本研究係針對超薄厚度之左旋聚乳酸的結晶型貌，和與右旋聚乳酸、聚己二酸二丁酯或聚對位乙烯基酚混摻系統下的相容性及球晶型貌的探討。晶板排列和厚度是影響聚乳酸產生不具雙折射，或聚雙折射之環狀消光環的控制因素。聚乳酸與聚乳酸錯合晶體一起結晶得到的球晶會比聚乳酸在聚乳酸錯合體為晶核之情況下來得更緊密並且可以減少聚乳酸產生龜裂。左旋聚乳酸與聚己二酸二丁酯混摻系統在聚乳酸熔點之下屬於上臨界溶液溫度(UCST)相行為，並且針對此混摻系統在一般厚度、塊材或超薄情況下的球晶型貌有深入的探討。左式聚乳酸/聚己二酸二丁酯 (50/50)混摻系統的結晶在上臨界溫度之下也就是結晶溫度在110oC呈現相域與環狀消光環的聚乳酸互相交疊，這種現象只會發生在短的熔融時間(Δtmax)，因為鏈纏絡密度是比較少的，導致聚己二酸二丁酯鏈段在聚乳酸結晶時容易被排除在外，所以才會呈現聚乳酸與聚己二酸二丁酯的相分離。相分離現象也可在塊材的斷裂面呈現兩種不同孔洞大小，且小的孔洞與大的孔洞分別代表聚乳酸比例較多和聚己二酸二丁酯比例較多的相。利用溶劑蒸氣蝕刻方法，左旋聚乳酸/聚己二酸二丁酯 (50/50)混摻系統中聚乳酸環狀消光環的谷狀區域中晶板排列方向會交錯出現並且可觀察到光折射現象由負型球晶轉變中性，並最後形成雙環帶球晶。第一次探討左旋聚乳酸/聚己二酸二丁酯混摻系統中聚乳酸單晶的球晶型貌，在添加30wt%的聚己二酸二丁酯進左式聚乳酸並在結晶溫度110oC下晶板會呈現出六軸枝狀伴隨著單晶排列成的菱形。然而，在左旋聚乳酸/聚己二酸二丁酯 (50/50)混摻系統在相同晶溫度下，球晶呈現出樹枝狀型態，並且向一定方向做彎曲。左旋聚乳酸/聚己二酸二丁酯(50/50)和右旋聚乳酸/聚己二酸二丁酯(50/50)混摻系統都是因為聚己二酸二丁酯的加入才會對導致樹枝狀球晶的晶板有彎曲的現象且彎曲方向主要是因為聚乳酸的chirality，分別是逆時針和順時針方向。隨著結晶溫度的增加，球晶型貌會由具有彎曲的樹枝狀轉變成只有徑向成長的樹枝狀。左旋聚乳酸/聚己二酸二丁酯(50/50)在130oC下熔融結晶時，左旋聚乳酸具有正交式球晶中會包含逆時針方向的螺旋片狀晶體。左旋聚乳酸/聚對位乙烯基酚混摻系統在具有微弱作用力下呈現相容系統，並在組成為70/30有3種球晶型態一起存在於結晶溫度為120oC下，並依照形狀、雙折射和光學標誌分類為Type-1 (hexagonal crystals)、Type-2 (dendritic crystal)和Type-3 (complex combination of Type-1 and Type-2)，左旋聚乳酸分子量、PVPh的存在、結晶溫度和成長速率都是對於形成此特殊現象必要的因素。

This study has been focused on the crystalline morphology of ultrathin film neat Poly(L-lactic acid) (PLLA), miscibility and crystalline morphology of its blend with Poly(D-lactic acid) (PDLA), poly(1,4-butylene adipate) (PBA) or poly(4-vinyl phenol) (PVPh). Lamellar arrangement and film thickness are the influencing factors for the formation of nonbirefringent or birefringent concentric ring-banded spherulites in neat PLLA. Co-crystallization of PLLA with stereocomplex polylactides (sc-PLA) spherulites tends to be more compact than that of PLLA spherulites crystallizing on sc-PLA nuclei and it can minimize the formation of cracks in PLLA spherulites. PLLA/PBA blend system exhibits upper-critical-solution-temperature (UCST) behavior below the melting temperature of PLLA. Crystalline morphology either in regular film thickness, bulk sample and ultrathin film of PLLA/PBA blends has been discussed in detailed. Crystallization of PLLA/PBA (50/50) blend below UCST (crystallization temperature (Tc) = 110 oC) shows that phase domains overlap with ring-banded spherulites of PLLA. This phenomenon only occur for short melting time (tmax) because the chain entanglement density is less, thus the PBA chains are easy to be mutually expelled from the PLLA chains during crystallization of PLLA, resulting in PLLA-rich and PBA-rich separate domains. Phase separation can also be observed in the fractured surface of bulk sample as shown by the appearance of two different pore sizes. Small and large pore sizes correspond to the PLLA-rich and PBA-rich domains, respectively. By using solvent-vapor-etching method, it shows that the alteration of lamellar orientation in the valley region of PLLA ring-banded spherulites in PLLA/PBA (50/50) blend induces the alteration of optical birefringence from negative to neutral and finally to double-ring-banded spherulites. For the first time, single-crystalline morphology of PLLA in PLLA/PBA blend has been discovered. At Tc = 110 oC, by adding 30 wt% PBA into PLLA, the lamellae exhibit six-stalk dendrites with single crystal packing in lozenge shape. However, for PLLA/PBA (50/50) blend at the same Tc, it exhibits dendritic spherulite with lamellar bending at certain direction. The formation of bending lamellae in dendritic spherulites of PLLA/PBA (50/50) and PDLA/PBA (50/50) blends is induced by the addition of PBA. Bending direction in the dendritic spherulites of PLLA or PDLA blended with PBA is dictated by the chirality, counter-clockwise and clockwise direction for PLLA/PBA (50/50) and PDLA/PBA (50/50) blends, respectively. With the increasing Tc, crystalline morphological change from dendritic spherulites with bending lamellae (Tc = 110 oC) to dendritic crystals in linear growth (Tc = 130 oC) is observed. PLLA dendritic crystals with straight branches in PLLA/PBA (50/50) blend melt-crystallized at 130 oC are composed by the framework of spiral lozenge crystals in counter-clockwise direction. PLLA/PVPh is miscible blend system with weak interaction. Three different types of spherulites co-exist at the same Tc (120 oC) of PLLA/PVPh (70/30) blend, code-named as Type-1 (hexagonal crystals), Type-2 (dendritic crystals), and Type-3 (complex-combination of Type-1 and Type-2), as distinguished from the shape, birefringence, and optical signs. A combination of several factors, such as PLLA molecular weights, presence of amorphous PVPh, crystallization temperature, and crystal growth rate, is necessary for formation of three uniquely different types of spherulites in PLLA.

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