臺灣博碩士論文加值系統

親水性的氧化石墨烯(GO)常用於與有機高分子共混形成複合材料，但合成GO的過程使用大量的強酸與強氧化劑，導致對於環境的嚴重污染，因此本研究擬透過多巴胺改質石墨烯(mGr)的方式製備環境友善的複合材料，應用於乙醇脫水程序，我們將mGr加於聚乙烯醇(PVA)中，製備PVA-mGr混成薄膜，以滲透蒸發分離程序探討薄膜透過效能，並利用全反射式傅立葉轉換紅外線光譜儀(ATR-FTIR)、表面接觸角量測儀(Water contact angle)、場發式電子顯微鏡(FESEM)及X-ray繞射儀(XRD)對薄膜化學結構、親水性及物理結構形貌進行鑑定。
無機相在有機相中的分散狀態會對混成薄膜的物理化學性質與分離效能造成很大的影響。由實驗結果顯示，本研究以多巴胺改質之mGr相較於石墨烯(Gr)，其親水性的提升有助於增加其在高分子基質中的分散性，並改善Gr在高添加量狀態下的由於凡德瓦爾力作用所產生之團聚現象。
探討不同添加量的石墨烯衍生物對薄膜滲透蒸發效能結果指出，相較於PVA-Gr薄膜，改質後的PVA-mGr薄膜展現優異的乙醇水分離效能，在mGr添加量為3wt%時，於25℃的進料溫度下分離90wt%乙醇水溶液展現最佳之分離效能，透過量及透過端水濃度分別為359 (g/m2 h)與98.4 wt%。 本研究進一步探討滲透蒸發操作條件對於分離效能之影響，包含進料溫度、進料濃度以及薄膜長時間穩定性測試。相較於PVA薄膜，混成薄膜能有效抑制薄膜膨潤現象，提升薄膜長時間操作穩定性。在高溫70℃進料環境下進行滲透蒸發操作，PVA-3mGr之透過端水濃度高於PVA-3Gr與PVA薄膜，其透過端水濃度為83 wt%，且透過量為982 (g/m2 h)；混成薄膜對滲透蒸發分離90 wt%乙醇水溶液長時間穩定性的影響，經過22天測試，PVA-3mGr與PVA-3Gr之透過端水濃度分別維持在97 wt%與93 wt%，且其透過量分別為537 (g/m2 h)與356 (g/m2 h)。

The hydrophilic graphene oxide (GO) is generally used to be nanocomposite materials by mixing it with polymer. But large amounts of strong acid and oxidants during GO synthesis produces environmental pollutants. In this study, we prepared an environmentally friendly nanocomposite materials through modified graphene(mGr) with dopamine for dehydration process of ethanol. PVA-mGr hybrid membranes were fabricated for pervaporation application by adding mGr in the PVA solution. The physicochemical properties, structure, and hydrophilicity of the fabricated membranes were characterized by attenuated total reflection - Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurement, field-emission scanning electron microscope (FE-SEM) and x-ray diffraction techniques (XRD).
The improvement of the physicochemical properties and pervaporation performance of the hybrid membranes are presumably due to the effect of nanoscale structure and the interaction between polymer and inorganic material. Graphene agglomerates because of Van der Waals forces between graphene layers. The mGr does not agglomerates since the hydrophilicity was increased because of the Gr modification with dopamine.
The effect of the content of graphene derivatives on pervaporation performance were investigated. The results showed that PVA-mGr hybrid membranes had excellent performance when added with 3 wt% mGr in the separation of 90 wt% aqueous ethanol solution at 25 ℃. The permeation flux and water concentration in permeate side of PVA-mGr membranes were 359 g/m2-h and 98.4 wt%, respectively. This study also investigated the effects of pervaporation conditions, including feed temperature, feed concentration, and durability test on pervaporation separation. Compared with PVA membrane, the hybrid membrane could effectively suppress swelling and enhance the stability of membranes.
At a high feed temperature of 70℃, the water concentration in permeate side was 83 wt%, and the permeation flux was 982 g/m2 h. The membrane life of pervaporation process through the durability test for 90 wt% aqueous ethanol solution. After 22 days, the water concentration in permeate side and permeation flux of PVA-3mGr and PVA-3Gr membranes were remained at 97 wt%, 93 wt% and 537 (g/m2 h), 356 (g/m2 h) respectively.

摘要 I
Abstract III
致謝 V
目錄 VI
圖索引 VIII
表索引 X
符號說明 XI
第一章 緒論 1
1.1前言 1
1.2薄膜分離技術 2
1.3滲透蒸發分離程序 5
1.3.1 滲透蒸發之發展 6
1.3.2 滲透蒸發之原理及其應用 7
1.4 薄膜結構型態 9
1.4.1 高分子緻密性薄膜 9
1.4.2 高分子多孔性薄膜 9
1.4.3無機薄膜 10
1.4.4 有機/無機混成薄膜 10
1.5 奈米複合材料之分類與特性 11
1.6石墨烯介紹及衍生物 14
1.6.1石墨烯簡介 14
1.6.2 石墨烯衍生物 15
1.7文獻回顧 17
1.7.1 有機/無機混成膜應用於滲透蒸發分離程序 17
1.7.2 石墨烯及其衍生物/高分子複合材料之製備方式 19
1.7.3 石墨烯及其衍生物/高分子複合材料之物性與應用 20
1.7.4 石墨烯/高分子複合材料應用於滲透蒸發分離程序 21
1.8動機與目的 23
第二章 實驗 24
2.1 實驗架構 24
2.2 實驗藥品 25
2.3 實驗儀器 26
2.4 石墨烯衍生物之製備 27
2.5 PVA-石墨烯衍生物混成薄膜之製備 27
2.5.1 鑄膜溶液之配製 27
2.5.2 PVA-石墨烯衍生物混成薄膜之製備 27
2.6 PVA-石墨烯衍生物混成薄膜之鑑定 28
2.6.1全反射式傅立葉轉換紅外線光譜儀(Attenuated Total Reflectance Fourier Transform Infrared spectroscopy, ATR-FTIR ) 28
2.6.2 表面親疏水性量測(Surface water contact angle) 29
2.6.3場發射掃描式電子顯微鏡(Field-emission scanning electron microscope, FE-SEM) 29
2.6.4 X射線繞射技術(X-ray diffraction, XRD) 30
2.6.5熱重分析測試(Thermogravimetric analysis, TGA) 31
2.6.6膨潤度測試(Degree of swelling, D.S.) 31
2.6.7滲透蒸發分離程序(Pervaporation procedure) 32
第三章 結果與討論 34
3.1 PVA-GR與PVA-MGR薄膜之性質分析 34
3.1.1 石墨烯與改質石墨烯對薄膜之化學結構的影響 34
3.1.2 薄膜親疏水性之鑑定 37
3.1.2 石墨烯與改質石墨烯對薄膜結構型態之影響 39
3.2 石墨烯與改質石墨烯對薄膜之熱穩定的影響 44
3.3 混成薄膜之滲透蒸發效能 46
3.3.1石墨烯衍生物添加量對薄膜滲透蒸發效能的影響 46
3.3.2 進料溫度對於滲透蒸發分離效能之影響 50
3.3.3 進料濃度對於滲透蒸發分離效能的影響 52
3.3.4 醇類水溶液種類對混成薄膜分離效能之影響 54
3.3.5 滲透蒸發長時間分離效能之穩定性 56
第四章 結論 57
第五章 參考文獻 58



圖索引
第一章
Figure 1 - 1 Schematic representation of two-phase system separated by a membrane . 2
Figure 1 - 2 McCabe-Thiele separation diagram. Coparison of pervaporation selectivity with distillation selectivity. System : water-ethanol. 5
Figure 1 - 3 Solution-diffusion mechanism. 7
Figure 1 - 4 Schematic illustrations of polymer/clay nanocomposite materials. 11
Figure 1 - 5 Proposed model for the torturous zigzag diffusion path in an exfoliated polymer–clay nanocomposite when used as a gas barrier. 13

第二章
Figure 2 - 1 membrane prepared procedure. 28
Figure 2 - 2 X-ray diffraction and Bragg''s Law. 30
Figure 2 - 3 The schematic diagram of pervaporation apparatus 33

第三章
Figure 3- 1 ATR-FTIR spectra for Gr material, PVA and PVA-Gr hybrid membranes with different Gr concentration. (a) Gr (b) PVA (c) PVA-0.5Gr (d) PVA-1Gr (e) PVA-3Gr (f) PVA-5Gr membranes. 36
Figure 3- 2 ATR-FTIR spectra for mGr material, PVA and PVA-mGr hybrid membranes with different mGr concentration. (a) mGr (b) PVA (c) PVA-0.5mGr (d) PVA-1mGr (e) PVA-3mGr (f) PVA-5mGr membranes. 36
Figure 3- 3 ATR-FTIR spectra for PVA-Gr and PVA-mGr hybrid membranes at 3 wt%. 37
Figure 3- 4 Effect of modifying PVA with different Gr and mGr concentration on the membrane hydrophilicity. 38
Figure 3- 5 Photo of Gr/water and mGr/water suspension. 38
Figure 3- 6 Effect of Gr concentration on the PVA-Gr membrane surface (×1k) and cross section (×1.5k) morphology. (a,f) PVA (b,g) PVA-0.5Gr (c,h) PVA-1Gr (d,i) PVA-3Gr (e,j) PVA-5Gr. 40
Figure 3- 7 Effect of mGr concentration on the PVA-mGr membrane surface (×1k) and cross section (×1.5k) morphology. (a,f) pure PVA (b,g) PVA-0.5mGr (c,h) PVA-1mGr (d,i) PVA-3mGr (e,j) PVA-5mGr. 41
Figure 3- 8 XRD for Gr and mGr. 43
Figure 3- 9 XRD for PVA-Gr hybrid membranes with different Gr concentration. (a) Gr (b) PVA (c) PVA-0.5Gr (d) PVA-1Gr (e) PVA-3Gr (f) PVA-5Gr. 43
Figure 3- 10 XRD for PVA-mGr hybrid membranes with different mGr concentration. (a) mGr (b) PVA (c) PVA-0.5mGr (d) PVA-1mGr (e) PVA-3mGr (f) PVA-5mGr. 44
Figure 3- 11 Temperature dependence of the weight loss for (a) PVA (b) PVA-3Gr (c) PVA-3mGr membranes. (Heating rate : 10℃/min under N2 flow) 45
Figure 3- 12 Effect of Gr concentration on the membrane pervaporation performance in 90 wt% ethanol solution at 25℃. 47
Figure 3- 13 Effect of Gr concentration on the degree of swelling for PVA-Gr membranes in 90 wt% ethanol solution at 25℃. 48
Figure 3- 14 Effect of mGr concentration on the membrane pervaporation performance in 90 wt% ethanol solution at 25℃. 48
Figure 3- 15 Effect of mGr concentration on the degree of swelling for PVA-mGr membranes in 90 wt% ethanol solution at 25℃. 49
Figure 3- 16Effect of operation temperature on pervaporation performance of PVA, PVA-Gr and PVA-mGr membranes in 90% ethanol solution at 25 ℃. ((■,□) PVA, (▲,△ ) PVA-Gr and (◆,◇) PVA-mGr ) 51
Figure 3- 17 Arrhenius plot of flux against 1000/T for PVA, PVA-Gr and PVA-mGr membranes. ( (■) PVA, (●) PVA-Gr and (▲) PVA-mGr) 52
Figure 3- 18 Effect of feed solution concentration on pervaporation performance of PVA, PVA-Gr and PVA-mGr membranes at 25 ℃. ((■,□) PVA, (▲,△) PVA-Gr and (◆,◇) PVA-mGr) 53
Figure 3- 19 Effect of operating time on pervaporation performance. (Feed: 90wt% aqueous ethanol solution at 25 ℃) 56



表索引
第一章
Table 1 - 1 Driving force and the two-phase systems separated by membranes for different membrane process . 3

第三章
Table 3- 1 Data obtained from TGA analysis of PVA, PVA-3G and PVA-3mG membranes. 45
Table 3- 2 Effect of modifying PVA with graphene and its derivative on the membrane pervaporation performance in 90 wt% ethanol solution at 25℃. 49
Table 3- 3 Effect of 90 wt% aqueous alcohols solution on the pervaporation performance through PVA-Gr hybrid membrane. 55
Table 3- 4 Effect of 90 wt% aqueous alcohols solution on the pervaporation performance through PVA-mGr hybrid membrane. 55
Table 3- 5 Molar volume of alcohols. 55

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