臺灣博碩士論文加值系統

摘要(第一部份)
本研究以苯乙烯磺酸鈉(SSS)接枝PVA所得聚(乙烯醇-苯乙烯磺酸鈉)水膠，利用DSC來量測水膠中水的狀態，水膠中水的狀態分為三種，分別為鍵結水、界面水和自由水，由不同吸水量之熱分析曲線中，可觀察出水膠在0℃附近會有兩個吸熱峰出現，其中出現於較低溫者為界面水表現之吸熱峰，另一者為自由水表現之吸熱峰，隨吸水量越高，二者之吸熱峰會越靠近，且隨SSS含量越高，二者表現之吸熱峰會無法分辨，從熱分析的結果，利用熔融焓與吸水量的關係，可求得鍵結水含量，發現高接枝率水膠有較高的鍵結水量。從Pulsed NMR量測出的弛緩時間(T1、T2)均隨溫度的升高而增加，PVA-g-SSS水膠的T1值均較純水的T1值低，利用自旋晶格弛緩時間的對數與溫度的倒數作圖，可由斜率來求得水膠中水分子的活化能和鍵結水的活化能值。綜合水膠的熱分析和Pulsed NMR的結果，可發現水合作用過程中，以鍵結水扮演主要角色。從網路密度與弛緩時間的關係圖中，可發現隨交聯密度越高，弛緩時間越長。
摘要(第二部份)
本研究在幾丁聚醣(Chitosan)溶液中添加不同比例的glutaraldehyde以製成化學交聯水膠。由膨潤的實驗結果得知，隨交聯劑量的增加，水膠的平衡吸水率下降。從熱分析曲線中，可以觀察出不同吸水量水膠在熔融過程中水的狀態，從圖中僅可觀察出界面水和自由水表現之吸熱峰，由於無法將此二個峰分離，因此無法定量出二者的相對含量。從升溫曲線中發現，隨吸水量的提高，界面水表現之吸熱峰會愈來愈明顯，且由水膠的熔融焓值和不同吸水量的關係圖可看出，交聯劑含量較高者其鍵結水含量會較低。從核磁共振中，可以觀察出不同幾丁聚醣水膠的弛緩現象，幾丁聚醣水膠的弛緩時間(T1、T2)均隨溫度的升高而增加，從水膠中水分子的活化能，可得知水膠中水分子與高分子間有較純水之氫鍵弱的交互作用力存在，另外，藉由DSC和NMR的結果，可進而求得鍵結水的活化能(△Eb)，發現其幾乎等於水膠中水分子運動的活化能值(△E1)。

Abstract (Part Ⅰ)
The study utilizes DSC to reveal the information about bound 、interface and free water in hydrogels made up of poly(vinyl alcohol) grafted with sodium styrenesulfonate (SSS).DSC thermograms for gels show two water melting peaks around 0℃, where the one at the lower temperature is attributed to the interfacial state, and another to the free water. The above two melting peaks come closer with the higher water content in gels and higher SSS grafting. Pulsed NMR gives the temperature dependence of spin-lattice relaxation time (T1) and spin-spin relaxation time(T2) .Both T1 and T2 decrease with water content in gels, and are below the T1 and T2 value of water, respectively. The activation energy of T1 in gels for total water and bound water are not equal , due to the influence exerted by interface water on the water motion. It is seen that the bound water plays a significant role in the hydration, and the relaxation times (T1 and T2) become longer with the crosslink density of gels.
Abstract (Part Ⅱ)
This study investigates the chitosan chemically crosslinked with the various proportion of glutaraldehyde in the acetic acid solutions, leading to the findings that the equilibrium water absorption drops with the crosslinker amount. DSC thermograms for the ice fusion around 0℃ show the fusion shoulders for the interface and free water, respectively, and these two peaks become distinguishable at high water content in gels. The higher crosslinking gives rise to a lower amount of bound water. The Pulsed NMR gives the spin-lattice relaxation time (T1) and spin-spin relaxation time(T2) , revealing the lower water-polymer interations in gels than water-water interactions the pure state. Further calcuation on the activation energy of bound water shows the same values as the total water, which indicates that the water interations and are completely controlled by the bound water or free water, with negligible influence by the interface water.
This is maybe unstandable by the high amount of bound water binding to each monomer unit.

目錄
摘要(第一部份)I
ABSTRACT (PART Ⅰ)II
摘要(第二部份)III
ABSTRACT (PART Ⅱ)IV
誌謝V
目錄VI
圖表索引VIII
第一部份 聚(乙烯醇-苯乙烯磺酸鈉)水膠中水三相結構對水緩和運動與水合效應
一、前言1
二、實驗方法6
2-1材料的製備6
2-2膠化成型6
2-3水膠接枝率分析6
2-3-1檢量曲線之標定6
2-3-2接枝率測定7
2-4平衡膨潤測定7
2-5膨潤水膠在不同溫度下之彈性模數與交聯密度測定7
2-6微差掃描熱卡計分析8
2-7氫質子脈衝核磁共振儀(1H PULSED NMR)分析9
三、結果與討論11
3-1水膠成份分析11
3-2溫度對水膠膨潤的影響11
3-3水狀態的量測11
3-4脈衝核磁共振的量測13
3-4-1由弛緩時間探討水膠的活化能14
3-5弛緩時間與網路密度關係17
四、結論37
五、參考文獻39
第二部份CHITOSAN水膠中水三相結構對水緩和運動與水合效應
一、前言42
二、實驗部份46
2-1幾丁聚醣水膠之材料製備46
2-2平衡膨潤測定46
2-3微差掃描熱卡計分析46
2-4核磁共振儀(NMR)分析47
三、結果與討論48
3-1成份分析48
3-2溫度對水膠平衡吸水率的影響48
3-3交聯密度與吸水率的關係49
3-4三態水特性49
3-5核磁分析51
3-6由鍵結水活化能探討水合作用情形53
四、結論69
五、參考文獻70

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