§ 瀏覽學位論文書目資料
  
系統識別號 U0002-2402202110375500
DOI 10.6846/TKU.2021.00624
論文名稱(中文) 聚乙二醇氣體分離膜之製備與其物性分析
論文名稱(英文) Preparation, characterization and gas separation properties of polyethylene oxide membranes
第三語言論文名稱
校院名稱 淡江大學
系所名稱(中文) 化學工程與材料工程學系碩士班
系所名稱(英文) Department of Chemical and Materials Engineering
外國學位學校名稱
外國學位學院名稱
外國學位研究所名稱
學年度 109
學期 1
出版年 110
研究生(中文) 黃冠誌
研究生(英文) KUAN-CHIH HUANG
學號 607400420
學位類別 碩士
語言別 繁體中文
第二語言別
口試日期 2021-01-14
論文頁數 92頁
口試委員 指導教授 - 賴偉淇
委員 - 童世煌
委員 - 楊大毅
關鍵字(中) 聚乙二醇
2,4-雙(3,4-二甲基苯基)山梨醇
氣體分離
關鍵字(英) PEO
DMDBS
gas separation
第三語言關鍵字
學科別分類
中文摘要
本研究以聚乙二醇(PEO)高分子與不同比例之2,4-雙(3,4-二甲基苯基)山梨醇(1,3:2,4-bis(3,4-dimethylbenzyliden) sorbitol, DMDBS)混摻,以溶劑揮發法製備成薄膜,探討分子間作用力、薄膜的結構型態、熱性質、晶體結構、機械性質與氣體分離性能。
由FTIR分析可得知PEO與DMDBS會形成分子間氫鍵,隨著DMDBS的添加,分子間氫鍵有增強的趨勢。由結構型態可以發現在本研究中薄膜為緻密無孔洞的結構。由SEM與TEM可發現DMDBS會自組裝形成10~100奈米細纖維,纖維平均直徑與DMDBS添加量形成正比關係。由熱性質可以發現在PEO中加入DMDBS後,經由TGA測試發現能增加其起始裂解溫度,但對於最大裂解溫度不會有變化。由DSC測試結晶度與融點變化,發現添加DMDBS沒有影響PEO的結晶度與融點。由DMA機械性質分析發現添加越多DMDBS會使儲存模數與損失模數均有提升的趨勢。由XRD晶體結構分析中可以發現添加越多的DMDBS會使PEO的結晶性能變差的趨勢。由氣體分離測試發現隨DMDBS添加CO2滲透率會先上升後下降,N2滲透率則下降,因此CO2/N2的選擇率也有先上升後下降的趨勢。經由Robeson上限值計算可以知道在本研究材料均無超過Robeson上限。
英文摘要
In this study the intermolecular forces, structure morphology, thermal properties, mechanical properties, crystal structure and gas separation performance, by using solvent evaporation method to prepared PEO blend 1,3:2,4-bis(3,4-dimethylbenzyliden) sorbitol (DMDBS) thin films.
By FTIR analysis, we found that PEO and DMDBS will form intermolecular hydrogen bonds. With the addition of DMDBS, the intermolecular hydrogen bonds tend to increase. By structure morphology, we found the thin film in this study is dense and nonporous, by SEM and TEM, it can be found that DMDBS will self-assemble to form 10-100 nanometer fine fibers, and the average fiber diameter is proportional to the amount of DMDBS added. By thermal properties, it can found that adding DMDBS will increase the initial pyrolysis temperature through TGA test, but the maximum pyrolysis temperature will not change. It is found that adding DMDBS did not affect the crystallinity and melting point of PEO, by DSC test for the crystallinity and melting point. By DMA mechanical properties, we found that the more DMDBS added, the storage modulus and loss modulus tend to increase. From the XRD crystal structure analysis, it can be found that the more DMDBS added will make the crystallization performance of PEO worse. By gas separation performance, we found that CO2 permeation will first increase and then decrease, N2 permeation will decrease, and the selectionof CO2/N2 also tends to increase first then decrease when the addition of DMDBS. By calculation the Robeson upper bound, it can be known that none of the materials in this study exceeds Robeson upper bound.
第三語言摘要
論文目次
目錄
致謝	I
中文摘要:	II
英文摘要:	III
目錄	V
圖目錄	VIII
表目錄	XI
第一章 緒論	1
1.1前言	1
1.2研究目的	2
第二章 理論背景	3
2.1薄膜分離技術	3
2.2二氧化碳分離技術	4
2.3薄膜氣體分離應用	5
2.4薄膜的製備方式	5
2.5氣體分離膜結構	7
2.5.1混和基質膜(Mixed matrix membrane,MMMs)	7
2.5.2金屬有機骨架(Metal-Organic Framework,MOF)	8
2.6氣體分離膜材料	9
2.7實驗材料介紹	11
2.7.1聚乙二醇(Poly(ethylene oxide),PEO)	11
2.7.2 1,3:2,4-雙(3,4-二甲基苯基)山梨醇(1,3:2,4-bis(3,4-dimethylbenzyliden) sorbitol ,DMDBS)	12
第三章 文獻回顧	13
3.1氣體過濾理論	13
3.2氣體分離方式	14
3.2.1變壓吸附(Pressure Swing Adsorption (PSA))	14
3.2.2低溫液化法(Cryogenic liquefaction)	15
3.2.3膜分離(Membrane Separation)	15
3.3氣體過濾膜材料	16
3.4聚乙二醇基底薄膜	16
第四章 實驗	19
4.1實驗藥品	19
4.2實驗設備	20
4.3實驗流程	25
4.4實驗樣品製備	25
4.4.1複合材料之官能基特性分析	25
4.4.2掃描式電子顯微鏡(SEM)	25
4.4.3穿透式電子顯微鏡(TEM)	26
4.4.4氣體過濾膜膜厚測試	26
4.4.5熱重損失分析儀 (TGA)	26
4.4.6示差掃描熱卡分析儀(DSC)	26
4.4.7X光繞射分析(XRD)	26
4.4.8氣體過濾膜機械性質測試	27
4.4.9氣體過濾測試	27
第五章 結果與討論	28
5.1複合材料間分子作用力分析	28
5.2薄膜結構分析	32
5.3薄膜熱性質分析	48
5.4薄膜機械性質分析	57
5.5薄膜晶體結構分析	62
5.6氣體過濾性質測試	65
5.7氣體過濾膜上限值計算	79
第六章 結論	80
第七章 參考文獻	82
 
圖目錄
圖2. 1不同混合氣體的應用	5
圖2. 2 MMMs結構示意圖	8
圖2. 3不同材料之有機金屬骨架結構示意圖	9
圖2. 4DBS結構圖	12
圖3. 1不同氣體滲透率比較圖	17
圖4. 1氣體過濾模組上模具規格	23
圖4. 2氣體過濾模組下模具規格	23
圖4. 3氣體過濾模組橡膠墊片規格	24
圖4. 4氣體過濾模組實驗裝置圖	24
圖5. 1實驗使用材料之FTIR圖	30
圖5. 2不同樣品FTIR圖譜	30
圖5. 3樣品局部IR圖	31
圖5. 4樣品0D上表面(a)倍率400(b)倍率30k	34
圖5. 5樣品5D上表面(a)倍率400(b)倍率30k	35
圖5. 6樣品10D上表面(a)倍率400(b)倍率30k	36
圖5. 7樣品15D上表面(a)倍率400(b)倍率30k	37
圖5. 8樣品20D上表面(a)倍率400(b)倍率30k	38
圖5. 9樣品0D TEM圖	39
圖5. 10樣品20D TEM圖	39
圖5. 11樣品5D纖維分佈	40
圖5. 12樣品10D纖維分佈	40
圖5. 13樣品15D纖維分佈	41
圖5. 14樣品20D纖維分佈	41
圖5. 15不同比例之纖維粗細	42
圖5. 16不同比例之薄膜厚度	42
圖5. 17樣品0D截面(a)倍率250(b)倍率10k	43
圖5. 18樣品5D截面(a)倍率250(b)倍率10k	44
圖5. 19樣品10D截面(a)倍率250(b)倍率10k	45
圖5. 20樣品15D截面(a)倍率250(b)倍率10k	46
圖5. 21樣品20D截面(a)倍率250(b)倍率10k	47
圖5. 22DMDBS TGA圖	50
圖5. 23DMDBS 一次微分TGA圖	50
圖5. 24不同樣品之TGA圖	51
圖5. 25不同樣品之一次微分TGA圖	51
圖5. 26 樣品1st DSC圖	52
圖5. 27樣品2nd DSC圖	53
圖5. 28不同比例DMDBS融點變化(DCS 1st run)	54
圖5. 29不同比例DMDBS融點變化(DSC 2nd run)	55
圖5. 30不同比例DMDBS結晶度變化(DCS 1st run)	55
圖5. 31不同比例DMDBS融點變化(DSC 2nd run)	56
圖5. 32樣品0D模數圖	58
圖5. 33樣品5D模數圖	58
圖5. 34樣品10D模數圖	59
圖5. 35樣品15D模數圖	59
圖5. 36樣品20D模數圖	60
圖5. 37不同比例儲存模數圖	60
圖5. 38不同比例損失模數圖	61
圖5. 39樣品0D與DMDBS XRD圖	63
圖5. 40不同樣品XRD圖	63
圖5. 41 不同進料壓力CO2滲透率(不含膜厚)	70
圖5. 42同進料壓力CO2滲透率(含膜厚)	70
圖5. 43不同進料壓力N2滲透率(不含膜厚)	71
圖5. 44不同進料壓力N2滲透率(含膜厚)	71
圖5. 45 CO2/N2選擇率	72
圖5. 46 樣品0D通過3atm CO2後SEM表面圖	72
圖5. 47 樣品5D通過3atm CO2後SEM表面圖	73
圖5. 48 樣品10D通過3atm CO2後SEM表面圖	73
圖5. 49 樣品15D通過3atm CO2後SEM表面圖	74
圖5. 50 樣品20D通過3atm CO2後SEM表面圖	74
圖5. 51 樣品0D通過3atm N2後SEM表面圖	75
圖5. 52 樣品5D通過3atm N2後SEM表面圖	75
圖5. 53 樣品10D通過3atm N2後SEM表面圖	76
圖5. 54 樣品15D通過3atm N2後SEM表面圖	76
圖5. 55 樣品20D通過3atm N2後SEM表面圖	77
圖5. 56氮氣測試後出現小顆粒放大圖(-2187,-2188)	78
圖5. 57 小顆粒之EDX圖	78
圖5. 58CO2/N2 Robeson上限值比較	79

 
表目錄
表4. 1 實驗配方與代號	25
表5. 1PEO官能基特徵峰位置表	29
表5. 2DMDBS官能基特徵峰位置表	29
表5. 3不同樣品之起始裂解與最大裂解溫度表	52
表5. 4不同比例之融點變化	53
表5. 5不同比例之結晶度變化	54
表5. 6不同樣品模數表	61
表5. 7不同樣品半高寬	64
表5. 8不同進料壓力之CO2進出口流量	67
表5. 9不同進料壓力之N2進出口流量	67
表5. 10壓力1atm下氣體過濾各項參數	68
表5. 11壓力2atm下氣體過濾各項參數	68
表5. 12壓力3atm下氣體過濾各項參數	69
表5. 13不同壓力下各樣品之選擇率	69
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