臺灣博碩士論文加值系統

本文有系統地實驗探討稀薄聚苯乙烯在單成分之高黏性溶液及雙成分之高黏彈性溶液其剪切流變的特性。一般對於高分子稀薄溶液系統在低剪切流場時皆能看到高分子的剪切黏度會呈現牛頓流體或剪切致稀的現象，但本研究發現於高剪切流場下，其剪切黏度會同時產生剪切致濃及第二個剪切致稀。此現象雖與分子理論預測相符，但到在此之前尚未有於實驗直接觀察到此種情形。此外，對於個別分子理論於高黏彈性之稀薄混合溶液系統的適用性，以及由長鏈聚苯乙烯之迴旋半徑的變化來分析其溶劑品質的差異，我們有詳細的比較與探討。

We performed systematical experimental investigations on the shearing rheology of dilute polystyrene in single, highly viscous (DOP) as well as in mixed, highly viscoelastic (DOP plus short-chain polystyrene) solvent systems. Following the usual shear thinning, a pronounced shear thickening followed by a second shear thinning was observed at even higher shear rates for both solvent systems. Significantly, this phenomenon is in excellent accord with the predictions based on dumbbell/bead-spring models that simultaneously consider the effects of hydrodynamic interactions, excluded volume, and finite extensibility, and this appears to be the first time that such a comprehensive rheological feature in shear flows has been experimentally verified. The previous phenomenon, nevertheless, vanishes for the mixed solvent system if there is only a moderate amount of short-chain polystyrene being added; namely, in this case one observed only a simple shear-shinning behavior. This was subsequently ascribed to the poor solvent quality with the addition of short-chain polystyrene, as suggested by earlier low-shear-rate viscometric measurements and light scattering data. This apparent change in solvent quality has been further verified here by the scaling behavior of the relaxation time constants evaluated at the onset of the first shear thinning, as well as by the molecular weight dependence of the measured intrinsic viscosity.

謝辭……………………………………………………………………………i
中文摘要……………………………………………………………………iii
英文摘要…………………………………………………………………….iv
目錄…………………………………………………………………………..v
圖目錄…………………………………………………………………….viii
表目錄……………………………………………………………………….ix
第一章 前言………………………………………………………………….1
1-1 文獻回顧………………………………………………………..1
1-2 研究動機………………………………………………………..3
第二章 理論背景…………………………………………………………….6
2-1 何謂高分子稀薄溶液…………………………………………..6
2-2 溶劑品質………………………………………………………..9
2-3 勞氏模型……………………………………………………...11
2-4 Zimm模型……………………………………………………...13
2-4-1 於θ溶劑之Zimm模型……………………………………..13
2-4-2 於好的溶劑之Zimm模型………………………………...15
2-5 Oldroyd-B模型………………………………………………..17
第三章 實驗方法…………………………………………………………..19
3-1 實驗藥品……………………………………………………...19
3-2 藥品配置……………………………………………………...20
3-2-1 純溶液系統的配置…………………………..……….…20
3-2-2 混合溶液系統的配置…………………………………...20
3-3 實驗儀器……………………………………………………...21
3-3-1 配置樣品之儀器………………………………………….21
3-3-2 樣品量測之儀器………………………………………….21
3-4 樣品的量測…………………………………………………...22
第四章 結果與討論………………………………………………………..24
4-1 高分子鏈之本質黏度的比較與探討.....................24
4-1-1 如何經由實驗來求得本質黏度………………………….24
4-1-2 本質黏度的應用………………………………………….26
4-2 高分子鏈之剪切黏度的比較與探討………………………...30
4-3 高分子鏈之鬆弛時間的比較與探討………………………...36
4-4 高分子鏈之迴旋半徑的比較與探討………………………….44
第五章 結論………………………………………………………………..48
參考文獻…………………………………………………………………….49
作者自述.....................................................52
圖目錄
圖2.1 高分子稀薄溶液示意圖………………………………………………6
圖2.2 高分子稀薄溶液之臨界濃度示意圖…………………………………7
圖2.3 高分子半稀薄溶液示意圖……………………………………………8
圖2.4 勞氏模型示意圖…………………………………………………….11
圖3.1 C.C.28.7夾具……………………………………………………….22
圖4.1 P 1之簡化黏度對高分子濃度作圖以求得本質黏度………………25
圖4.2 M 1之簡化黏度對長鏈高分子濃度作圖以求得本質黏度………..25
圖4.3 P 4至P 6之本質黏度對分子量的關係圖………….............29
圖4.4 P 7之高分子黏度對剪切速率的關係圖……………………………34
圖4.5 P 4至P 6之高分子黏度對剪切速率的關係圖…………………….34
圖4.6 M 1之長鏈高分子黏度對剪切速率的關係圖……………………..35
圖4.7 M 2之長鏈高分子黏度對剪切速率的關係圖……………………..35
圖4.8 M 1及M 2於325 K時長鏈高分子之 與 ……………………......41
圖4.9 M 1至M 4之鬆弛時間與分子量的關係圖………………………….42
圖4.10 M 1至M 4之本質黏度與分子量的關係圖………………………..43
表目錄
表3.1 本研究所使用的藥品表…………………………………………….19
表3.2 稀薄混合溶液系統………………………………………………….23
表3.3 稀薄純溶液系統…………………………………………………….23
表4.1 證明圖4.1及4.2皆屬於高分子稀薄溶液的狀態…………….....29
表4.2 M 1及M 2於325 K經實驗測得鬆弛時間與臨界剪切速率值……..40
表4.3 M 1及M 2於325 K經計算得知鬆弛時間與臨界剪切速率值……..40
表4.4 P 7、M 1及M 2於325 K之長鏈聚苯乙烯的迴旋半徑…………….47
表4.5 P 7、M 1及M 2在純溶液及混合溶液中高分子與溶劑的體積比..47

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