臺灣博碩士論文加值系統

本文為研究聚四甲基一戊烯(Poly(4-methyl-l-pentene), TPX)於非等溫結晶過程的動力行為。我們針對TPX(聚四甲基一戊烯之商業用名)的試片各照射250 kGy到1000 kGy的四種加瑪射線(gamma-ray)劑量，研究照射劑量對動力行為影響，照射環境分別為在空氣及氧氣的兩種條件。對非等溫過程取七種不同的冷卻速率為每分鐘1℃、2.5℃、5℃、10℃、20℃、40℃ 及 60℃以研究非等溫結晶。
經由熱差分析儀(Differential Scanning Calorimetry, DSC)測到資料顯示，低加瑪射線劑量條件下的波形是較高的加瑪射線劑量顯得明顯意見，在通入氧氣的條件後照射，波形是更不易見的，藉由波形計算放熱量以求得相對結晶曲線，而照射劑量與冷卻速率皆會影響結晶溫度。
獲得相對結晶曲線後利用Ozawa理論對聚四甲基一戊烯研究其結晶參數。在研究過程我們對部份發生雙波的曲線使用修改過的高斯函數做分離，以獲得正確的相對結晶曲線，解決原相對結晶曲線在同劑量下不同冷卻速率卻發生相交的問題。
使用Ozawa理論分析後，我們發現Ozawa指數有兩種趨勢，一是相同冷卻速率區間中，隨著結晶溫度下降(照射影響)Ozawa指數亦隨之下降，而另一趨勢為相同照射劑量下，隨著冷卻速率增加Ozawa指數亦隨之增加。分析結果顯示Ozawa指數在1.0~3.0之間。
經由研讀Ozawa非等溫結晶動力理論，我們發現其理論之原始實驗數據是基於低冷卻速率(1℃~4℃)下建立的，因此許多文章提及Ozawa理論不合用，是應先回歸其理論適用範圍，再進一步討論為宜，相當多論文之冷卻速率選取是超過範圍的。另外我們亦對活化能進行估算，採用Kissinger理論，根據其原始文獻推導，其活化能計算式為適用於結晶成長速率最大值處的溫度，相當於結晶量對時間的二次微分處，而不一定發生於峰值溫度處。

We apply gamma ray irradiation from 250 kGy to 1000 kGy on Poly(4-methyl-l-pentene) (commercial name is TPX) specimens in air and oxygen environment. During DSC tests, we set different cooling rates to measure the data of TPX specimens. We proceeded the cooling rate by 1℃、2.5℃、5℃、10℃、20℃、40℃ and 60℃ per minute.
The DSC data indicated that the specimens with low gamma-ray dose have large peak which is clear to see, and in high gamma-ray dose the peak become small and not easy to see, especially the specimens irradiated in oxygen environment.
In order to proceed the non-isothermal crystallization kinetics of irradiated Poly(4-methyl-1-pentene), we separate the double peak curve by modified Gaussian equation with gama distribution .
For TPX non-isothermally crystallized by cooling at constant rates, we can find exponent n in Ozawa plots with two tendencies. One is that Ozawa exponent n decreases with decreasing crystallization temperature for the same interval of cooling rates, the other is the exponent n increasing with increasing cooling rates. We have a conclusion that Ozawa apparach method can not meet the high cooling rates data. For the study of Poly(4-methyl-l-pentene), it can be seen that Ozawa exponent n increases with increasing crystallization temperature, n is almost from 1.0 to 3.0, which means the pre-determined nuclei might exist before cooling.

Abstract
Acknowledgment
Contents
Introduction1
Experimental Procedure8
Results and Discussion10 Conclusions20
References22
List of Tables26
Tables29
Figure Captions46
Figures52

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