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研究生:潘美卉
研究生(外文):Mei-Hui Pan
論文名稱:奈米纖維交聯聚氨酯材料之形狀記憶研究
論文名稱(外文):The study of shape memory behavior of polyurethane networks crosslinked by nanofibers
指導教授:吳昌謀
指導教授(外文):Chang-Mou Wu
口試委員:鄭國彬楊銘乾徐錦祥
口試委員(外文):Kuo-Bing ChengMing-Chien YangChing-Hsiang Hsu
口試日期:2019-01-22
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:材料科學與工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2019
畢業學年度:107
語文別:中文
論文頁數:70
中文關鍵詞:聚氨酯中空管狀高嶺土奈米纖維素纖維交聯密度形狀記憶
外文關鍵詞:PolyurethaneHalloysite nanotubesCellulose nanofibersCrosslink densityShape memory property
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聚氨酯(Polyurethane, PU)之形狀記憶行為,其機制為利用PU中軟段的PCL之熔點(Tm)及結晶溫度作為兩個相轉移溫度,並藉由軟硬鏈段的相互影響,使之擁有記憶不同形狀的功能,且最後可回復至初始形態。
本研究分別利用中空管狀高嶺土(Halloysite nanotubes, HNTs)及奈米纖維素纖維(cellulose nanofiber, CNF)來改質PU的系統,藉此改善循環記憶效應不佳,製備出擁有高回復率及高固定率的形狀記憶高分子。本研究利用HNT表面上的羥基(-OH)與PU預聚物末端的異氰酸酯官能基(-NCO)產生共價鍵,除形成網狀交聯的結構藉以提供在材料內部儲存應力所需的硬鏈段外,更使兩物質在非晶區產生結晶,以記憶較多應力,相對地在回復時亦能釋放較多應力。利用這兩部分來改善材料回復形狀的性能,以及比較兩者對形狀記憶效應的影響;而因應相同增強硬段的概念,本研究另外選擇一具可撓性且表面同具有-OH的CNF,來比較其不同改質的特性。
本研究分別探討0、0.5、1和3wt%的HNT及CNF對形狀記憶效果的影響。經試驗的結果得出,HNT及CNF的改質皆能有效的改善形狀記憶回復率至約90%並同時保持99%以上之固定率。
Polyurethanes nanocomposites were synthesized with 4,4’- Methylene diphenyl diisocyanate (MDI), poly(Ɛ-caprolactone) (PCL) and nanofiller. The hydroxyl groups on halloysite (HNT) and cellulose fibers (CNF) were reacted with MDI to form a crosslinked network structure. Effects of diffrtent content on the surface morphology, mechanical, thermal, thermo-mechanical and shape memory properties were investigated by using tensile tester, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA), respectively. The crosslinking density of the polyurethanes was determined by using swelling test.
The results showed that both PU/HNTs and PU/CNF nanocomposites exhibited a significant improvement in the thermal, mechanical and shape memory properties comparing with pristine polyurethane. The shape memory properties improvement may be attributed to appreciable crosslink density.
摘要
Abstract I
第一章 前言 1
1.1引言 1
1.2形狀記憶材料簡介 3
1.3 研究動機 5
第二章 文獻回顧 6
2.1形狀記憶聚氨酯 6
2.2聚合方法及奈米填料添加 8
2.2.1高分子摻合(Polymer Blend) 8
2.2.2原位聚合(in situ polymerization) 8
2.2.3交聯(cross-linking) 10
2.2形狀記憶高分子循環 10
第三章、實驗 14
3.1實驗藥品 14
3.2實驗流程 15
3.3實驗試片製備流程 16
3.3.1合成步驟 16
3.3.2 PU/HNT試片製備 17
3.3.3 PU/CNF試片製備 18
3.4實驗設備與測試儀器 20
3.4.1實驗設備 20
3.4.2檢測方法 21
4.1合成及有機結構鑑定 26
4.2結晶型態及分散影像分析 28
4.2.1 POM 28
4.3.1 SEM/TEM影像 29
4.3熱性質分析 31
4.2.1 HNT對PU Tm及Tc之影響 31
4.2.2 CNF對PU Tm及Tc之影響 33
4.4 動態黏彈性質分析 35
4.4.1 PU/HNT之黏彈性質分析 35
4.4.2 PU/CNF之黏彈性質分析 38
4.5力學性質 40
4.5.1 PU/HNT力學性質影響 40
4.5.2 PU/CNF力學性質影響 42
4.6 交聯密度分析 44
4.7形狀記憶行為 46
4.7.1 PU/HNT形狀記憶效能研究 47
4.6.2 PU/CNF形狀記憶效能研究 52
第五章、結論 55
參考文獻 57
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