臺灣博碩士論文加值系統

高分子結晶形態學是高分子科學中一個重要的領域，主要是研究並觀察晶體大小，形態及其聚集方式。但是由於高分子材料的特性，同時具有結晶態與非晶態，使得結晶形態更具有多樣性。而高分子結晶形態可透過顯微鏡直接觀察，所以在本研究中將利用偏光顯微鏡著重於高分子遠程結構「球晶」的形態觀察，並列舉一些關於球晶形態的特性與理論。

在本研究中，以PTT、PHB、PCL/SAN(9:1重量比)、PVDF等四個系統來討論同心消光圓環的形態與週期長度的問題。首先利用旋轉塗佈法製備三個系統之薄膜，之後利用偏光顯微鏡來觀察不同等溫結晶化溫度下的球晶同心消光環生長形態，並用CCD將其拍攝以便分析。然後再利用量測軟體來準確的求出同心消光環之週期長度與溫度之關係。
在觀察PTT與PHB同心環形態時，發現了雙色消光環的存在，此現象的產生與球晶的雙折射率值有關。當徑向折射率與切向折射率的差大於零，轉變至等於零，再到小於零，如此週期循環下，將有雙色消光環產生。除此之外，還發現同心消光環之中心具有兩種不同形態，分別為靶狀中心與螺旋狀中心。同時也發現同心消光環的圓環結構會隨著等溫結晶化溫度增加而從十分規整的圓環轉變至鬆散且呈zigzag的結構。至於同心消光環週期長度與過冷度之間的關係，採用彈性能量與晶板扭轉的關係並結合Thomson-Gibbs equation來描述。研究結果顯示PTT與PHB系統其同心環週期長度與過冷度之power law關係分別為-10與-8，和理論值(-3/2)相差甚遠，而PCL/SAN系統之power law值為-1.7則是與理論值相近，而PVDF系統則是考量不同分子量將由分子鏈的mobility大小影響，因此跳脫以分子鏈軸傾斜的為結構思考模式來研究同心消光環週期行為。研究發現PTT系統在不同厚度與不同的等溫結晶化溫度下，同心消光環出現範圍隨厚度的減小而變少，在所有厚度下之球晶現性成長速率可以疊成master curve且各厚度下之週期長度也呈現此一現象，因此認為球晶成長速率與膜厚無關也與同心環形態出現範圍無關，週期長度也不受膜厚影響。另外觀察PTT同心環形態分布圖發現在等溫結晶化溫度185℃之下不存在同心環結構，而從非等溫結晶化過程中，得到高溫區到185℃再到低溫區形態變化呈現有同心環到無同心環再到有同心環的形態出現，推測這一過程存在臨界行為。

The morphological study of crystalline polymer is very important field in polymer science, because polymer materials contain the property of crystalline as well as the amorphous state simultaneously. Such structural characteristic leads to various crystallization morphologies. We observed the morphological change during isothermal crystallization with a polarized light microscope. In this study, we paid attention to morphological change and periodic behavior of the ring banded spheroids.

Observing the morphologies of ring banded spheroids, we found that the double ring morphology was showed in PTT and PHB spherulites. We also observed the target or spiral morphologies in the center of PTT ring banded spherulites. Simultaneously, we observed the ring banded structure would be breakup with promoting isothermal crystallization temperature. In this study, four polymeric systems, PTT, PHB, PCL/SAN, PVDF, were studies to understand the morphological change and periodic spacing in ring banded spherulites. The theory proposed by Keith and Padden about the unbalance surface stress inducing lamellar twisting, was not compatible with the experimental results obtained by us. In thin film crystallization, we examine the distribution of PTT ring banded spherulites at different isothermal crystallization temperature which varied with film thickness. And then, we experiment with the linear growth rate and periodic spacing of PTT spherulites with all film thickness. The results proved that the linear growth rate was not influenced by distribution of PTT ring banded morphology; its periodic spacing and linear growth rate was not affected by the film thickness variation. It is worthwhile to mention that the appearance and disappearance of banded to non-banded structure was characterised in PTT as well. The morphologies of PTT spherulites changed from ring banded to non-ring banded, and then back to ring banded while the isothermal crystallization temperature jumps form 195℃ to 185℃ to 180℃ respectively. This result demonstrates that there might be a critical behavior during this process and a shape morphological transition would take place.

論文提要內容 I
Abstract II
目 錄 III
圖 表 目 錄 V
論 文 符 號 表 VII
第一章 前言 1
1.1 高分子鏈折疊 1
1.1.1 纓狀微束模型 2
1.1.2 折疊鏈模型 2
1.2 高分子球晶 3
1.2.1 球晶的形成 4
1.2.2 黑十字消光 5
1.2.3 正、負球晶 6
1.2.4 同心消光圓環的形態 6
1.3 同心消光圓環的生成理論 7
1.3.1 Bassett理論 7
1.3.2 Keith and Padden 理論 8
1.3.3 相場與同心消光環 9
1.3.4 形態轉變理論 10
1.3.5 晶板堆疊模型 11
1.4 研究目的 11
第二章 實 驗 13
2.1 實驗藥品 13
2.2 實驗儀器 14
2.3 實驗步驟 14
2.3.1 高分子薄膜製備與厚度量測 14
2.3.2 偏光顯微鏡觀察 15
2.3.3 同心消光環週期長度量測 15
第三章 結果與討論 18
3.1 高分子球晶形態觀察 18
3.1.1 雙色同心消光環形態研究 18
3.1.2 同心消光環中心形態觀察 19
3.1.3 同心消光環之圓環形態觀察 20
3.2 同心消光環週期性討論 22
第四章 總結 32
參考文獻 33

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