臺灣博碩士論文加值系統

本研究是利用超臨界二氧化碳製造TPU發泡材料，並探討其操作條件如含浸溫度與泡孔形態之關係。之後在熱塑性聚氨酯中添加少量不同的無機奈米顆粒，製備成奈米複合發泡材料，觀察其泡孔形態，找尋最佳之奈米填充材料。將TPU奈米複合材料進行分散形態、黏度、力學性質等表徵之測試。最後，也將TPU奈米複合發泡材料進行力學性能之測試，探討泡孔型態對力學性能之影響。
實驗結果顯示，在TPU內添加五種不同的奈米顆粒(Clay30B、Clay20A、CNT、CNF、H05)，以Clay30B作為異相成核劑之效果最好，明顯縮小泡孔及提升泡孔密度。添加Caly30B含量增加，cell density上升，且foam density隨之下降，而含浸溫度下降到50℃，成功獲得cell size小至450nm之奈米泡，且cell density維持在1011cells/cm3。添加奈米顆粒可以增加材料之機械性質，經拉伸試驗結果，在未發泡時Clay30B添加量提升，楊氏模數和降伏強度上升，但是斷裂伸長率會下降。而材料經發泡程序後，泡孔大小會影響材料之機械性質，當泡孔小至數百奈米時，其機械性質下降程度也愈小，添加1wt%的Clay30B可以增加發泡體的楊氏模數和降伏強度，而且材料的斷裂伸長率不變。因此可以利用含浸溫度及Clay30B含量來操控泡孔大小和發泡材之密度，獲得理想之發泡材料。

In this study, thermoplastic polyurethane (TPU) was foamed by batch foaming using CO2 as the blowing agent, and the effect of saturation temperature on cell morphology TPU foam was examined. Five different nanoparticles were compounded with TPU as the nucleation agent. Among the five different nanoparticles(Clay30B、Clay20A、CNT、CNF、H05), Clay30B seems to be the best nucleation agent, because it had the smallest cell size and the highest cell density in the result of batch foaming.
Adding 1wt% 30B nanoclay resulted in submicron sized foam. With the increasing content of Clay30B led to increase in the cell density, while the foam density decreases. The cell size could be as low as 450 nm while the cell density could be as high as 1011 cells/cm3.
Finally, the effect of cell morphology to the mechanical properties of foamed samples was also investigated. It was found that adding 1wt% nanoclay not only could improve the mechanical properties of the solid, it can also increase the modulus of the foamed nanocomposite significantly.

摘　要 I
ABSTRACT III
誌　謝 V
目錄 VI
表目錄 X
圖目錄 XI
第一章 緒論 1
1.1 前言 1
1.2 研究動機 3
第二章 相關理論與文獻回顧 5
2.1 熱塑性聚氨酯(Thermoplastic Polyurethane)簡介 5
2.1.1 熱塑性聚氨酯之反應及原料 5
2.1.2 熱塑性聚氨酯之機械性質 7
2.2 高分子發泡材料 8
2.2.1 發泡過程 9
2.2.2 發泡劑 12
2.2.2.1化學發泡劑 12
2.2.2.2物理發泡劑 13
2.2.3 超臨界微細發泡技術 14
2.2.3.1 超臨界流體之特性 14
2.2.3.2 超臨界CO2之溶解度 17
2.3 高分子奈米複合材料 22
2.3.1 高分子奈米複合材料之製備 22
2.3.2 高分子奈米複合材料之結構 24
2.3.3 高分子奈米複合材料之性能 25
2.3.3.1 機械性能(Mechanical property) 25
2.3.3.2 熱穩定性能(Thermal stability) 26
2.3.3.3 氣體阻隔性能(Barrier property) 26
2.3.3.4 阻燃性能(Flame retardancy) 27
2.4 黏土之簡介 27
2.5 碳材之簡介 31
第三章 實驗方法 35
3.1實驗藥品 35
3.2實驗儀器 39
3.3 實驗流程圖 42
3.4 實驗步驟 43
3.4.1 樣品比例 43
3.4.2熱塑性聚氨酯奈米複合材料之製備 44
3.4.3 批式發泡程序 46
3.4.3.1 顆粒發泡 46
3.4.3.2 啞鈴型試片發泡 47
3.5 測量方法 48
3.5.1 X-ray繞射儀(XRD) 48
3.5.2 穿透式電子顯微鏡(TEM) 49
3.5.3 掃描式電子顯微鏡(SEM) 49
3.5.4 流變測試 49
3.5.5 二氧化碳含浸量測量 50
3.5.6 發泡材之密度測量 50
3.5.7 泡孔孔徑尺寸(cell size)計算 51
3.5.8 泡孔密度(cell density)計算 51
3.5.9 機械性質之測量 51
3.5.10 FTIR 53
第四章 結果與討論 54
4.1 純TPU之二氧化碳含浸量測量 54
4.2 添加各種不同的奈米顆粒發泡之泡孔型態分析 56
4.3 TPU/CLAY30B奈米複合材料 58
4.3.1 TPU/Clay30B奈米複合材料之XRD分析 58
4.3.2 TPU/Clay30B奈米複合材料之TEM分析 60
4.3.3 TPU/Clay30B奈米複合材料之黏度分析 62
4.3.4 TPU/Clay30B奈米複合材料之FTIR分析 62
4.4 泡孔型態分析 65
4.4.1 含浸溫度對泡孔型態之影響 65
4.4.2 Clay30B的含量對泡孔型態之影響 66
4.5 TPU/Clay30B奈米複合材料之機械性質 72
4.5.1 固體之機械性質 72
4.5.2 發泡體之機械性質 75
第五章 結論 81
未來工作 82
參考文獻 83
附錄A 高壓批式發泡 93
第一章 實驗步驟 93
第二章 實驗結果 95
附錄B TPU之CO2含浸飽和時間計算 103

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