臺灣博碩士論文加值系統

本研究使用聚縮醛(POM)與聚乳酸(PLA)為基材，分別以奈米碳管(CNT)與石墨烯薄片(GNP)為填充材，利用雙螺桿押出機(Twin-screw extruder)製備POM/PLA摻合體、與摻合體為基材的奈米複合材料；並探討所製備樣品的相形態、晶體結構、熱性質、機械性質、流變性質與導電性。研究中以掃描式電子顯微鏡與光學顯微鏡分析相形態，證明摻合體樣品呈現單一相，且填充材分散良好。由熱重分析儀與微差掃描量熱儀分析樣品發現，熱穩定性降低與結晶度降低，確認了CNT與GNP表面之羧酸基團(－COOH)會使POM於摻混過程容易裂解。廣角X-ray繞射測試結果顯示，添加奈米碳管與石墨烯薄片並不影響POM/PLA摻合體之晶型結構。POM/PLA摻合體之拉伸模數、彎曲模數、固態儲存模數、熱變形溫度、熔融態儲存模數、複黏度與導電度皆因奈米碳管的添加而提升。雖然石墨烯薄片與奈米碳管同為擁有高剛性之填充材，但石墨烯薄片因其尺寸較大以及羧酸基團較多，和奈米碳管對POM/PLA摻合體性質的影響有顯著的不同。

In this study, carbon nanotube (CNT) and graphene nanoplate (GNP) served as reinforcing fillers to successfully prepare polyoxymethylene (POM)/ polylactide (PLA) blend-based nanocomposites by a twin-screw extruder. Morphology, thermal properties, mechanical properties, rheological properties, crystal structure, and electrical resistivity of the prepared samples were examined and compared with the another. Scanning electron microscope and polarized light microscope results confirmed the single phase of the POM/PLA blend and the nanofillers was finely dispersed in the blend matrix. The Fourier transform infrared spectroscopy data revealed weaker POM characteristic peaks in the composites. Thermogravimetric analysis showed that the thermal stability decreased with increasing CNT and GNP content in the composites compared to the blend. Differential scanning calorimetry results showed that POM crystallinity decreased with increasing CNT and GNP loading. The wideangle X-ray diffraction results showed that the addition of CNT and GNP did not affect the crystal structure of POM in the blend and composites. The tensile strength/modulus, flexural strength/modulus, solid state storage modulus, heat deflection temperature, and electrical conductivity improved with increasing CNT content in composites. The rheological properties measurement confirmed the achievement of pseudo-network structure in the composites after CNT loading in the composites.
Keywords：Polyoxymethylene, Polylactide, Blends, Nanocomposites, Physical properties

指導教授推薦書
口試委員審定書
致謝 iii
摘要 iv
英文摘要 v
目錄 vi
圖目錄 x
表目錄 xv
第一章 緒論 1
第二章 文獻回顧 4
2.1聚縮醛(Polyoxymethylene，POM) 4
2.2聚乳酸(Polylactide，PLA) 6
2.3奈米碳管(Carbon nanotube，CNT) 8
2.4石墨烯薄片(Graphene nanoplate，GNP) 11
2.5聚縮醛/聚乳酸摻合體 13
2.6聚縮醛奈米複合材料 17
2.7聚乳酸奈米複合材料 21
第三章 實驗 26
3.1 材料 26
3.2 儀器設備 26
3.3 樣品製備 29
3.3.1 押出樣品製備 29
3.3.2 射出試片製備 31
3.4 性質分析 31
3.4.1 掃描式電子顯微鏡 (SEM) 31
3.4.2 偏光顯微鏡 (PLM) 31
3.4.3 廣角X-ray繞射儀 (WAXD) 32
3.4.4 熱重損失分析儀 (TGA) 32
3.4.5 示差掃描量熱儀 (DSC) 32
3.4.6 耐衝擊試驗機 (Impact Test Machine) 33
3.4.7 萬能試驗機 (Universal Test Machine) 33
3.4.8 動態機械熱分析儀 (DMA) 33
3.4.9 流變儀 (Rheometer) 33
3.4.10 熱變形溫度試驗機 (HDT Test Machine) 34
3.4.11 電阻係數測試儀 (Resistance Meter) 34
3.5 實驗流程 35
第四章 結果與討論 36
4.1相形態 36
4.1.1掃描式電子顯微鏡 36
4.1.2光學顯微鏡 44
4.2晶體結構 52
4.3熱性質 55
4.3.1熱穩定性 55
4.3.2結晶行為 60
4.4.3熔融行為 66
4.4機械性質 71
4.4.1耐衝擊性質 71
4.4.2拉伸性質 74
4.4.3彎曲性質 79
4.4.4動態機械性質 82
4.4.5熱變形溫度 87
4.5流變性質 90
4.6導電性質 93
第五章 結論 96
參考文獻 98

 
圖目錄
圖2-1 聚縮醛近年來需求趨勢 5
圖2-2 丙交酯合成機制 7
圖2-3 富勒烯分類 9
圖2-4 (a) 單壁奈米碳管；(b) 多壁奈米碳管 之理想結構圖；(c) 單壁奈米碳管；(d) 雙壁奈米碳管；(e) 多壁奈米碳管 之TEM圖 10
圖2-5 扶椅型(Armchair)、拉鍊型(Zigzag)及對掌型(Chiral)奈米碳管 10
圖2-6奈米碳材分類 12
圖2-7 聚縮醛氧化機制 20
圖2-8 聚縮醛酸水解機制 20
圖3-1 樣品製備及分析流程圖 35
圖4-1-1 樣品SEM影像 (1000x)：(a) POM；(b) PLA；(c) M7A3；(d) M7A3-C0.5；(e) M7A3-C1.0 38
圖4-1-2 樣品SEM影像 (1000x)：(a) M7A3-C1.5；(b) M7A3-C2.0；(c) M7A3-C2.5；(d) M7A3-C3.0；(e) M7A3-G0.5 39
圖4-1-3 樣品SEM影像 (1000x)：(a) M7A3-G1.0；(b) M7A3-G1.5；(c) M7A3-G2.0；(d) M7A3-G2.5；(e) M7A3-G3.0 40
圖4-1-4 樣品SEM影像 (3000x)：(a) POM；(b) PLA；(c) M7A3；(d) M7A3-C0.5；(e) M7A3-C1.0 41
圖4-1-5 樣品SEM影像 (3000x)：(a) M7A3-C1.5；(b) M7A3-C2.0；(c) M7A3-C2.5；(d) M7A3-C3.0；(e) M7A3-G0.5 42
圖4-1-6 樣品SEM影像 (3000x)：(a) M7A3-G1.0；(b) M7A3-G1.5；(c) M7A3-G2.0；(d) M7A3-G2.5；(e) M7A3-G3.0 43
圖4-1-7 樣品於190 oC熔融之偏光顯微鏡影像 (20x)：(a) POM；(b) PLA；(c) M7A3；(d) M7A3-C0.5；(e) M7A3-C1.0 46
圖4-1-8 樣品於190 oC熔融之偏光顯微鏡影像 (20x)：(a) M7A3-C1.5；(b) M7A3-C2.0；(c) M7A3-C2.5；(d) M7A3-C3.0；(e) M7A3-G0.5 47
圖4-1-9 樣品於190 oC熔融之偏光顯微鏡影像 (20x)：(a) M7A3-G1.0；(b) M7A3-G1.5；(c) M7A3-G2.0；(d) M7A3-G2.5；(e) M7A3-G3.0 48

圖4-1-10 樣品以10 oC/min冷卻至室溫後之偏光顯微鏡影像 (20x)：(a) POM；(b) PLA；(c) M7A3；(d) M7A3-C0.5；(e) M7A3-C1.0 49
圖4-1-11 樣品以10 oC/min冷卻至室溫後之偏光顯微鏡影像 (20x)：(a) M7A3-C1.5；(b) M7A3-C2.0；(c) M7A3-C2.5；(d) M7A3-C3.0；(e) M7A3-G0.5 50
圖4-1-12 樣品以10 oC/min冷卻至室溫後之偏光顯微鏡影像 (20x)：(a) M7A3-G1.0；(b) M7A3-G1.5；(c) M7A3-G2.0；(d) M7A3-G2.5；(e) M7A3-G3.0 51
圖4-2-1 CNT奈米複合材料以10 ℃/min冷卻至室溫後之XRD圖譜 53
圖4-2-2 GNP奈米複合材料以10 ℃/min冷卻至室溫後之XRD圖譜 53
圖4-2-3 CNT奈米複合材料以40 ℃/min冷卻至室溫後之XRD圖譜 54
圖4-2-4 GNP奈米複合材料以40 ℃/min冷卻至室溫後之XRD圖譜 54
圖4-3-1 CNT奈米複合材料於氮氣中以20 ℃/min升溫之TGA圖譜 56
圖4-3-2 GNP奈米複合材料於氮氣中以20 ℃/min升溫之TGA圖譜 56
圖4-3-3 CNT奈米複合材料於空氣中以20 ℃/min升溫之TGA圖譜 57
圖4-3-4 GNP奈米複合材料於空氣中以20 ℃/min升溫之TGA圖譜 57
圖4-3-5 CNT奈米複合材料以10 oC/min降溫之DSC圖譜 62
圖4-3-6 GNP奈米複合材料以10 oC/min降溫之DSC圖譜 62
圖4-3-7 CNT奈米複合材料以40 oC/min降溫之DSC圖譜 63
圖4-3-8GNP奈米複合材料以40 oC/min降溫之DSC圖譜 63
圖4-3-9 CNT奈米複合材料以10 oC/min降溫後以20 oC/min升溫之DSC圖譜 68
圖4-3-10 GNP奈米複合材料以10 oC/min降溫後以20 oC/min升溫之DSC圖譜 68
圖4-3-11 CNT奈米複合材料以40 oC/min降溫後以20 oC/min升溫之DSC圖譜 69
圖4-3-12 GNP奈米複合材料以40 oC/min降溫後以20 oC/min升溫之DSC圖譜 69
圖4-4-1 樣品耐衝擊性質 72
圖4-4-2 樣品拉伸強度 76
圖4-4-3 樣品拉伸模數 76
圖4-4-4 樣品斷裂延伸率 77
圖4-4-5 樣品彎曲強度 80
圖4-4-6 樣品彎曲模數 80
圖4-4-7 樣品動態機械性質 (a) 儲存模數；(b) Tan δ 85
圖4-4-8 樣品熱變形溫度 88
圖4-5-1 樣品於190 ℃之流變性質：(a) 儲存模數；(b) 複粘度 對角頻率圖 92
圖4-6-1 樣品體電阻率 94

 
表目錄
表3-1 複合材料樣品配方表 30
表4-3-1 樣品於氮氣環境下TGA數據 58
表4-3-2 樣品於空氣環境下TGA數據 59
表4-3-3 樣品以10 °C /min降溫之DSC數據 64
表4-3-4 樣品以40 ℃/min降溫之DSC數據 65
表4-3-5 樣品以不同速率降溫後以20 ℃/min升溫之DSC數據 70
表4-4-1樣品耐衝擊強度數據 73
表4-4-2 樣品拉伸性質數據 78
表4-4-3 樣品彎曲性質數據 81
表4-4-4 樣品動態機械性質數據 86
表4-4-5 樣品熱變形溫度數據 89
表4-6-1 樣品體電阻率數據 95

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