臺灣博碩士論文加值系統

為了觀察高分子中單純的層晶成長過程，此研究準備了十五奈米以
下的聚左乳酸薄膜。不同分子量與不同結晶溫度都會在此研究中被探討。
高分子在結晶初期會先出現粒狀的聚集，這些粒狀的聚集如果可以進一
步互相聚集，則正立層晶可以在其中發展，若這些粒狀的聚集無法有效
率的合併，側立層晶則會先發展。如何有效的讓這些粒狀區間擴散就取
決於持溫溫度，溫度越高，高分子鏈段越容易移動，粒狀區間也就越容
易向彼此聚集，因此在聚左乳酸薄膜中低溫比較傾向形成側立層晶而高
溫比較傾向形成正立層晶。
當層晶開始增厚，包覆結晶區域的非晶質區域會開始參與結晶並消
失，又因為非晶質區域和結晶區域的體積和密度差異，從形貌來看這些
層晶會開始變窄變細。在低溫的層晶增厚中，因為溫度不足以讓分子鏈
自由的移動，非晶質區域無法有效率的參與結晶，其形貌將不會有劇烈
的改變。
不同分子量的聚左乳酸對結晶的影響在於當分子量越高，分子鏈段
越不容易解除互相纏繞的狀態，分子鏈也就不容易移動聚集，於相同的
溫度下跟低分子量的高分子比起來比較容易產生側立層晶，在層晶增厚
的時候也需要比較多時間與比較高的溫度。

Both temperature and molecular-weight effects on lamellar growth of
polylactide acids (PLA) with thin film of 15 nm thick have been
systematically studied in this research. The presence of granular domains and
further coalescence behavior were found and comprehensively explored as a
critical factor for determining lamellar growth orientation to be flat-on or
edge-on. If the coalescence of granular domains can efficiently progress, the
growth of flat-on lamellae is favored, because sufficient space is available for
crystalline lamellae to extensively grow in the orientation parallel to substrate
surface. Based on obtained results, this research has proposed that, with
sufficient undercooling, the adopted crystallization habit within thin film is to
quickly lower the free energy by optimally increasing the volume fraction of
crystalline domain.
At the late growth stage of flat-on lamellae, the domain impingement
causes the further crystallization of remaining amorphous fraction to progress
through the lamellar thickening process. This route of further crystallization
thus reduces the covered area by crystalline domains. For the reorganization
of edge-on lamellae originally growing at a lower temperature, the occurrence
of lamellar coalescence within vein-like domains has been proposed for
explaining the gradual decrease of the areas covered by lamellar stacking.

摘要…………………………………………………………………………i
Abstract……………………………………………………………………iii
致謝…………………………………………………………………………iv
Contents……………………………………………………………………v
List of Figures…………………………………………………………vii
Chapter I Introduction…………………………………………………1
Chapter II Literature study……………………………………………6
II.1 Lamellar growth orientation………………………………7
II.2 Growth morphology of flat-on and edge-on lamellae…14
II.3 Lamellar thickening and coalescence within thin film….26
Chapter III Experimental……………………………………………40
III.1 Materials…………………………………………………40
III.2 Instrument………………………………………………41
III.3 Procedures………………………………………………44
III.3.1 Sample preparation…………………………………44
III.3.1 Film thickness………………………………………44
III.3.2 Isothermal evolution of flat-on lamellae……………44
III.3.3 Evolution of edge-on lamellae at higher temperature..45
III.3.5 TEM analyze…………………………………………45
vi
III.3.6 AFM analyze…………………………………………45
Chapter IV Results and Discussion…………………………………46
IV.1.1 Growth of edge-on lamellae……………………………48
IV.1.2 Growth of flat-on lamellae……………………………55
IV.2.1 Reorganization of flat-on lamellae……………………68
IV.2.2 Reorganization of edge-on lamellae…………………78
IV.2.3 Temperature effect on the reorganization of edge-on
lamellae………………………………………………87
Chapter V Conclusion…………………………………………………93
References…………………………………………………………………95

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