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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 童世煌(Shih-Huang Tung) | |
| dc.contributor.author | Chih-Hung Lee | en |
| dc.contributor.author | 李治宏 | zh_TW |
| dc.date.accessioned | 2021-06-08T04:16:02Z | - |
| dc.date.copyright | 2010-08-11 | |
| dc.date.issued | 2010 | |
| dc.date.submitted | 2010-08-04 | |
| dc.identifier.citation | 參考文獻
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/22352 | - |
| dc.description.abstract | 本實驗是研究直鏈狀-梳狀共聚合物超分子在薄膜中的微相分離情形，並利用溶劑退火處理得到高度規整性的奈米結構薄膜。我們所選用的材料是以PS-b-P4VP為主幹，PDP小分子利用氫鍵作用力與主鏈上的P4VP端鍵結形成直鏈狀-梳狀共聚合物超分子。此一超分子材料不只會因為PS與P4VP的不相容性而產生微相分離，還會因為PDP的長鏈尾基與P4VP的排斥力進行更小尺度的相分離。控制共聚合物兩鏈段PS與P4VP(PDP)的比例可以得到不同的微相分離形態，例如層狀、六角堆積的圓柱、體心立方堆積的球狀結構(大約40nm)，而P4VP(PDP)所存在的區間還會進行小尺度的相分離(大約4nm) ，因此整體的結構會形成一個結構內有結構的等級(hierarchical)結構。我們將此材料的相分離限制在薄膜中(大約100nm)進行，並用溶劑退火處理可以得到垂直於基材的大尺度圓柱或是層狀結構。我們發現垂直結構的產生是由於小尺度相分離的帶動，因此梳狀結構的接枝密度是很重要的參數，以圓柱結構來說，要形成垂直的結構其接枝比例x(PDP與4VP單體的比值)要接近1，而對於層狀結構x要等於2.5結構才會由平躺翻轉為垂直的結構。也由於小尺度分離對整體結構的重要性，因此若是所選用之退火溶劑極性過大且足以破壞P4VP與PDP之間的氫鍵時(例如THF、1,4-dioxane)便無法得到上述之垂直結構，我們實驗上所使用之溶劑為chloroform以及toluene。我們也發現退火時的蒸氣壓對系統也有很大的影響，在低壓進行溶劑退火時可以得到垂直的結構，但是在高溶劑氣壓下進行溶劑退火便無法形成完美的垂直結構。另外在旋轉塗佈製作薄膜時所選用的溶劑對後續的結構也有一定程度的影響。
此外我們也將氫鍵所形成之PDP系統推展到離子鍵鍵結之DBSA系統，此時圓柱系統的方向性轉變與PDP的系統相類似，在x=1.0時也會傾向形成垂直的結構，而且改變溶劑進行退火處理時，由於離子鍵不會被溶劑所壞所以仍可維持垂直的結構。 | zh_TW |
| dc.description.abstract | Our research is based on comb-coil supramolecular microphase separation. Well-ordered nanostructured polymer thin films have been fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-P4VP) and 3-n-Pentadecylphenol (PDP) by solvent annealing. In this system, the microphase separation occurs not only between PS and P4VP but also P4VP and PDP hydrophobic tails. Therefore, these thin films form both large-scaled microdomains (~40nm) and small-scaled (~4nm) lamellae, i.e. hierarchical structures. Interestingly, the orientation can be tailored by PDPs: after thin films are solvent annealed, the microdomains formed by block copolymers, including cylinders and lamellae, can be oriented perpendicular to the surface, while the small-scaled lamellae formed by PDP are parallel to the surface. We found that the amount of incorporated PDP is the key for such transformation and thus we conclude that the orientation is controlled by small-scaled lamellae. The mechanism will be discussed in the thesis.
In this research we also found that the use of high polar solvents, such as THF and 1,4-dioxane, to anneal thin films will reduce the strength of hydrogen bonds between PDP and 4VP, which would hinder the formation of perpendicular block copolymer microdomains. In the final part of the thesis, we will discuss how solvent vapor pressure and different casting solvents affect the final morphology of thin films. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-08T04:16:02Z (GMT). No. of bitstreams: 1 ntu-99-R97549011-1.pdf: 9520000 bytes, checksum: 809fce91d60ca345aec642ed23232641 (MD5) Previous issue date: 2010 | en |
| dc.description.tableofcontents | 謝詞 I
中文摘要 II Abstract III 目錄 IV 圖目錄 VII 表目錄 XI 第一章 緒論 1 1-1前言 1 1-2研究動機 3 第二章 文獻回顧 4 2-1超分子化學的發展 4 2-2團聯式共聚物之微相分離形態 6 2-3梳狀超分子共聚物 13 2-4共聚合物薄膜的製備 19 2-4.1旋轉塗佈 19 2-4.2 溶劑退火 19 2-4.3 Dewetting(反濕潤) 21 2-5共聚合物在薄膜中的微相分離形態 26 2-5.1 層狀結構Lamella 26 2-5.2圓柱狀結構 Cylinder 27 第三章 實驗方法與儀器 31 3-1材料 31 3-2實驗步驟 33 3-2.1樣品的製備 33 3-2.2薄膜側面TEM與底部AFM 34 3-2.3 P4VP(PDP)溶解度 34 3-2.4薄膜厚度的量測 34 3-3儀器原理 37 3-3.1 旋轉塗佈機(Spin coater) 37 3-3.2傅立葉轉換紅外光光譜儀(FT-IR) 37 3-3.3多波長折射率測量儀(interferometer) 37 3-3.4 原子力顯微鏡(AFM) 38 3-3.5 穿透式電子顯微鏡(TEM) 38 3-3.6 濺鍍機 39 3-3.7 掠角入射小角度x光散射儀(Grazing-in) 39 第四章 結果與討論 44 4-1梳狀超分子共聚合物的結構鑑定 44 4-1.1 PS-b-P4VP(PDP)x 44 4-1.2 PS-b-P4VP(DBSA)x 44 4-2 PS-P4VP超分子系統中溶劑之選擇性 48 4-3 梳狀超分子共聚合物在薄膜中微相分離形態 56 4-3.1 PS(20,000)-P4VP(17,000)與小分子接枝後的相分離行為 56 4-3.2 PS(40,000)-P4VP(5,600)與小分子接枝後的相分離行為 60 4-4 高蒸氣壓下進行溶劑退火對梳狀超分子型態的影響 91 4-4.1 PDP超分子系統 91 4-4.2 DBSA系統 91 4-5不同溶劑所製作的薄膜對其後之形態影響 97 第五章 結論 99 | |
| dc.language.iso | zh-TW | |
| dc.subject | 接枝度 | zh_TW |
| dc.subject | 超分子 | zh_TW |
| dc.subject | 共聚物薄膜 | zh_TW |
| dc.subject | 自組裝 | zh_TW |
| dc.subject | 溶劑退火 | zh_TW |
| dc.subject | self-assembly | en |
| dc.subject | Supramolecular | en |
| dc.subject | bonding fraction | en |
| dc.subject | solvent annealing | en |
| dc.subject | copolymer thin film | en |
| dc.title | 接枝效應對超分子共聚物薄膜微相分離形態之影響 | zh_TW |
| dc.title | Grafting effects on the morphology of block copolymer–based supramolecular thin films | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 98-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 黃慶怡(Ching-I Huang),戴子安(Chi-An Dai) | |
| dc.subject.keyword | 超分子,共聚物薄膜,自組裝,溶劑退火,接枝度, | zh_TW |
| dc.subject.keyword | Supramolecular,copolymer thin film,self-assembly,solvent annealing,bonding fraction, | en |
| dc.relation.page | 105 | |
| dc.rights.note | 未授權 | |
| dc.date.accepted | 2010-08-04 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
| 顯示於系所單位： | 高分子科學與工程學研究所 | |
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