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研究生:陳欣平
研究生(外文):Hsin-PingChen
論文名稱:左、右式聚乳酸非等莫耳混合物之熔融結晶及左式聚乳酸於溶液結晶之球晶形貌與晶板組裝
論文名稱(外文):Spherulitic Morphology and Lamellar Assembly in Nonequimolar Mixtures of Poly(L-lactic acid) with Poly(D-lactic acid) and Solution-Cast Poly(L-lactic acid) Films
指導教授:吳逸謨
指導教授(外文):Ea-Mor Woo
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2017
畢業學年度:105
語文別:中文
論文頁數:67
中文關鍵詞:聚乳酸球晶形貌立體錯合物輻射狀球晶溶劑揮發
外文關鍵詞:poly(lactic acid)morphologystereocomplexradiating-stripesolvent evaporation
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本研究應用偏光顯微鏡 (polarized optical microscopy,POM)、廣角X光繞射儀 (wide angle X-ray diffraction,WAXD)、微分掃描熱卡計 (differential scanning calorimeter,DSC)、原子力顯微鏡 (atomic force microscopy,AFM)和掃描式電子顯微鏡 (scanning electron microscopy,SEM)分別探討:左式聚乳酸 poly(L-lactic acid) (PLLA)/右式聚乳酸 poly(D-lactic acid) (PDLA)非等莫耳混摻系統,及PLLA以溶劑揮發的方式,形成的結晶形態、晶態分析與晶板結構。
在PLLA/PDLA非等莫耳混摻系統中,藉由聚乳酸錯合物stereocomplexed-PLA (sc-PLA)之熔點較PLLA、PDLA高50 oC的特性,使用不同的熔融溫度 (Tmax)處理試樣,由POM發現在PLLA-rich系統中,不論Tmax高或低於sc-PLA之熔點皆會同時出現兩種不同的結晶形貌:輻射狀 (radiating-stripe) 球晶與小顆的結晶或負型球晶 (negative-type spherulite),其中,輻射狀球晶是PLLA較為少見的球晶形貌。經由加熱定點觀察與WAXD分析得知,輻射狀球晶是由PLLA構成,屬於α-form的晶格。利用AFM觀察輻射狀球晶上表面,因主幹 (main stalk)與主幹間區域的晶板形狀與排列方向不同,才會造成在同一象限內同時出現不同的雙折射 (birefringence),得以形成輻射狀的球晶形貌。
在PLLA之溶劑揮發結晶系統中,溶劑的種類、揮發速率、揮發溫度都是影響球晶形貌的重要條件。藉由改變不同的溶劑或揮發速率,可以得到截然不同的球晶形貌。當PLLA溶於四氫呋喃,在26 oC~30 oC會形成環帶狀球晶,屬於α-form的晶格。藉由SEM,環帶狀球晶上表面的晶板排列呈現樹枝狀 (dendritic),內部則是長條狀之晶板呈放射狀,並構成層狀堆疊之結構。
Investigations on the morphology resulted from melt-crystallization of nonequimolar blends of PLLA with PDLA with regard to the prior melting temperature and crystallization temperature were conducted. When crystallized after melting at 190 oC, the PLLA/PDLA (95/5) blend exhibits large radiating-stripe spherulites surrounded by tiny spherical crystals. When crystallized after melting at 240 oC, the radiating-stripe spherulites appear with negative-type spherulites. Melting observation show that radiating-stripe spherulites belong to PLLA α-crystals, while negative-type spherulites belong to sc-PLA crystals. From the top surfaces of radiating-stripe spherulites, the lamellae are arranged at an angle of 60o with radial direction on the main stalk, while lamellae on the region between main stalks are arranged perpendicular to the main branch. Because of the difference in lamellar assembly, the blend shows different birefringence in the same quadrant, resulting in special morphology.
For neat PLLA crystallized by solvent evaporation, PLLA exhibits ring-banded morphology at 26~30 oC with tetrahydrofuran as solvent. The top surface of ring-banded spherulites shows lamellae arranged in dendritic shape. Lamellae inside spherulites arrange in radial direction, and show layer structure from lateral view.
中文摘要 I
Abstract II
誌謝 XII
目錄 XV
表目錄 XVII
圖目錄 XVIII
第一章 研究目的與文獻回顧 1
1.1簡介 1
1.2高分子球晶與偏光顯微鏡之理論 2
1.3聚乳酸相關特性及研究 5
1.3.1聚乳酸 Poly(lactic acid) 5
1.3.2錯合物之相關研究 8
1.4溶劑揮發結晶之相關研究 11
1.5研究動機與方向 13
第二章 實驗 15
2.1實驗所使用之高分子及溶劑 15
2.2實驗樣品製備 17
2.3實驗所使用之儀器 18
第三章 結果與討論 20
3.1 PLLA/PDLA混摻系統 20
3.1.1結晶形貌之分析 20
3.1.2 X光繞射與熱分析 35
3.1.3 球晶上表面晶板排列之分析 43
3.2 PLLA系統之溶劑揮發結晶 51
3.2.1 結晶形貌之分析 51
3.2.2 X光繞射、熱行為與球晶結構之分析 56
第四章 結論 61
4.1 PLLA/PDLA混摻系統 61
4.2 PLLA系統之溶劑揮發結晶 61
參考文獻 63
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