本研究利用微分掃描熱卡計(differential scanning calorimeter, DSC)、偏光顯微鏡(polarized optical microscopy, POM)、傅立葉轉換紅外光譜儀(Fourier-transform infrared spectroscopy, FT-IR)、廣角X光繞射儀(wide-angle X-ray diffraction, WAXD)、掃描式電子顯微鏡(scanning electron microscopy, SEM)以及原子力顯微鏡(atomic force microscopy, AFM) 分別探討：低分子量左式聚乳酸 [low-molecular-weight poly(L-lactic acid), LMw-PLLA]/右式聚乳酸 [ploy(D-lactic acid), PDLA]/聚對位乙烯基酚poly(4-vinyl phenol), PVPh] 高分子摻合體系統的球晶形貌、晶板微結構、成長機制；以及長碳鏈之聚對苯二甲酸十二二酯 (poly(dodecamethylene terephthalate, P12T) 的球晶形貌、晶態行為與晶板形貌結構分析。

LMw-PLLA/PDLA/PVPh 摻合系統部分，先將之PLLA與PDLA同比例摻合形成立體錯合物 (stereocomplex) 再添加不同比例的非晶形高分子 PVPh 形成三成份摻合體 (sc-PLA/PVPh)。透過調整組成比例、結晶溫度，於 sc-PLA/PVPh摻合比例 70/30，及結晶溫度區間Tc = 165~172 oC內，首次發現有結合 ring/ringless 雙重形貌的球晶生成，球晶特徵為在中心生成環帶，球晶達到一定程度的直徑後，改以無環帶的狀態繼續生長到完全結晶，這種特殊的現象需調整相關條件參數 (熔融時間、結晶溫度、樣品膜厚) 才能生成，造成這種雙重形貌的球晶，可能原因為樣品在消除熱歷史時，並未完全消去晶核，加上非晶形高分子 PVPh 添加比例高達 30 wt%，在熔融時間較低的樣品上分散不均勻，造成球晶在成長過程中受到阻礙，進而形成結合 ring/ringless 雙重形貌的球晶。

P12T 的系統中，在POM下可以觀察到兩種類型環帶球晶，一為生成結晶溫度較低 (Tc = RT~99 oC) 的雙重環帶球晶 (double ring-banded)，能夠同時在薄膜 (厚度1~5 μm) 與塊材 (厚度10~30 μm) 樣品中觀察到。P12T 在薄膜狀態下，利用 AFM 掃描樣品，發現隨著熱處理時間改變，球晶表面晶板從圓球形晶板轉變為皺褶狀與平坦的晶板。研究中不只對環帶球晶的表面進行觀察亦將P12T的塊材樣品進行結晶及斷裂，分析其三維尺度下環帶球晶內部的晶板。另一種生成結晶溫度較高 (Tc = 100~110 oC) 的同心暗線環帶球晶 (concentric ring-banded) ,此種球晶只能在薄膜狀態下 (厚度500nm~3μm) 生成。透過原子力顯微鏡觀察，球晶表面全由 flat-on 晶板組成，其生成原因為晶板於成長過程中，由非線性的擴散造成crystal-rich band及crystal-poor band 規律且交替性的出現，而生成此類環帶的構造。

This study has been focused on the ring-banded spherulite morphology and behavior of sc-PLA/PVPh blends system, and synthesized poly(dodecamethylene terephthalate) (P12T) in either thin-film or bulk forms. These crystalline morphologies and behaviors were characterized by differential scanning calorimeter (DSC), polarized optical microscopy (POM), Fourier-transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and atomic force microscopy (AFM).

Under POM, the sc-PLA/PVPh blend systems display negative ringless spherulites. However, by controlling the composition, crystallization temperature (Tc), and melting time (Δtmax) of the blend, a special morphology of mixed ring-banded (at the center) and ringless (at the following growth) spherulite is observed under the OM. The sc-PLA/PVPh 70/30 blend melted at 240 oC for 1 minute and crystallized at Tc = 165-172 oC was found to show the most obvious ring/ringless spherulitic pattern. The reason is that the higher content of PVPh with shorter melting time might hinder the growth of sc-PLA crystal, inducing the formation of ring-banded morphology. By melting the crystallized sample, it was found that ring-banded region of the spherulite consists of stable crystal compare to the outer ringless region.

P12T shows two types of ring-banded morphology according to Tc. At lower Tc (RT-99 oC) double ring-banded is observed, whereas concentric ring-banded is found at higher Tc (100-110 oC). For lower Tc samples, in order to get larger spherulite, longer melting time was applied to the sample. The WAXD results show that the crystal form of P12T does not change by Tc and tmax. However, the DSC and AFM results show that the longer tmax will induce the formation of the more stable crystal which has wrinkled lamellae pattern instead of the less stable spherical lamellae. The correlation between top and fracture surface of the bulk sample has been observed by SEM to show the lamellar arrangement in three-dimension (3-D). At the higher Tc, the concentric ring-banded spherulite consists of flat-on lamellae which are only observed in thin film. The characteristics of these ring-banded morphologies have been exposed and investigated in this study.

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