高分子環帶狀球晶於近世紀以來受到廣泛的注意，不僅因其獨特的外型和有系統性的排列，其潛在的應用價值更是值得關注。許多研究致力於解釋環帶狀球晶之生長機制，至今仍持續進行。近年來，比較能夠被廣泛接受的理論分為兩派，一派為Rhythmic deposition，另一派為Radial lamellar twisting，但理論本身尚不夠完備。因此本研究利用新穎的角度及模型，嘗試以新的觀點來檢視聚己二酸乙二醇酯 (PEA) 及聚苯二甲酸丙二醇酯 (PTT) 此兩種聚酯所形成的環帶狀球晶，並藉由球晶外部表面與內部三維的結構之晶板排列來幫助解釋環帶狀球晶的形成機制。
PEA是一種聚酯類高分子，其厚膜樣品在結晶溫度為28 oC時，會形成核心為碗狀及圓頂狀兩種不同類型的環帶狀球晶。三維結構的晶板自組裝，使球晶外部呈現環帶形貌，並於內部形成類似瓦楞紙板的多殼層狀結構。PEA鏈段生長前端的濃度密度 (x1) 會隨著徑向方向逐漸改變，由剛開始以切線方向生長轉為以徑向方向生長，形成瓦楞紙板狀的結構。由於高分子鏈段的濃度梯度在生長過程中週期性的升降，造成晶板從片狀結構轉為薄的纖毛狀晶板堆疊。PEA的環帶狀球晶是由兩互相垂直的片狀晶板互相交替生長形成 (由切線往徑向彎曲)，說明PEA薄膜樣品在偏光顯微鏡下，所觀察到的環帶狀球晶干涉色週期性的交替變化，是因為晶板排列做交替性的週期改變而導致的結果。而厚膜樣品在SEM的斷截面觀察下，其瓦楞紙板的層厚也與薄膜樣品的環帶寬度相吻合。
接著，由於聚己二酸丁二醇酯 (PBA) 和PEA各自都可以形成環帶狀球晶，在本研究中，利用結晶速率較快的PBA及結晶速率較慢的PEA，在不同的混摻比例下於相同的結晶溫度共同結晶。透過觀察其球晶形貌、相行為及熱行為，分析此雙成份系統的晶板組裝及球晶結構。在PBA/PEA的中間區段組成(10/90~40/60)中，由於PEA與PBA在晶板之間會相互滲透並重新排列，造成PEA會與PBA同時結晶，並形成多孔性結構的鳥巢狀球晶形貌。藉由觀察塊材斷截面之內部構造，可知PEA的瓦楞紙板結構和PBA的瓦楞紙板結構會以3-D的形式在晶板內互相交替。PBA與PEA之間的相互作用力會隨著混摻比例的不同而不同，被認為是形成多孔性結構的驅動力。
為了能更清楚的觀察晶板組裝，會以蝕刻劑洗淨非結晶的區域，讓球晶形貌上有更強烈的對比。甲胺，在眾多蝕刻劑中，已被廣泛使用於許多研究，但顯然地，甲胺不只會造成高分子樣品上的覆蓋層被蝕刻，同時也會導致脂肪族與芳香族聚合物和其產生劇烈的化學變化。甲胺和聚酯類高分子之間所產生的化學反應，會使化學鍵–C(=O)O–被替換成–C(=O)NH–，這樣的改變終會導致不同化學結構的生成、球晶形貌與晶板上的改變，有時甚至會形成完全不同的晶板層狀結構並出現不一樣的熔融峰。由上述可以得知，要慎重的選用甲胺作為蝕刻劑以避免對其產生的變化造成誤解。
PTT，具備高強度雙折射性質的芳香族聚酯類高分子，利用熔融再結晶的方式以薄膜厚度(1 µm ~ 100 µm)在結晶溫度為165 oC時，主要會出現三種不同的環帶狀球晶形貌(同心環帶狀、單一螺旋狀、以及雙重螺旋狀)，為了瞭解PTT在晶板自組裝的多樣性，進而導致球晶形貌在光學性質的各種變化，以PTT本身的高強度雙折射性質做進一步的探討。在不同的PTT環帶狀形貌中主要控制的三個因素為：球核直徑、環帶間距以及在球核周圍的高度差（ΔZ）。從最一開始球核的成長過程以三維的機械吸引力，而導致在PTT斷截面的塊材樣品上能觀察到以有趣的波浪型、扭曲型以及分支型晶板所組成。從球核的幾何形狀可以發現到與三種不同環帶狀球晶形貌的形成機制有高度的相關性。

Banded spherulite in polymer has aroused considerable interest over a century; not only because of their beautiful outward appearances and systematic arrangements, but also because of their potential application values. Much effort has been put in explaining the crystallization mechanism of banded spherulite; yet the discussion is still going on. The two most widely accepted theories, rhythmic deposition and especially radial lamellar twisting, are still poorly understood with many unexplainable defects. Hence in this study, novel approaches and schematic models have been taken to provide insights in viewing lamellar assembly in ring-banded spherulites of two model polyesters, poly(ethylene adipate) (PEA) and poly(trimethylene terephthalate) (PTT), via correlations between outer-surface and three-dimensional interior morphology.
PEA, an aliphatic polyesters, in thick bulk forms exhibits a ring-banded top surface with bowl-like and dome-like height profile centering on its nucleus when crystallized at 28 oC. The 3-D periodical assembly leads to not only noticeable ring bands on exterior surfaces, but also corrugated-board like multi-shell structures in the interior of the spherulites. The concentration density of crystalline polymer chains in the growth front (x1) has been found to change gradually with respect to the radius forming a corrugated-board structure, which firstly grew in tangential direction, then turned to radial direction. The radial plates taper to form thinner cilia-like lamellae due to the polymer chain concentration gradient being periodically precipitated during the growth. Alternating sequences of plate-like lamellae in two perpendicular orientations (bending from tangential to radial) in PEA ring-banded spherulites during growth in radial direction account for the spherulites confined in thin films to display two contrast circumferential rings with alternating interference colors. The SEM dissection graphs clearly reveal interior corrugated layer thickness in bulk forms, which matches well with the inter-ring spacing in thin-films.
Moreover, faster-crystallizing poly(1,4-butylene adipate) (PBA) and much slower-crystallizing poly(ethylene adipate) (PEA), each with the ability to form ring-banded morphology at same Tc, were simultaneously crystallized from mixtures of various compositions. Investigations on morphology, phase and thermal behavior were conducted in order to reveal lamellar packing and spherulitic structures in this binary system. At intermediate compositions PBA/PEA (10/90 ~ 40/60), PEA has the ability to simultaneously crystallize with PBA in forming a bird-nest-like spherulites with porous structure as a result of interpenetration and re-orientations of PBA and PEA lamellae. The corrugated-board structure of PBA is to be followed by another corrugated-board structure of PEA, leading to interwoven lamellae in 3-D forms observed from bulk fractured interiors. The interaction between PBA and PEA along with the composition ratio in the blend are supposed to be the driving force of such porous structure formation.
Etching agents, with methylamine being one among several others, have been used in many studies for exposing the crystal assembly in contrast to amorphous domains in polymer samples for better morphology contrast. Apparently, the methylamine does not simply just induce physical etching of peeling off a covered layer from polymer samples but also causes severe chemical changes in not only aliphatic but also aromatic polymers. The chemical reactions between methylamine and polyesters ultimately lead to different chemical structures, alteration in spherulites and lamellae, and sometimes completely different lamellar structures with a different melting peak, with –C(=O)O– in polymers being replaced with –C(=O)NH– bonding. Cautions should be taken when using methylamine as etching agent or else misinterpretation may be a consequence.
PTT, a highly birefringent aromatic polyester, exhibits spherulites with three main types of banded structure (i.e., neat concentric, single spiral, and double spiral) co-existing in a same sample film melt-crystallized at 165 oC, regardless of sample thickness (1 µm ~ 100 µm). The nature of high birefringence in PTT ring-banded spherulites is utilized for probing the origins of diversification of lamellar assemblies into spherulites of multiple optical patterns. Three controlling factors: core diameter, band spacing, and height difference (Δz) around the core, are the key parameters of different banding patterns in PTT spherulites. Formation mechanism for three types of ring-banded spherulites has been interpreted, and found to be highly correlated with the initial nuclei geometry shapes.

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