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研究生:楊凱勛
研究生(外文):Kai-Hsun Yang
論文名稱:無機層狀材料奈米混成於高分子分散膽固醇液晶之光電性質探討
論文名稱(外文):Study on Electro-optical Properties of Polymer DispersedCholesteric Liquid Crystals by Hybridizing Inorganic Layered Materials
指導教授:蔡宗燕徐芝珊
指導教授(外文):Tsung-Yen TsaiJy-Shan Hsu
學位類別:碩士
校院名稱:中原大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2015
畢業學年度:103
語文別:中文
論文頁數:129
中文關鍵詞:無機層狀材料高分子分散膽固醇液晶電活性寡聚物奈米複合材料
外文關鍵詞:Inorganic layered materialsPDCLCelectroactive oligomernanocomposites
相關次數:
  • 被引用被引用:1
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高分子分散液晶(PDLC)在光電領域中被廣泛的使用,例如智慧型薄膜、平板、軟性顯示器等。本研究利用膽固醇液晶(Cholesteric Liquid Crystal)混和光敏感高分子,製備出新型且具有熱致變色能力的高分子分散膽固醇液晶奈米複合材料(Polymer Dispersed Cholesteric Liquid Crystal, PDCLC/nanocomposite),其組成包含向列型液晶E7、旋性劑S811、光敏感高分子NOA-65、無機層狀材料。無機層狀材料主要為天然黏土、苯環結構之電活性寡聚物(Pentamerous oligo-aniline, POA)改質型黏土、鋰鋁層狀雙氫氧化合物。實驗中利用廣角X光繞射光譜儀 (Wide Angle X-Ray Diffraction, XRD)、傅立葉轉換紅外線光譜儀(Fourier Transform Infrared, FTIR)及熱失重分析儀(Thermogravimetry Analyzer, TGA )、電子掃描式顯微鏡(Scanning Electron Microscope, SEM) 對有機化改質型黏土與鋰鋁層狀雙氫氧化物進行結構鑑定。將無機層狀材料以兩種不同製程(A製程:將無機層材膨潤於液晶、B製程:將無機層材膨潤於光敏感性高子)製備成PDCLC nanocomposites,利用偏振光光學顯微鏡(Polarizing Optical Micro-scope, POM)觀察膽固醇液晶於高分子系統中顯色型態,發現無機層狀材料的添加,在A製程中會影響膽固醇液晶的顯色型態。在外加交流電電場1 kHz下定溫量測閾值電壓、驅動電壓、對比度及瞬態時變之光學特性,發現驅動電壓降幅並沒有所預期的來的大,唯有苯胺寡聚體改質之黏土利用B製程所製備樣品(CL120-POA 0.5 % B)在相近螺距狀態下驅動電壓由124.39 Vrms降至115.62 Vrms。進一步利用掃描式電子顯微鏡觀察CL120-POA 0.5 % B高分子孔洞表面型態,發現其液晶滴粒徑最小。因此證明在B製程中改質型黏土的添加確實可增加高分子導電率,但受液晶滴粒徑的限制無法有效的降低驅動電壓。

Polymer-dispersed liquid crystals (PDLC) are widely used for electro-optic applications such as smart film, flat panel and flexible display etc. In this research work, a new kind of PDCLC/inorganic layered material nanocomposites has been synthesized by using thermochromic Polymer Dispersed Cholesteric Liquid Crystal (PDCLC), including nematic liquid crystal E7, chiral dopant S811, photocurable monomer NOA-65 and inorganic layered materials. Inorganic layered materials such as clay, modified clay, and Lithium Aluminum layered double hydroxide (LiAl LDH) were used. The morphology, thermal stability and organomodified inorganic layered materials identified by Wide Angle X-Ray Diffraction (WXRD), Scanning Electron Microscope (SEM), Thermogravimetry Analyzer (TGA), and Fourier Transform Infrared (FTIR). PDCLC/inorganic layered material nanocomposites were fabricated by two different methods (Method A: inorganic layered materials swelling in LC, Method B: inorganic layered materials swelling in photo curable monomer). The colour change of PDCLC nanocomposite observed by Polarizing Optical Microscope (POM). The colour of cholesteric liquid crystal in polymer system was affected by inorganic layered materials doped which were synthesized by Method A. Those samples threshold voltage, drive voltage, contrast ratio, response time will measure under 1 kHz AC electric field at constant temperature. The drive voltage were not lowering as expected but only one sample that doped modified clay- pentamerous oligo-aniline which was synthesized by Method B have lowered drive voltage at similar pitch, and voltage reduced from 124.39 Vrms to 115.62 Vrms. Further, morphology and polymer pore of PDCLC nanocomposites observed by SEM, the smallest liquid crystal droplet observed among all sample CL120-POA. Therefore, it is evidence that the CL120-POA doped by method B can raise conductivity of polymer, thus the small liquid crystal droplet effected the drive voltage.

目錄
中文摘要 I
Abstract III
謝誌 V
目錄 VII
圖目錄 X
表目錄 XIII
第一章 緒論 1
1.1 文獻回顧 3
1.2 專利分析 5
1.3 商情情報 9
1.4 研究動機 12
第二章 基礎理論 13
2.1 液晶簡介 13
2.1.1 液晶的分類 15
2.1.2 液晶的特性 20
2.2 高分子分散液晶之簡介 26
2.2.1 高分子分散液晶製備方法 27
2.2.2 高分子分散向列型/膽固醇液晶工作原理 30
2.3共軛結構之電活性苯胺寡聚物之簡介 32
2.4無機層狀材料簡介 34
第三章 藥品儀器與實驗步驟 41
3.1 藥品與儀器 41
3.1.1 實驗藥品 41
3.1.2 實驗儀器 47
3.2實驗步驟 53
3.2.1 天然黏土純化 53
3.2.2 苯胺五聚體改質天然黏土 55
3.2.3 鋰鋁層狀雙氫氧化合物之合成 57
3.2.4 高分子分散膽固醇液晶-無機層狀材料混成製備 59
第四章 結果與討論 63
4.1 無機層狀材料改質與合成鑑定 63
4.1.1 改質天然黏土之結構與官能基鑑定 64
4.1.2 改質型黏土之改質劑含量計算 67
4.1.3 鋰鋁層狀雙氫氧化合物合成鑑定 72
4.1.4 鋰鋁層狀雙氫氧化合物粒徑大小 74
4.2高分子分散膽固醇液晶奈米複合材料光電特性 75
4.2.1 高分子分散膽固醇液晶/無機層材顯色型態 77
4.2.2 高分子分散膽固醇液晶/無機層材驅動電壓 87
4.2.3 膽固醇液晶/無機層材之介電常數 97
4.2.4 高分子分散膽固醇液晶/無機層材液晶滴型態 99
4.2.5 奈米複合材料之分散型態 103
第五章 總結與未來展望 106
第六章 參考文獻 109


圖目錄
圖1-1液晶調光玻璃原理示意圖 2
圖1-2 負型高分子分散膽固醇液晶通電示意圖 4
圖1-3 台灣專利件數歷年趨勢分析圖 5
圖1-4 台灣專利技術公告生命週期分析圖 7
圖1-5 台灣公司別專利分析圖 7
圖1-6 美國專利件數歷年趨勢分析圖 8
圖1-7 美國技術生命週期分析圖 9
圖1-8 美國公司別專利分析圖 9
圖2-1 溶致型液晶微胞及囊胞示意圖 15
圖2-2 熱致型液晶相變式意圖 16
圖2-3 膽固醇液晶週期性螺旋結構示意圖 19
圖2-4 膽固醇液晶通電狀態下示意圖 19
圖2-5 盤狀液晶結構示意圖 20
圖2-6 液晶分子雙折射三維空間示意圖 23
圖2-7 熱致型液晶折射率與溫度之關係圖 23
圖2-8 液晶分子感應電場的排列方向 25
圖2-9 熱致型液晶介電係數與溫度之關係圖 25
圖2-10 不同比例之液晶/高分子複合材料 26
圖2-11 高分子分散液晶工作室示意圖 31
圖2-12 PDCLC在不同旋性劑比例下之RGB圖譜 31
圖2-13 苯胺五聚體氧化還原態圖示 33
圖2-14 苯胺五聚體循環伏安圖 33
圖2-15 Smectite層狀結構示意圖 36
圖2-16 LDHs結構示意圖 40
圖2-17不同系列LDHs相對於AEC之值關係圖 40
圖3-1穿透度與電壓關係自動化量測系統示意圖 49
圖3-2純化黏土步驟流程圖 54
圖3-3黏土改質步驟流程圖 56
圖3-4 LiAl LDH合成步驟流程圖 58
圖3-5 PDCLC/黏土方法A步驟流程圖 61
圖3-6 PDCLC/黏土方法B步驟流程圖 62
圖4-1 改質前後CL120之XRD圖譜 66
圖4-2 苯胺五聚體插層示意圖 66
圖4-2 改質前後CL120之FT-IR圖譜 67
圖4-4 改質前後CL120之TGA圖譜 71
圖4-5 CL120-POA失重量一次微分之TGA圖譜 71
圖4-6 LiAl-LDH不同水熱時間之XRD圖譜 73
圖4-7 LiAl-LDH不同水熱時間之IR圖譜 73
圖4-8 鋰鋁層狀雙氫氧化合物之SEM 75
圖4-9不同製程PDCLC在不同溫度下之POM圖 80
圖4-10 純膽固醇液晶之DSC圖譜 81
圖4-11 不同製程PDCLC之DSC圖譜 82
圖4-12 水熱時間1小時PDCLC-LiAl-LDH之POM圖 85
圖4-13 水熱時6小時PDCLC-LiAl-LDH在不同溫度之POM圖(A)PDCLC-LiAl-LDH6 (B)放置一周後之PDCLC-LiAl-LDH6 86
圖4-14 不同製程PDCLC定溫及1 kHz下交流電電壓–光穿透度關係圖(a)PURE(b)CL120 0.5 % A(c)CL120 0.5 % B(d)CL120-POA 0.5 % A(e)CL120-POA 0.5 % B 89
圖4-15 PDCLC通電示意圖 91
圖4-16 不同製程PDCLC穿透頻譜(a)PURE(b)CL120 0.5 % A(c)CL120 0.5 % B(d)CL120-POA 0.5 % A(e)CL120-POA 0.5 % B 94
圖4-17 不同製程PDCLC反射光波長數據圖 95
圖4-18 不同製程PDCLC在相近螺距下之1 kHz交流電−光穿透圖譜 96
圖4-19 膽固醇液晶/無機層材介電常數頻譜 98
圖4-20 膽固醇液晶/無機層材導電率頻譜 99
圖4-21 不同製程PDCLC之SEM圖 102
圖4-22 PDCLC/CL120 0.5 % B黏土於高分子相TEM圖 104
圖4-23 PDCLC/CL120-POA 0.5 % B黏土於高分子相TEM圖 104
圖4-24 PDCLC/CL120-POA 0.5 % B黏土零星分散於高分子相TEM圖 105

表目錄
表2-1 天然黏土分類表 36
表4-1 無機層狀材料與改質劑官能基對照表 67
表4-2 黏土/改質土/改質劑之不同溫度時之失重量 69
表4-3無機層狀材料與改質劑官能基對照表 74
表4-2 膽固醇液晶相轉變溫度數據整理 82
表4-3 不同製程PDCLC 1 kHz下交流電系統中之電壓、穿透度與對比度 90
表4-5 不同製程PDCLC反射光波長數據整理 95
表4-6 不同製程之PDCLC在相近螺距、1 kHz交流電下之電壓、穿透度與對比度 96
表4-7 不同製程PDCLC相近螺距下反應時間表 97



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