本實驗主要是以小角度X光散射 (small-angle X-ray scattering, SAXS)，與微差掃瞄式卡計 (differential scanning calorimetry, DSC)，來研究無定形-結晶性團聯式共聚合物 (amorphous-crystalline block copolymer, A-b-C) 之摻合體在不同摻合比例下的微相分離形態及結晶行為。
團聯式共聚合物多會因自我聚集行為而形成微相分離 (microphase separation)，隨著兩段鏈長的比例不同，會產生不同的微結構。當A-b-C共聚合物摻合入A段的均聚物時，隨著摻合比例的不同，將對A段的高分子體積分率產生影響，進而改變微相分離形態，因此我們可利用摻合的方法，得到不同微相分離形態。若結晶段 (C段) 所形成的微相為非連續相 (microdomains)，則其結晶行為將有別於純高分子在bulk的結晶行為，我們可將這類的結晶視為在奈米級限制空間下 (nano-confined space) 的結晶。隨著結晶空間急遽減少的情形下，結晶性高分子的結晶行為將有很大的改變。

我們研究的系統，主要是 poly(butadiene-b-ethylene oxide) (PB-b-PEO) 與不同比例PB之摻合。由SAXS的結果可得知，摻合體的微相分離形態會因摻合入的PB比例不同而隨之轉變，在PB總體積分率達0.65之前，屬於層狀 (lamellae) 排列之微相分離形態；當PB總體積分率達0.69∼0.81之間時，則形成六角形堆積之圓柱 (hexagonally packed cylinder) 排列；而當PB總體積分率在0.83以上時，微相分離形態即轉變為體心立方堆積之圓球 (body-centered cubic packed sphere)。

此外，將這些具有不同微相分離形態的摻合體做DSC降溫實驗，可以發現在不同的微相分離形態下，摻合體中的PEO段之結晶溫度 (Tf) 有極明顯的變化，層狀形態的摻合體所表現的結晶速率最快，其次為圓柱狀形態，而兩者間的結晶速率有極大的差異，至於圓球形態的摻合體則有最慢的結晶速率。這結果顯示團聯式共聚合物的結晶行為會受到微相分離形態的影響。主要是因為結晶速率的快慢取決於結晶成分在空間上的連續與否，當結晶成分在空間上不連續時，為了順利達成結晶程序，各microdomain內必須有自己的晶核，因此總體來說要大量增加晶核數目，所以整體而言結晶速率會下降。由於成核需要較長的時間，所以結晶的速率決定步驟便在成核步驟，另外在microdomain中無法包含巨觀的粒子 (macroscopic particle) 來引發非均相成核 (heterogeneous nucleation) ，因此在microdomain中的成核步驟是屬於均勻相成核 (homogeneous nucleation)，此均勻相成核步驟是在不同微相分離形態下結晶速率的控制主因。

Microdomain structures of binary mixtures of poly(butadiene-b-ethylene oxide) diblock polymer (PB-b-PEO) and homopolybutadiene (PB) were investigated as a function of volume fraction of PB in the mixtures by using small angle X-ray scattering (SAXS). The crystallization behaviors of these blends were also studied by differential scanning calorimetry (DSC) to combine the data with microstructures. When blending in 0.69 volume fraction of PB, the morphology were changed from lamellae to hexagonally packed cylinder and an enormous change on the freezing point when crystallizing were observed. As adding more PB into block copolymer, the morphology was transferred further to spherical microdomain and the freezing point were more depressed. It was assumed that the crystallization rate was related with the continuities of microdomains. Different microdomain needed its own nucleus to enlarge PEO spherulite. Such a nucleation process became the rate-determined step in crystallization. In a word, the crystallization rate was controlled by 〝homogeneous nucleation〞.

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