt%之表面型態 55
圖4-5奈米纖維經過0.5wt%懸浮液處理之處理SEM圖 56
圖4-6奈米纖維經過懸浮液濃度0.1wt%之SEM圖 57
圖4-7奈米纖維經過0.5wt%懸浮液處理之TEM圖 58
圖4-8奈米纖維經過0.1wt%懸浮液處理之TEM圖 59
圖4-9奈米纖維經過0.1wt%懸浮液處理之高倍率TEM圖 59
圖4-10奈米纖維懸浮液處理後之TGA分析圖 61
圖4-11聚乳酸與奈米纖維複合材料之TGA分析圖 63
圖4-12聚乳酸與奈米纖維複合材料之DTG分析圖 64
圖4-13奈米纖維添加於聚乳酸中的DSC分析圖 67
圖4-14奈米纖維添加於聚乳酸中的Tg分析圖 68
圖4-15奈米纖維複合材料的Tc分析圖 68
圖4-16奈米纖維複合材料的Tm分析圖 69
圖4-17聚乳酸與複合材料之HDT分析圖 71
圖4-18聚乳酸與奈米纖維複合材料之抗張強度之分析圖 73
圖4-19聚乳酸與奈米纖維複合材料耐衝擊強度測試分析圖 74
圖4-20聚乳酸與奈米纖維複合材料DMA測試之儲存模數與溫度關係圖 78
圖4-21聚乳酸與奈米纖維複合材料DMA測試之損失模數與溫度關係圖 79
圖4-22聚乳酸與奈米纖維複合材料DMA測試之tanδ與溫度關係圖 80
圖4-23聚乳酸之結晶形態 82
圖4-24未處理奈米纖維/聚乳酸PC3複合材料之結晶形態 82
圖4- 25經處理奈米纖維/聚乳酸複合材料PSC0.5之結晶形態 83
圖4-26經處理奈米纖維/聚乳酸複合材料PSC3之結晶形態 83
圖4-27聚乳酸經耐衝擊測試後之斷裂表面SEM圖 85
圖4-28未處理奈米纖維/聚乳酸複合材料之耐衝擊試驗後斷裂面SEM圖 85
圖4-29經處理奈米纖維/聚乳酸複合材料之耐衝擊試驗後之斷裂面SEM圖 86
圖4-30聚乳酸與奈米纖維複合材料生物可分解性分析圖 88
圖4-31聚乳酸與奈米纖維複合材料的透光性分析 90
圖4-32聚乳酸與奈米纖維複合材料薄膜的透光性示意 90

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