臺灣博碩士論文加值系統

本研究將苯乙烯寡聚物-鈀(S-Pd)複合奈米粒子添加於聚碳酸酯(Polycarbonate, PC)中，以乾式相轉換法製備出緻密的混合基質氣體分離膜，探討不同濃度奈米粒子添加對S-Pd/PC混合基質薄膜氣體分離行為之影響。
SEM觀察發現，PC緻密薄膜經由添加不同濃度的S-Pd奈米粒子後，奈米粒子會在薄膜內產生團聚現象，DSC與DMA測量結果顯示薄膜之玻璃轉移溫度（Glass transition temperature，Tg）隨著奈米粒子添加量增加有很明顯的下降，氣體透過測試結果顯示，隨著S-Pd奈米粒子添加量之增加，氣體透過效能沒有因為玻璃轉移溫度的降低而有所提高，因此本研究利用「正子湮滅光譜分析技術」，分析奈米粒子添加對S-Pd奈米粒子混合基質薄膜自由體積之影響，藉由自由體積變化解析薄膜之氣體分離行為。S-Pd奈米粒子添加可改善薄膜對二氧化碳塑化之抵抗能力。

In this thesis, various concentrations of polystyrene-based oligomer-Pd (S-Pd) nanoparticle were added into a polycarbonate matrix. Then, oligomer-Pd (S-Pd) nanoparticle olycarbonate was cast for preparing a polycarbonate mixed matrix membrane using the dry-phase separation method. The effect of nanoparticle concentration on gas separation phenomena of S-Pd/PC mixed matrix membrane was discussed.
SEM results showed that aggregation of nanoparticle in S-Pd/PC mixed matrix membrane occurred when the concentration of S-Pd nanoparticle increased. DSC and DMA results showed that the glass transition temperature of mixed matrix membranes decreased significantly when the concentration of S-Pd nanoparticle increased. Gas permeation test results showed the opposite trend, that is, gas permeance decreased when glass transition temperature of mixed matrix membranes decreased. In addition, positron annihilation lifetime spectroscopy was utilized to detect the changes in free volume and observe the variation jn free volume change with the additional concentration of S-Pd nanoparticle. Membrane gas separation phenomena was discussed with the analytical results of free volume. However, S-Pd nanoparticle added into the PC membrane enhanced the anti-plasticization ability of the membrane.

摘要 I
ABSTRACT II
致謝 IV
目錄 V
表目錄 VIII
圖目錄 IX
第一章 緒論 1
1-1 薄膜分離 1
1-2 氣體分離膜 4
1-3 促進傳輸薄膜 9
1-4氣體透過理論 15
1-4-1多孔性薄膜 15
1-4-2 緻密薄膜 17
1-4-3 雙重吸附理論 18
1-5氣體分離膜之塑化效應 20
1-6 文獻回顧 21
1-7 研究動機與目的 24
第二章 實驗 25
2-1 實驗藥品 25
2-2 實驗儀器 26
2-3 實驗方法 28
2-3-1聚碳酸酯薄膜的製備 28
2-3-2 S-Pd/PC混合基質薄膜的製備 28
2-3-3 熱性質分析 29
2-3-4 薄膜氣體透過測試 29
2-3-5薄膜結構分析 31
2-3-6薄膜氣體恆溫吸附測試 32
2-3-7正子湮滅壽命光譜（Positron annihilation lifetime spectroscopy, PALS） 34
2-3-8實驗流程 38
第三章 結果與討論 39
3-1奈米粒子濃度對混合基質薄膜結構型態之影響 39
3-2 S-Pd/PC混合基質薄膜之熱性質 42
3-3 S-Pd/PC混合基質薄膜之氣體吸附 43
3-4 S-Pd/PC混合基質薄膜之氣體分離效能 47
3-5 S-Pd/PC混合基質薄膜之塑化效應 51
3-6 自由體積變化對S-Pd/PC MMMs氣體分離行為之影響 53
第四章 結論 57
參考文獻 58

1.藍立文、姜生年、張秋禹，功能性高分子材料，西北工業大學出版社。
2.R.W. Baker, “Membrane technology and applications”, McGraw-Hill, Menlo Park, California, (2000).
3.D.R. Paul and Y.P. Yampol’skii, ”Polymeric gas separation membranes”, CRC Press,(1994).
4.Marcel Mulder, “Basic principles of membrane technology”, Kluwer Academic Publishers, (1997).
5.L.M. Robeson, “Correlation of separation factor versus permeability for polymeric membranes”, J. Membr. Sci., 62, 165(1991).
6.Z. Wang, T. Chen and J. Xu, “Gas transport properties of novel cardo poly(aryl ether ketone)s with pendant alkyl groups”, Macromolecules, 33, 5672 (2000).
7.Z. Wang, T. Chen and J. Xu, “Novel poly(aryl ether ketone)s containing various pendant groups. II. Gas-transport property”, J. Appl. Polym. Sci., 64, 1725 (1997).
8.J. Zhang and X. Hou, “ The gas permeation property trimethyl silyl-substituted PPO and triphenylsilyl-substituted PPO”, J. Membr. Sci., 97, 275 (1994).
9.J. H. Kim, S. B. Lee and S. Y. Kim, “ Incorporation effects of fluorinated side groups into polyimide membranes on their physical and gas permeation properties ”, J. Appl. Polym. Sci., 77, 2756 (2000).
10.S. Takahashi, M. Yoshida, M. Asano, T. Tanaka and T. Nakagawa, ”Effect of heavy-ion irradiation on the gas permeability of poly(ethylene terephthalate) (PET) membranes”, J. Appl. Polym. Sci., 82, 206 (2001).
11.J. Won, M. H. Kim, Y. S. Kang, H. C. Park, U. Y. Kim, S. C. Choi and S. K. Koh, “ Surface modification of polyimide and polysulfone membranes by ion beam for gas separation ”, J. Appl. Polym. Sci., 75, 1554 (2000).
12.C. T. Wright and D. R. Paul, “ Gas sorption and transport in UV- irradiated poly(2,6-dimethyl-1,4-phenylene oxide)films”, J. Appl. Polym. Sci., 67, 875 (1998).
13.M. H. Kim, J. H. Kim, C. K. Kim, Y. S. Kang, H. C. Park and J. O. Won, “ Control of phase separation behavior of PC/PMMA blends and their application to the gas separation membranes”, J. Polym. Sci. Pt. B-Polym. Phys., 37, 2950 (1999).
14.F. A. Ruiz-Trevino and D. R. Paul, “ Gas permselectivity properties of high Free volume polymers modified by a low molecular weight additive ”, J. Appl. Polym. Sci., 68, 403 (1998).
15.S. H. Chen, S. S. Lin, D. J. Chang and J. S. Chang, “ Gas transport properties of CoAlPO4-5/PC Membranes ” J. Appl. Polym. Sci., 77, 89 (2000).
16.A. B. Fuertes, “ Adsorption-selectivity carbon membrane for gas separation”, J. Membr. Sci., 177, 9 (2000).
17.C.L. Aitken, W.J. Koros and D.R. Paul, “Effect of structural symmetry on gas separation properties of polysulfones”, Macromolecules, 25, 3424(1992).
18.D.R. Paul and W.J. Koros, “Effect of partially immobilized transport with ixed site carrier membranes”, J. Polym. Sci., Polym. Phys. Ed., 14, 675(1976).
19.R.D. Noble,” Facilitated transport mechanism in fixed site carrier membranes”, J. Membr. Sci.,60,297(1991).
20.E.L. Cussler, R. Aris and A. Bhown,” On the limits of facilitation diffusion”, J. Membr. Sci., 43,149(1989).
21.Y. S. Kang, Jae-Min Hong, J. Jang, U. Y. Kim,” Analysis of facilitated transport in solid membranes with fixed site carriers 1. Single RC circuit model”, J. Membr. Sci., 109, 149 (1996).
22.Jae-Min Hong , Y. S. Kang, J. Jang, U. Y. Kim,” Analysis of facilitated transport in polymeric membrane with fixed site carrier 2. Series RC circuit model”, J. Membr. Sci., 109, 159 (1996).
23.R. E. Kesting and A. K. F ritzsche, “ Polymeric gas separation membranes”, JOHN WILEY & SONS, Inc., New York, (1993).
24.W. R. Vieth, J. M. Howell and J. H. Hsieh, “ Dual sorption theory”, J. Membr. Sci., 1, 177 (1976).
25.D. R. Paul and W. J. Koros, “ Effect of partially immobilizing sorption on permeability and the diffusion time lag ”, J. Polym. Sci. Pt. B-Polym. Phys., 14, 675 (1976).
26.J. H. Petropoulos, “ Quantitative analysis of gaseous diffusion in glassy polymers”, J. Polym. Sci., part A-2, 8, 1791 (1970).
27.W. R. Vieth and K. J. Sladek, “ A model for diffusion in a glassy polymer”, J. Colloid Sci., 20, 1014 (1965).
28.W. J. Koros and R. Mahajan, “ Pushing the limits on possibilities for large scale gas separation: which strategies ”, J. Membr. Sci., 175, 181 (2000).
29.M. Wessling, M. L. Lopez and H. Strathman, “ Accelerated plasticization of thin-film composite membranes used in gas separation ”, Separ. Purif. Technol., 24, 223 (2001).
30.J. J. Krol, M. Boerrigter and G. H. Koops, “ Polyimide hollow fiber gas separation membranes: Preparation and the suppression of plasticization in propane/propylene environments ”, J. Membr. Sci., 184, 275 (2001).
31.M. Wessling, L. Huisman, T. H. V. d. Boomgaard and C. A. smoulders, “ Time-dependent permeation of carbon dioxide through a polyimide membrane above the plasticization pressure ”, J. Appl. Polym. Sci., 58, 1959 (1995).
32.L. S. White, T. A. Blinka, H. A. Kloczewski and I.-F. Wang, “ Properties of a polyimide gas separation membranes in natural gas streams ”, J. Membr. Sci., 103, 73 (1995).
33.A. F. Ismail and W. Lorna, “ Penetrant-induced plasticization phenomenon in glassy polymers for gas separation membrane ”, Separ. Purif. Technol., 27, 175 (2002).
34.A. Bos, I. G. M. Pünt, M. Wessling and H. Strathmann, “ CO2-induced plasticization phenomena in glassy polymers ”, J. Membr. Sci., 155, 67 (1999).
35.A. G. Wonders and D. R. Paul, “ Effect of CO2 exposure history on sorption and transport in polycarbonate ” , J. Membr. Sci., 5, 63 (1979).
36.A. F. Ismail and W. Lorna, “ Suppression of plasticization in polysulfone membranes for gas separations by heat-treatment technique ”, Separ. Purif. Technol., 30, 37 (2003).
37.B. J. Briscoe and C. T. Kelly, “ The plasticization of a polyurethane by carbon dioxide at high pneumatic stresses ”, Polymer, 36, 3099 (1995).
38.J. H. Petropoulos, “ Plasticization effects on the gas permeability and permselectivity of polymer membranes ”, J. Membr. Sci., 75, 47 (1992).
39.A. Y. Houde, S. S. Kulkarni and M. G. Kulkarni, “ Permeation and plasticization behavior of glassy polymers: a WAXD interpretation ”, J. Membr. Sci., 71, 117 (1992).
40.R. T. Chern and C. N. Provan, “ Gas induced plasticization and the permselectivity of poly(tetrabromophenolphthhalein terephthalate) to a mixture of carbon dioxide and methane ”, Macromolecules, 24, 2203 (1991).
41.G. S. Huvard, V. T. Stannett, W. J. Koros and H. B. Hopfenberg, “ The pressure dependence of CO2 sorption and permeation in poly(acrylonitrile) ”, J. Membr. Sci., 6, 185 (1980).
42.J. S. Chiou and D. R. Paul, “ Effects of CO2 exposure on gas transport properties of glassy polymers ”, J. Membr. Sci., 32 , 195 (1987).
43.Y. He, J. Yang, H. Li and P. Huang, ” The effect of oxygen carriers on gas transport through polysiloxane and ethylcellulose membranes”, Polymer, Vol.39, No.15, 3393 (1998).
44.N. Preethi, H. Shinohara and H. Nishide,” Reversible oxygen-bihding and facilitated oxygen transport in membranes of polyviylimidazole complexed withcobalt-phthalocyanine”, Reactive & Functional polymers 66, 851 (2006).
45.H. Nishide, Y. Tsukahara and E. Tsuchida, ” Highly selective oxygen permeation through a poly(vinylidene dichloride)-cobalt porphyrin membrane: Hopping transport of oxygen via the fixed cobale porphyrin carrier”, J. Polym. Sci. Pt. B-Polym. Phys. 102, 8766 (1998) .
46.Y. Nagasaki, Y. Hashimoto, M. Kato and T. Kimijima,” Gas permeation properties of organosilicon-containing polystyrenes”, J. Membr. Sci., 110, 91 (1996).
47.Y. Xiao, M. L. Chng, T. S. Chung, M. Toriida, S. Tamai, H. Chen and Y. C. Jerry Jean, ”Asymmetric structure and enhanced gas separation performance induced by in situ growth of silver nanoparticles in carbon membranes”, Carbon,48,408 (2010).
48.J.-P. Yuan, H. Cao, E. W. Hellmuth and Y. C. Jean, “ Subnanometer hole properties of CO2-exposed polysulfone studied by positron annihilation lifetime spectroscopy ”, J. Polym. Sci. Pt. B-Polym. Phys., 36, 3049 (1998).
49.Y.C Jean, X. Hong, J. Liu, C.M. Huang, H. Cao, C.Y. Chung, G.H. Dai, K.L. Cheng and H. Yang, “ High sensitivity of positron annihilation lifetime to time and pressure effects in gas-exposed polymers ”, J. Rad. Nucl. Chem., Articles, 210, 513 (1996).
50.H. Chen, M. L. Cheng, Y. C. Jean, L. J. Lee and J. Yang, “ Effect of CO2 exposure on free volumes in polystyrene studied by positron annihilation spectroscopy ”, J. Polym. Sci. Pt. B-Polym. Phys., 46, 388 (2008).
51.Chun-Chieh Tseng, Chang-Pin Chang, Yuh Sung, Jinn-Luh Ou,Ming-Der Ger,” Noble metallic nanoparticles reduced by PS-based oligomers through one-step synthesis”, Colloid and Surfaces A: Physicochem. Eng. Aspects 333, 138 (2009).
52.H. M. Chen, W. S. Hung, J. H. Lo, S. H. Huang, M. L. Cheng, G. Liu, K. R. Lee, J. Y. Lai, Y. M. Sun, C. C. Hu, R. Suzuki, T. Ohdaira, N. Oshima and Y. C. Jean, “ Free-volume depth profile of polymeric membranes studied by positron annihilation spectroscopy: layer structure from interfacial polymerization ”, Macromolecules, 40, 7542 (2007).
53.D. M. Schrader and Y. C. Jean, “ Position and positronium chemistry ”, Elsevier Sci., Amsterdam, (1988).
54.Y. C. Jean, P. E. Mallon and D. M. Schrader, “ Principles and applications of position and positronium chemistry ”, World Scientific, Singapore, (2003).
55.A.F. Ismail and W. Lorna, “ Penetrant-induced plasticization phenomenon in glassy polymers for gas separation membrane ”, Separ. Purif. Technol., 27, 173 (2002).