臺灣博碩士論文加值系統

本研究主要對於絲素蛋白(Silk fibroin)進行微纖化(Filament)及結晶化(Crystallization)製備成絲素蛋白奈米微纖(Silk nanofibril)，並將其利用壓力過濾的方式沉積在水解聚丙烯腈(HPAN)基材之上，並應用於奈米過濾程序之中；另一方面亦探討氧化石墨烯(GO)添加量對於薄膜奈米過濾效能之影響。
利用FT-IR、TGA以及DSC分析SNF之微結構組成，並將其與蠶繭、未處理SF及傳統醇誘導SF相比較；利用UV-vis探討不同SF、SNF之溶解性；利用SEM、XPS、及水接觸角鑑定SNF、SNF/GO薄膜表面性質以及利用過濾裝置測量薄膜奈米過濾效能。
SNF擁有最接近於蠶繭的微結構，並且其奈米過濾的效能在SF之中最為優異，其具有18.55LMH的通量、對於硫酸鈉有86.15%的阻擋性，並在添加5%GO之後薄膜通量提升至31.86LMH，硫酸鈉阻鹽率維持在87.09%，對於分子量在616g/mol以上的負電染料具有94%以上的阻擋率。

In this study, silk nanofibril(SNF) is used as main material of nanofiltration membrane. After fibrilling and crystallizing, silk fibroin(SF) transfer itself to SNF. SNF is pressure-filtrated on HPAN substrate to form composite membrane.
FT-IR, TGA and DSC were chosen to characterize the fine structure and obtain the most cocoon-like fine structure which make it have the best performance compared to the rest SF membrane. UV-vis was used for solubility test of SFs and SNF. Surface properties and NF tests of SNF composite membrane and SNF/GO nanocomposite membrane were obtained by SEM, XPS, W.C.A and filtration set-up respectively.
Among all of the SFs and SNF membranes, SNF have 18.55LMH of the flux and 86.15% of the rejection for Na2SO4 due to its hydrophilic crystal structure. The flux gets twice and the rejection is fixed after 5% GO addition. Furthermore, SNF/GO nanocomposite membrane have at least 94% of rejection for negatively charged organic dyes.

目錄

摘要 I
Abstract II
目錄 III
圖索引 VI
表索引 IX
第一章 緒論 1
1-1前言 1
1-1-1 水資源概況 1
1-1-2 薄膜分離程序 2
1-1-3 奈米過濾 3
1-2天然高分子 5
1-3蠶絲絲素蛋白 7
1-4蠶絲蛋白奈米微纖 11
1-5有機無機奈米混成 14
1-6氧化石墨烯 17
1-7 文獻回顧 19
1-8 研究動機 24
第二章 實驗 25
2-1實驗藥品 25
2-2實驗儀器 26
2-3薄膜製備 28
2-3-1基材膜製備 28
2-3-2 聚丙烯腈之水解 28
2-3-3 絲素蛋白溶液之製備 29
2-3-4蠶絲蛋白奈米微纖溶液之製備 29
2-3-5複合薄膜之製備 30
2-4薄膜鑑定 31
2-4-1場發射掃描式電子顯微鏡(FE-SEM). 31
2-4-2熱重分析儀(TGA) 32
2-4-3示差掃描量熱儀(DSC) 33
2-4-4全反射式傅立葉轉換紅外線光譜儀(ATR-FTIR) 34
2-4-5 接觸角測量儀(Contact Angle Measurement) 35
2-4-6 X射線光電子能譜學(XPS) 36
2-4-7 表面介達電位儀(SurPASS) 36
2-4-8 紫外光/可見光光譜儀(UV/vis) 37
2-4-9 奈米過濾測試 37
第三章 結果與討論 39
3-1 絲素蛋白(SF)、絲素奈米微纖(SNF)之鑑定 39
3-1-1 蛋白質微結構之鑑定 39
3-1-2 溶解度測試 45
3-2 高分子濃度對薄膜效能之影響 47
3-2-1 絲素蛋白奈米微纖(SNF)濃度變化 47
3-3不同微結構之絲素蛋白複合薄膜奈米過濾效能之探討 54
3-4 氧化石墨烯(GO)添加量對薄膜效能之影響 57
3-4-1 SNF/GO複合薄膜之鑑定 57
3-4-2 SNF/GO複合薄膜之奈米過濾效能 61
3-5 操作條件變化對薄膜效能之影響 67
3-5-1 操作壓力變化對薄膜效能之影響 67
第四章 結論 71
第五章 參考文獻 73





圖索引
Fig. 1-1 Application range of various pressure-driven membrane filtration processes 2
Fig. 1-2 Schematic drawing of a composite membrane 4
Fig. 1-3 The raw silk consists of two fibroin fibers held together with a layer of sericin on their surfaces.[19] 8
Fig. 1-5 Schematic presentation of the silk fibroin (SF) structure; d represents the diameter of a single silkworm thread [19] 10
Fig. 1-6 A schematic diagram of filament and crystallization of silk nanofibril 13
Fig. 1-7 Schematic of the microstructures that can develop in clay-filled polymer composites 16
Fig. 2-1 Partially hydrolyzed reaction of PAN [56] 28
Fig. 2-2 A schematic of scanning electron microscope 32
Fig. 2-3 A digital photo of DSC Q100 cell 34
Fig. 2-4 A schematic diagram of contact angle 35
Fig. 2-5 A schematic diagram of nanofiltration device 38
Fig. 3-1 SEM images of (A) silk fibroin and (B) silk nanofibril. 40
Fig. 3-2 ATR-FTIR spectra of (a) untreated silk fibroin, (b) heat treated silk fibroin, (c) methanol treated silk fibroin, (d) silk nanofibril and (e) degummed silk cocoon (d-SC). 41
Fig. 3-3 TGA curves for the SFs, SNF and d-SC. (Sample gas : N2, Heating rate 10℃/min) 42
Fig. 3-4 TMDSC curves for the SFs, SNF and d-SC. (Sample gas : N2, Heating rate 3℃/min) 43
Fig. 3-5 UV-vis spectra of different SFs and SNF in water. (A)SF30℃,(B)SF50℃,(C)SFMeOH and (D)SNF 46
Fig. 3-5 Surface SEM images of HPAN substrate and SNF membranes with different concentration. Magnifications of (A-E) are 5k and of (A′-E′) are 100k. 49
Fig. 3-6 Cross-section SEM images of HPAN substrate and SNF membranes with different concentration 50
Fig. 3-7 (A) ATR-FTIR spectra and (B) water contact angle of HPAN substrate and SNF membranes with different concentration. 51
Table 3-3 Hydrated ionic radii [57] 52
Fig. 3-8 Effect of SNF concentration on nanofiltration performance. (Feed condition: 1000 ppm of Na2SO4, 0.6MPa, 25℃) 53
Fig. 3-9 SEM surface images of SF30℃, SF50℃, SFMeOH and SNF composite membrane Magnifications of (A-D) are 5k and of (A′-D′) are 100k. 55
Fig. 3-11 SEM surface images of the SNF/GO composite membranes with different GO loading 58
Fig. 3-12 Water contact angle of the SNF/GO composite membranes 59
Fig. 3-13 Zeta potential of HPAN, SNF, SNF/GO and GO membranes 61
Fig. 3-14 Effect of GO loading on SNF/GO composite membranes. (Feed condition: 1000 ppm of Na2SO4, 0.6MPa, 25℃) 62
Fig. 3-15 NF performance of SNF2ppm/GO5% composite membrane with different salts. (Feed condition: 1000 ppm of each salt, 0.6MPa, 25℃) 64
Fig. 3-16 NF performance of SNF2ppm/GO5% composite membrane with different dyes. (Feed condition: 50 ppm of each dye, 0.6MPa, 25℃) 65
Fig. 3-17 Molecular weight cut-off of SNF2ppm/GO5% membrane. (Feed condition: 100 ppm of each PEG, 0.6MPa, 25℃) 66
Fig. 3-18 Effect of operating pressure on nanofiltration performance through SNF2ppm/GO5%. (Feed condition: 1000 ppm of Na2SO4, pH7, 25℃) 68
Fig. 3-19 Effect of feed concentration on nanofiltration performance through SNF2ppm/GO5%. (Feed condition: 0.6MPa, pH7, 25℃) 69
Fig. 3-20 Effect of feed pH value on surface zeta potential and nanofiltration performance of SNF2ppm/GO5% composite membrane. (Feed condition: 1000 ppm of Na2SO4, 0.6MPa, 25℃) 70










表索引
Table 2-1 Condition of membrane fabrication 30
Table 3-1 Thermal properties of SFs, SNF and d-SC 45
Table 3-2 NF performance of SNF2ppm with and without hydrolysis 47
Table 3-3 Hydrated ionic radii 52
Table 3-4 NF performance, water contact angle, and crystalline structure of different SF and SNF 56
Table 3-5 The element ratio of SF, SNF, SNF/GO membranes 60

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