高分子結晶化機制是高分子物理領域中相當重要的議題。我們使用時間解析傅立葉變換紅外光譜、廣角X-ray 繞射、小角光散射與偏光顯微鏡得到的數據分析來了解全同立構聚苯乙烯冷結晶機制。
藉由紅外光譜特徵峰相關參數的物理意義搭配廣角X-ray 繞射、去極化光散射的資訊，我們發現全同立構聚苯乙烯的螺旋結構在結晶相出現前會有分子聚集現象發生；接著，分子鏈為了排入晶格之中，需要消除分子內π-π 相互作用力；最後當結晶成長到了一定厚度後，紅外光譜中m≥16 的螺旋含量增加來源於結晶沿分子間方向生長。
透過小角度光散射與偏光顯微鏡的資訊，我們發現在全同立構聚苯乙烯的等溫冷結晶會出現球晶的型態，分析小角度光散射的數據可以計算球晶尺寸隨時間的變化，我們推測球晶產生的原因或許與結晶化前期的分子聚集有關。
最後，我們將不同結晶溫度所得結果綜合起來，繪出一張完整的時間-溫度-轉變相圖來表徵結晶動力學上的狀態，並透過二維相關光譜可發現，在不同的結晶溫度下，所表現出的初始狀態可能會有所不同，而差異主要來源於3/1 螺旋m≥5 與苯環-苯環二聚體之含量。

The mechanism of polymer crystallization was one of the important issue in polymer physics. The data of time-resolved Fourier transform infrared spectroscopy, wide-angle Xray diffraction, small-angle light scattering and polarized optical microscope were analyzed to clarify the mechanism of cold crystallization on isotactic polystyrene.
We proposed a mechanism for cold crystallization of isotactic polystyrene by comparing the IR, wide-angle X-ray diffraction and depolarized light scattering data. Before the crystalline generated, aggregation of polymer chain occurred. The polymer chain then adjusted the conformation and eliminated the inter-chain π-π interaction in order to align to lattice. At the last period of crystallization, the increasing helix content of m≥16 was come from the growth along inter-chain direction instead of intra-chain direction.
We found that spherulite structure appear in cold crystallization of isotactic polystyrene by data of depolarized small-angle light scattering and polarized optical microscope. The growth of spherulites could calculate by small-angle light scattering data. We assumed that the aggregation in the induction period impact on the morphology.
Lastly, we compared results for different cold crystallization temperature and sketched a time-temperature-transition diagram to represent the crystallization kinetics. It was found that there was some differences for the initial state of different crystallization temperature by two dimensional correlation spectroscopy. The differences came from the amounts of 3/1 helix with sequential length m≥5 and phenyl-phenyl dimer in the system.

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