臺灣博碩士論文加值系統

本研究主旨在於分析高分子材料於熔融狀態之暫態剪切流動行為，探討兩次剪切間隔時間、剪率、溫度對材料暫態黏度（或應力增長）之影響，並且嘗試量化黏彈性流體在啟動剪切之後，其分子結構恢復所需時間。本研究所選用之材料為聚碳酸酯，其為一常見的熱塑型工程塑膠，具優良耐衝擊性，並常應用於樹酯鏡片、燈罩等光學相關產品。本研究首先利用平板式流變儀進行暫態剪切流動實驗，取得暫態黏度數據，其次應用流變學模式(White-Metzner and the convected Jeffrey model)來分析瞬間啟動剪切之流變行為，並且聚焦在觀察啟動流動瞬間的應力過衝現象。由結果得知，於第一次啟動剪切，因為高分子鏈之不定向排列，其應力過衝會很明顯，而且當剪切率越高，高分子鏈的彈性效應也較顯著，應力過衝數值亦會越高。在進行第二次剪切實驗，其與第一次剪切結束不同間隔時間，高分子鏈產生不同程度的重新排列，時間隔越久分子鏈恢復就越多，遂造成其應力過衝程度較趨近於第一次剪切應力過衝數值。再者，實驗溫度是影響高分子材料黏彈性之重要因素，本研究發現於相同剪率下，溫度較低其材料彈性效應較強，所得的應力過衝現象也較顯著。

The main purpose of this research is to analyze the transient shear flow behavior of polymer materials in the molten state. The effects of two shear intervals, shear rate, and temperature on the transient viscosity (or stress increase) of the material were investigated, and attempts were made to quantify the time required for the recovery of the molecular structure of the viscoelastic fluid between two consecutive instant shearing. The material selected for this study is polycarbonate, which is a common thermoplastic engineering plastic with highimpact resistance. In this study, the plate-type rheometer was used to obtain thetransient viscosity data. BoththeWhite-Metzner and the convected Jeffrey models were used to analyze the rheologyof the instantshear flow, focusing on tracking the stress overshoot accompanying thestart-up of the shearing flow. From the results, it can be seen that when the shear flow starting for the first time, the stress overshoot could be very apparent because the polymer chains are randomly coiled, and the higher the shear rates, the more elastic the polymer chainsare; thus the extent of the overshoot becomes higher.Bytheimmediateconsecutiveshearing, the polymer chains couldberecoiled to variantextentsinaccordancewiththetimeintervalsfrom the first shearing. The longer the time intervals, the more the molecular chainsare recovered, and thusthe stress is growing up more obviously. Ultimately, itisapproaching the stress overshoot for the first-time shearing. It is known that the temperature is an important factor influencing the viscoelastic properties forthe polymer materials. In this study, it was found that under the same shear rate, the material at lower temperature possessed stronger elasticity, and the resulting stress overshoot at the start-up of shear flow wasmore significant.

中文摘要 I
英文摘要 II
致謝 IV
本文目錄 V
表目錄 IX
圖目錄 X
符號說明 XIV
第一章 緒論 1
1.1 前言 1
1.2 文獻回顧 4
1.3 研究動機與目的 12
1.4 論文架構 14
第二章 理論介紹 16
2.1 射出成型製程 16
2.2 流變學理論介紹 17
2.2.1 White Metzner model 17
2.2.2 The convected Jeffrey’s model 19
第三章 研究方法 23
3.1 實驗材料 23
3.1.1 PC(聚碳酸酯) 23
3.1.2 改質蒙脫土(Cloisite 30B) 24
3.1.3 高分子/蒙脫土複合材料之製備方法 26
3.1.4 高分子/蒙脫土複合材料之分析 30
3.2 實驗設備及分析儀器 31
3.2.1 塑譜儀(Mixer) 31
3.2.2 熱壓成型機(Hydraulic Compression Molding Machine) 31
3.2.3 烘箱(Vacuum Dry Oven) 32
3.2.4 熱重損失分析儀(Thermal Gravimetric Analyzer, TGA) 32
3.2.5 示差掃描式熱卡計(Differential Scanning Calorimeter, DSC) 33
3.2.6 X光繞射分析儀(X-ray Diffractometer, XRD) 33
3.2.7 流變儀(Rheometer) 34
3.3 實驗流程 35
3.4 材料性質測試與分析 36
3.4.1 穩態剪切測試 37
3.4.1 頻率掃描 38
3.4.2 啟動剪切實驗 39
3.4.3 熱重損失測試(TGA) 40
3.4.1 示差掃描式熱卡計(Differential Scanning Calorimeter, DSC) 40
3.4.2 X光繞射分析儀(XRD) 41
第四章 結果與討論 42
4.1 熱重損失分析實驗 42
4.2 示差掃描式熱卡計(Differential Scanning Calorimeter, DSC) 48
4.3 X光繞射分析儀(XRD) 50
4.4 穩態實驗 52
4.5 動態實驗 56
4.6 溫度掃描實驗 60
4.7 暫態剪切實驗 63
4.7.1 暫態實驗改變剪率之比較(0.1~0.9 1/s) 63
4.7.2 暫態實驗改變溫度之比較(220℃~260℃) 69
4.7.3 暫態實驗改變摻合物比例(1wt%~5wt%) 70
4.7.4 暫態實驗改變休息時間比較(0sec~1200sec) 71
4.7.5 暫態實驗數值擬合分析 80
第五章 結論 86
第六章 未來研究方向 88
第七章 參考文獻 89
附錄(A)The ConvectedJeffreys Model 數學模型推導 93
附錄(B)White-Metzner Model公式推導 98
附錄(C) White-Metzner model 暫態黏度公式推導 101
作者簡介 103

 
第5章 表目錄
表3.4.1穩態剪切實驗操作條件 37
表3.4.2頻率掃描實驗操作條件 39
表3.4.3暫態實驗操作條件表 40
表4.1.1不同比例PC/Cloisite30B摻合物熱重損失數據表 47
表4.7.1純PC暫態實驗擬合結果整理(鬆弛時間) 83
 
第6章 圖目錄
圖1.1.1泛用塑膠、工程塑膠與高性能塑膠分類 3
圖2.2.1 Whtie-Metzner model 暫態黏度公式預測圖 19
圖2.2.2數據擬合流程圖 22
圖3.1.1蒙脫土層狀結構[41] 24
圖3.1.2蒙脫土化學結構[25] 25
圖3.1.3高分子複合材料原位聚合示意圖[42] 26
圖3.1.4高分子複合材料以溶劑法聚合示意圖[42] 27
圖3.1.5以熔融法製備高分子/蒙脫土複合材料[42] 28
圖3.1.6不同比例PC/Cloisite30B摻合物摻混樣品圖 29
圖3.2.1塑譜儀 31
圖3.2.2熱壓成型機 31
圖3.2.3烘箱 32
圖3.2.4熱重損失分析儀 32
圖3.2.5示差掃描式熱卡計 33
圖3.2.6 X光繞射分析儀 33
圖3.2.7 MCR 101 流變儀 34
圖3.3.1實驗流程圖 35
圖3.4.1不同流變黏度量測範圍 36
圖4.1.1純Cloisite 30B熱重損失 45
圖4.1.2純 Cloisite 30B 熱重損失(於240℃維持13分鐘) 45
圖4.1.3不同比例PC/Cloisite30B摻合物熱重損失圖 46
圖4.2.1不同比例PC/Cloisite30B摻合物於第二次升溫示意圖 49
圖4.3.1不同比例PC/Cloisite30B摻合物之XRD圖 51
圖4.4.1純料聚碳酸酯不同溫度下穩態剪切剪切黏度 53
圖4.4.2不同比例PC/Cloisite30B摻合物於220℃穩態剪切黏度 53
圖4.4.3不同比例PC/Cloisite30B摻合物於240℃穩態剪切黏度 54
圖4.4.4不同比例PC/Cloisite30B摻合物於260℃穩態剪切黏度 54
圖4.4.5純料PC與不同比例PC/Cloisite30B摻合物於240℃穩態剪切黏度結果比較 55
圖4.5.1純聚碳酸酯不同溫度下複合黏度比較 57
圖4.5.2純聚碳酸酯不同溫度下儲存及損失模數比較 58
圖4.5.3不同比例PC/Cloisite30B摻合物於220℃複合黏度 58
圖4.5.4不同比例PC/Cloisite30B摻合物於220℃儲存及損失模數 59
圖4.6.1純料聚碳酸酯溫度掃描 61
圖4.6.2不同比例聚碳酸酯/PC/Cloisite30B摻合物溫度掃描 61
圖4.6.3純料聚碳酸酯與不同比例PC/Cloisite30B摻合物溫度掃描 62
圖4.7.1純PC暫態黏度實驗於220℃改變剪切速率 65
圖4.7.2純PC暫態黏度實驗於240℃改變剪切速率 65
圖4.7.3純PC暫態黏度實驗於260℃改變剪切速率 66
圖4.7.4 PC摻混1wt% Cloisite30B暫態實驗改變剪切速率 66
圖4.7.5PC摻混3wt% Cloisite30B暫態實驗改變剪切速率 67
圖4.7.6PC摻混5wt% Cloisite30B暫態實驗改變剪切速率 67
圖4.7.7純料聚碳酸第一次暫態剪切實驗(剪率= 0.01 1/s) 69
圖4.7.8不同比例PC/Cloisite30B摻合物於240℃暫態黏度比較 70
圖4.7.9純料聚碳酸酯暫態剪切改變休息時間 72
圖4.7.10純料聚碳酸酯暫態剪切改變休息時間 72
圖4.7.11純料聚碳酸酯暫態剪切改變休息時間 73
圖4.7.12純料聚碳酸酯暫態剪切改變休息時間 73
圖4.7.13純料聚碳酸酯暫態剪切改變休息時間 74
圖4.7.14純料聚碳酸酯暫態剪切改變休息時間 74
圖4.7.15純料聚碳酸酯暫態剪切改變休息時間 75
圖4.7.16純料聚碳酸酯暫態剪切改變休息時間 75
圖4.7.17純料聚碳酸酯暫態剪切改變休息時間 76
圖4.7.18純料聚碳酸酯暫態剪切改變休息時間 76
圖4.7.19純料聚碳酸酯暫態剪切改變休息時間 77
圖4.7.20純料PC暫態剪切改變休息時間 77
圖4.7.21 PC摻混1wt% Cloisite 3B 240℃暫態實驗改變休息時間 78
圖4.7.22 PC摻混3wt% Cloisite 3B 240℃暫態實驗改變休息時間 78
圖4.7.23 PC摻混5wt% Cloisite 3B 240℃暫態實驗改變休息時間 79
圖4.7.24純PC於剪切速率0.1(1/s)不同溫度下休息時間擬合結果 81
圖4.7.25純PC於剪切速率0.3(1/s)不同溫度下休息時間擬合結果 81
圖4.7.26純PC於剪切速率0.5(1/s)不同溫度下休息時間擬合結果 82
圖4.7.27純PC於剪切速率0.7(1/s)不同溫度下休息時間擬合結果 82
圖4.7.28純PC 不同溫度暫態擬合結果整理(鬆弛時間) 83
圖4.7.29純PC於220℃暫態實驗數據與擬合預測結果比較 84
圖4.7.30純PC於240℃暫態實驗數據與擬合預測結果比較 84
圖4.7.31純PC於260℃暫態實驗數據與擬合預測結果比較 85

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