臺灣博碩士論文加值系統

本研究擬以聚丙氧基-聚乙氧基甘油醚（GP-b-E）寡聚物或形狀相異之胺改質中空二氧化矽（NH2-HS）作為添加劑，添加至乙基纖維酯（EC）高分子中，製備一系列EC複合膜，應用於氣體分離程序，探討鑄膜液濃度與寡聚物添加量對薄膜性質與氣體分離效能的影響。亦探討中空二氧化矽之形狀、表面胺改質與添加量對薄膜性質與氣體分離效能的影響。
研究中利用掃描式電子顯微鏡（SEM）觀察薄膜與中空二氧化矽的結構型態，以傅立葉紅外線轉換光譜儀（FTIR）鑑定胺改質中空二氧化矽表面的化學結構，以能量散佈分析儀（EDX）觀察中空二氧化矽於薄膜中的分佈情形，以熱重分析儀（TGA）與熱示差掃瞄卡量計（DSC）檢測薄膜的熱性質，使用萬能拉力機量測薄膜的機械性質，利用微量天平進行氣體吸附實驗，以量測薄膜的氣體吸附量。
於GP-b-E寡聚物的添加系統中，由SEM觀察的結果可知，在EC高分子薄膜中添加GP-b-E寡聚物，會使薄膜型態由較封閉的多孔隙結構，轉變為較連通的多孔隙結構，且隨著GP-b-E添加量增加，薄膜之連通孔洞有增加的趨勢。由DSC與機械性質的測試結果發現，GP-b-E寡聚物的添加，使薄膜的熔點下降，薄膜的楊氏模數與抗張強度下降，而薄膜的伸長率增加。由氣體透過實驗的結果可知，於EC高分子薄膜中添加含醚基團的寡聚物，確實能有效提升二氧化碳與氧氣的透過係數。添加比例為EC:GP-b-E=1:0.5（重量比）的GP-b-E寡聚物，其所製備的EC/GP-b-E複合膜有較理想的氣體分離效能，其二氧化碳與氧氣的透過係數分別為1506.3 barrer與228.5 barrer，二氧化碳/氮氣與氧氣/氮氣選擇性分別為17.5與2.7。由溶解-擴散機制的分析可知，EC/GP-b-E複合膜的氣體透過係數與氣體選擇性分別由氣體擴散係數與氣體擴散選擇性主導。
於HS與NH2-HS的添加系統中，由SEM觀察與FTIR分析的結果可知，本研究確實成功製出形狀相異的中空二氧化矽，並將-NH2基團接枝於其表面。由SEM觀察與EDX分析的結果顯示，球狀NH2-HS可均勻分散於EC高分子薄膜中。由機械性質量測的結果可知，在薄膜中添加球狀NH2-HS，使其楊氏模數、抗張強度與伸長率皆下降。由TGA與DSC的測試結果可知，球狀NH2-HS的添加，僅略提升薄膜的熱穩定性，但薄膜的玻璃轉移溫度(Tg)與熔點(Tm)皆下降。由氣體透過實驗的結果可知，於EC高分子薄膜中添加球狀中空二氧化矽，確實能夠提升二氧化碳與氧氣的透過係數。添加比例為EC:NH2-HS=1:0.1（重量比）之球狀NH2-HS，其所製備的EC/spherical NH2-HS複合膜有較理想的氣體分離效能，其二氧化碳與氧氣的透過係數分別為190.1 barrer與33.7 barrer，二氧化碳/氮氣與氧氣/氮氣選擇性分別為19.7與3.5。

In this study, the oligomer, glycerol propoxylate-block-ethoxylate (GP-b-E) or the amino-modified hollow silica (NH2-HS) with different shaps as the additives were added in the ethyl cellulose (EC) polymer to prepare a series of EC composite membranes. These composite membranes were applied to the gas separation processes. The effects of the concentration of casting solution and the oligomer content on the properties and gas separation performance of membrane were investigated. The effects of the shape, surface amino-modification, and content of hollow silica on the properties and gas separation performance of membrane were also studied in this study.
Scanning electron microscope (SEM) was used to observe the morphologies of the membranes and hollow silica. Fourier transform infrared (FTIR) was used to analyze the surface chemical structure of amino-modified hollow silica. Energy Dispersive X-ray spectrometer (EDX) was used to observe the distribution of hollow silica in the membrane. Thermogravimetric analysis (TGA) and Differential scanning calorimetry (DSC) were used to analyze the thermal properties of the membranes. Tensile tester (Instron) was used to measure the mechanical properties of the membranes. The gas sorption measurement was carried out by the microbalance to determine the adsorbed amount of gas.
In the addition system of GP-b-E oligomer, from the SEM observation, the addition of the GP-b-E oligomer in the EC membrane causes the membrane morphology converts the more closed porous structure to the more connected porous structure. With an increase in the added amount of GP-b-E, connected porous structure in the membrane increased. From the results of the DSC and mechanical property measurements, the addition of the GP-b-E oligomer causes a decrease in the melting point, Young's modulus, and tensile strength and an increase in the elongation. From the results of the gas permeation experiments, the addition of the oligomer having the ether groups in the EC membrane can effectively promote the permeability coefficients of carbon dioxide and oxygen. The EC/GP-b-E composite membrane prepared by the addition content of EC:GP-b-E=1:0.5 (by weight) has the desirable gas separation performance which is the carbon dioxide and oxygen permeability coefficients of 1506.3 barrer and 228.5 barrer and the carbon dioxide/nitrogen and oxygen/nitrogen selectivities of 17.5 and 2.7, respectively. From the analysis of the solution-diffusion mechanism, the gas permeability coefficient and selectivity of the EC/GP-b-E composite membrane are dominated by it’s the gas diffusivity coefficient and diffusivity selectivity.
In the addition system of HS and NH2-HS, from the results of SEM observation and FTIR analysis, the amino-modified hollow silica with different shaps was prepared successfully. From the SEM observation and EDX analysis, the spherical NH2-HS can be distributed in the EC membrane uniformly. From the result of mechanical property measurement, the addition of the spherical NH2-HS causes a decreases in Young's modulus, tensile strength and elongation. From the TGA and DSC measurements, the addition of the spherical NH2-HS in the EC membrane enhances the thermal stability of the membrane slightly but decreases the glass transition temperature (Tg) and melting point (Tm). From the results of the gas permeation experiments, the addition of the spherical HS in the EC membrane can effectively promote the permeability coefficients of carbon dioxide and oxygen. The EC/spherical NH2-HS composite membrane prepared by the addition content of EC:spherical NH2-HS=1:0.1 (by weight) has the desirable gas separation performance which is the carbon dioxide and oxygen permeability coefficients of 190.1 barrer and 33.7 barrer and the carbon dioxide/nitrogen and oxygen/nitrogen selectivities of 19.7 and 3.5, respectively.

摘要 I
ABSTRACT IV
致謝 VII
目錄 IX
圖索引 XIII
表索引 XVII
第一章 緒論 1
1-1 薄膜分離技術 1
1-2 氣體分離薄膜 7
1-3 氣體分離薄膜傳送理論 9
1-3-1 多孔性薄膜之透過理論 11
1-3-2 非多孔性薄膜之透過理論 14
1-3-3雙重吸附理論 17
1-4 高分子薄膜之製備與改質 21
1-4-1 高分子薄膜之製備 21
1-4-2 高分子薄膜之改質 24
1-5 中空二氧化矽（HOLLOW SILICA） 28
1-6 旋轉塗佈技術 31
1-7 文獻與回顧 33
1-8 研究動機與目的 42
第二章 實驗 44
2-1 實驗藥品 44
2-2 實驗儀器 47
2-3 實驗流程圖 49
2-4 實驗步驟 50
2-4-1 EC/GP-b-E複合膜之製備 50
2-4-2 中空二氧化矽（Hollow silica，HS）之製備 51
2-4-3 中空二氧化矽（Hollow silica，HS）之改質 52
2-4-4 EC/HS與EC/NH2-HS複合膜之製備 53
2-4-5 掃描式電子顯微鏡（SEM） 54
2-4-6 穿透式電子顯微鏡（TEM） 55
2-4-7 高分子鑄膜液黏度之量測 56
2-4-7 熱重分析（TGA） 56
2-4-9 熱示差掃瞄卡量計（DSC） 57
2-4-10 溶出測試 57
2-4-11 機械性質測試 58
2-4-12 傅立葉轉換紅外線光譜儀（FTIR） 58
2-4-13 氣體透過測試（Gas Permeability Analyzer） 59
2-4-14 氣體恆溫吸附實驗 61
第三章 結果與討論 63
3-1 EC高分子濃度對EC/GP-B-E複合膜氣體分離效能之影響 63
3-2 寡聚物添加量對EC/GP-B-E複合膜性質與氣體分離效能之影響 71
3-2-1 GP-b-E添加量對薄膜型態之影響 71
3-2-2 GP-b-E添加量對薄膜機械性質之影響 74
3-2-3 GP-b-E添加量對薄膜熱性質之影響 76
3-2-4 GP-b-E添加量對薄膜氣體分離效能之影響 80
3-3 NH2-HS的添加對EC複合膜性質與氣體分離效能之影響 91
3-3-1 HS與NH2-HS顆粒之鑑定 91
3-3-2形狀相異之NH2-HS顆粒的添加對複合膜性質與氣體分離效能之影響 95
3-4 球狀NH2-HS添加量對EC複合膜性質與氣體分離效能之影響 102
3-4-1球狀NH2-HS顆粒添加量對薄膜表面型態與顆粒分散性之影響 102
3-4-2 球狀NH2-HS顆粒添加量對薄膜機械性質之影響 105
3-4-3 球狀NH2-HS顆粒添加量對薄膜熱性質之影響 108
3-4-4 球狀NH2-HS顆粒添加量對薄膜氣體分離效能之影響 113
第五章 參考文獻 120
自述 130
著作 131

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