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SNIPS 공정을 이용한 블록공중합체 분리막의 구조 형성에 관한 연구

Fabrication of Block Copolymer Membranes via SNIPS Process

  • 우상훈 (고려대학교 화공생명공학과) ;
  • 김진희 (고려대학교 화공생명공학과) ;
  • 이정현 (고려대학교 화공생명공학과) ;
  • 방준하 (고려대학교 화공생명공학과)
  • Woo, Sanghoon (Department of Chemical & Biology, Korea University) ;
  • Kim, Jinhee (Department of Chemical & Biology, Korea University) ;
  • Lee, Junghyun (Department of Chemical & Biology, Korea University) ;
  • Bang, Joona (Department of Chemical & Biology, Korea University)
  • 투고 : 2016.09.09
  • 심사 : 2016.12.22
  • 발행 : 2017.04.01

초록

본 연구에서는 블록공중합체의 자기조립(Self-assembly) 성질과 상전이를 통한 비대칭의 다공성 구조를 형성하는 NIPS 기술을 결합한 SNIPS (Self-assembly and non-solvent induced phase separation) 공정을 이용하여 PS-b-P4VP 블록공중합체 분리막을 제조하였다. 기존의 연구는 단순히 원하는 구조 구현에만 집중되었고 SNIPS 공정상의 내재 변수(농도, 증발시간, 용매의 조성, 습도)들에 대한 체계적인 연구는 보고되지 않았다. 본 연구에서는 PS-b-P4VP 와 DMF, 1,4-Dioxane, THF, DI를 이용해 내재 변수의 영향을 정성적으로 분석하였다. 그 결과, 용액의 농도와 휘발성 용매의 비율이 적당하고 습도가 낮은 환경에서 모폴로지가 최적화 되었으며, PS-b-P4VP 분리막은 표면에 잘 구현된 실린더 구조가 형성되었고 75%의 높은 기공도와 약 18%의 표면 기공도를 가지는 것을 확인하였다.

In this work, we fabricated PS-b-P4VP block copolymer membranes from self-assembly and non-solvent induced phase separation (SNIPS), which combines the block copolymer self-assembly and conventional NIPS process. While previous studies mostly focused on the fabrication of well-defined structures, we systematically examined various processing parameters such as polymer concentration, solvent evaporation duration, solvent composition, and humidity, to optimized the membrane structures. As a result, the morphology of PS-b-P4VP membranes was optimized at a certain polymer concentration in solution and composition of volatile solvent at low humidity conditions, resulting in SNIPS separation membranes with well-defined nanopores on the surface, 75% of membrane porosity, and 18% of surface porosity.

키워드

참고문헌

  1. Geise, G. M., Lee, H. S., Miller, D. J., Freeman, B. D., McGrath, J. E. and Paul, D. R., "Water Purification by Membranes: the Role of Polymer Science, " J. Polym. Sci. Polym. Phys., 48(15), 1685-1718(2010). https://doi.org/10.1002/polb.22037
  2. Guillen, G. R., Pan, Y., Li, M. and Hoek, E. M., "Preparation and Characterization of Membranes Formed by Nonsolvent Induced Phase Separation: a Review," Ind. Eng. Chem. Res., 50(7), 3798- 3817(2011). https://doi.org/10.1021/ie101928r
  3. Cho, E. H. and Rhim, J. W., "Preparation of a New Charged Nanofiltration Membrane Based on Polyelectrolyte Complex by Forced Fouling Induction for a Household Water Purifier," Macromol. Res., 23(2), 183-188(2015). https://doi.org/10.1007/s13233-015-3017-1
  4. Chen, Y., Ying, L., Yu, W., Kang, E. and Neoh, K., "Poly(vinylidene fluoride) with Grafted Poly(ethylene glycol) Side Chains via the RAFT-Mediated Process and Pore Size Control of the Copolymer Membranes," Macromolecules, 36(25), 9451-9457(2003). https://doi.org/10.1021/ma035194s
  5. Kim, I.-C., Yun, H.-G. and Lee, K.-H., "Preparation of Asymmetric Polyacrylonitrile Membrane with Small Pore Size by Phase Inversion and Post-treatment Process", J. Membrane Sci., 199(1), 75-84(2002). https://doi.org/10.1016/S0376-7388(01)00680-9
  6. Jung, B. S., "Preparation of Hydrophilic Polyacrylonitrile Blend Membranes for Ultrafiltration," J. Membrane Sci., 229(1), 129-136(2004). https://doi.org/10.1016/j.memsci.2003.10.020
  7. Cha, B. and Chi, S., "Polymeric Membranes for Water Treatment," Polym. Sci. Tech., 22(6), 553-560(2011).
  8. Jung, H., Kim, T. J. and Bang, J., "The Vertical and Lateral Ordering of PDMA-b-PS Block Copolymer Thin Film via Control of Relative Humidity," Korean Chem. Eng. Res., 49(3), 352-356(2011). https://doi.org/10.9713/kcer.2011.49.3.352
  9. Lee, J., Park, B., Kim, J. and Park, S. B., "Effect of PVP, Lithium Chloride, and Glycerol Additives on PVDF Dual-layer Hollow Fiber Membranes Fabricated Using Simultaneous Spinning of TIPS and NIPS," Macromol. Res., 23(3), 291-299(2015). https://doi.org/10.1007/s13233-015-3037-x
  10. Kim, T. H., Jee, K. Y. and Lee, Y. T., "The Improvement of Water Flux and Mechanical Strength of PVDF Hollow Fiber Membranes by Stretching and Annealing Conditions", Macromol. Res., 23(7), 592-600(2015). https://doi.org/10.1007/s13233-015-3087-0
  11. Lee, S. and Kim, S. S., "Structural Changes of PVDF Membranes by Phase Separation Control," Korean Chem. Eng. Res., 54(1), 57-63(2016). https://doi.org/10.9713/kcer.2016.54.1.57
  12. Peinemann, K.-V., Abetz, V. and Simon, P. F., "Asymmetric Superstructure Formed in a Block Copolymer Via Phase Separation," Nat. Mater., 6(12), 992-996(2007). https://doi.org/10.1038/nmat2038
  13. Abetz, V., "Isoporous Block Copolymer Membranes," Macromol. Rapid Comm., 36(1), 10-22(2015). https://doi.org/10.1002/marc.201400556
  14. Rangou, S., Buhr, K., Filiz, V., Clodt, J. I., Lademann, B., Hahn, J., Jung, A. and Abetz, V., "Self-organized Isoporous Membranes with Tailored Pore Sizes", J. Membrane Sci., 451, 266-275(2014). https://doi.org/10.1016/j.memsci.2013.10.015
  15. Clodt, J. I., Bajer, B., Buhr, K., Hahn, J., Filiz, V. and Abetz, V., "Performance Study of Isoporous Membranes with Tailored Pore Sizes," J. Membrane Sci., 495, 334-340(2015). https://doi.org/10.1016/j.memsci.2015.07.041
  16. Yu, H., Qiu, X., Nunes, S. P. and Peinemann, K. V., "Self-Assembled Isoporous Block Copolymer Membranes with Tuned Pore Sizes," Angew. Chem. Int. Ed., 126(38), 10236-10240(2014). https://doi.org/10.1002/ange.201404491
  17. Nunes, S. P., Sougrat, R., Hooghan, B., Anjum, D. H., Behzad, A. R., Zhao, L., Pradeep, N., Pinnau, I., Vainio, U. and Peinemann, K. V., "Ultraporous Films with Uniform Nanochannels by Block Copolymer Micelles Assembly," Macromolecules, 43(19), 8079-8085(2010). https://doi.org/10.1021/ma101531k
  18. Clodt, J. I., Rangou, S., Schroder, A., Buhr, K., Hahn, J., Jung, A., Filiz, V. and Abetz, V., "Carbohydrates as Additives for the Formation of Isoporous PS-b-P4VP Diblock Copolymer Membranes, " Macromol. Rapid Comm., 34(2), 190-194 (2013). https://doi.org/10.1002/marc.201200680
  19. Gallei, M., Rangou, S., Filiz, V., Buhr, K., Bolmer, S., Abetz, C. and Abetz, V., "The Influence of Magnesium Acetate on the Structure Formation of Polystyrene-block-poly(4-vinylpyridine)-Based Integral-Asymmetric Membranes", Macromol. Chem. Phys., 214(9), 1037-1046(2013). https://doi.org/10.1002/macp.201200708
  20. Hahn, J., Filiz, V., Rangou, S., Lademann, B., Buhr, K., Clodt, J. I., Jung, A., Abetz, C. and Abetz, V., "PtBS-b-P4VP and PTMSS-b-P4VP Isoporous Integral-Asymmetric Membranes with High Thermal and Chemical Stability," Macromol. Mater. Eng., 298(12), 1315-1321(2013). https://doi.org/10.1002/mame.201300012
  21. Hilke, R., Pradeep, N., Behzad, A. R., Nunes, S. P. and Peinemann, K. V., "Block Copolymer/homopolymer Dual-layer Hollow Fiber Membranes," J. Membrane Sci., 472, 39-44(2014). https://doi.org/10.1016/j.memsci.2014.08.031
  22. Li, X. and Han, Y., "Tunable Wavelength Antireflective Film by Non-solvent-induced Phase Separation of Amphiphilic Block Copolymer Micelle Solution," J. Mater. Chem., 21(44), 18024-18033(2011). https://doi.org/10.1039/c1jm13704b
  23. Jung, A., Rangou, S., Abetz, C., Filiz, V. and Abetz, V., "Structure Formation of Integral Asymmetric Composite Membranes of Polystyrene-block-poly(2-vinylpyridine) on a Nonwoven," Macromol. Mater. Eng., 297(8), 790-798(2012). https://doi.org/10.1002/mame.201100359
  24. Stegelmeier, C., Filiz, V., Abetz, V., Perlich, J., Fery, A., Ruckdeschel, P., Rosenfeldt, S. and Förster, S., "Topological Paths and Transient Morphologies During Formation of Mesoporous Block Copolymer Membranes," Macromolecules, 47(16), 5566-5577(2014). https://doi.org/10.1021/ma5004908
  25. Hahn, J., Filiz, V., Rangou, S., Clodt, J., Jung, A., Buhr, K., Abetz, C. and Abetz, V., "Structure Formation of Integral-asymmetric Membranes of Polystyrene-block-poly(Ethylene Oxide)," Procedia Eng., 44, 1844-1847(2012). https://doi.org/10.1016/j.proeng.2012.08.972
  26. Karunakaran, M., Nunes, S. P., Qiu, X., Yu, H. and Peinemann, K.-V., "Isoporous PS-b-PEO Ultrafiltration Membranes via Self-assembly and Water-induced Phase Separation, " J. Membrane Sci., 453, 471-477(2014). https://doi.org/10.1016/j.memsci.2013.11.015
  27. Phillip, W. A., O'Neill, B., Rodwogin, M., Hillmyer, M. A. and Cussler, E., "Self-assembled Block Copolymer Thin Films as Water Filtration Membranes," ACS Appl. Mater. Inter., 2(3), 847-853(2010). https://doi.org/10.1021/am900882t
  28. Cha, B. J., Chi, S. D. and Kim, J. H., Membrane Market for Water Treatment, KIC News, 14(6), 2-8(2011).
  29. Phillip, W. A., Hillmyer, M. A. and Cussler, E., "Cylinder Orientation Mechanism in Block Copolymer Thin Films Upon Solvent Evaporation," Macromolecules, 43(18), 7763-7770(2010). https://doi.org/10.1021/ma1012946
  30. Susanto, H. and Ulbricht, M., "Characteristics, Performance and Stability of Polyethersulfone Ultrafiltration Membranes Prepared by Phase Separation Method Using Different Macromolecular Additives", J. Membrane Sci., 327(1), 125-135(2009). https://doi.org/10.1016/j.memsci.2008.11.025
  31. Ramakrishna, S., Ma, Z. and Matsuura, T., Polymer Membranes in Biotechnology: Preparation, Functionalization and Application. Imperial College Press: 2011.
  32. Yip, Y. and McHugh, A. J., "Modeling and Simulation of Nonsolvent Vapor-induced Phase Separation," J. Membrane Sci., 271(1), 163-176(2006). https://doi.org/10.1016/j.memsci.2005.06.063
  33. Chaturbedy, P., Jagadeesan, D. and Eswaramoorthy, M., "pH-Sensitive Breathing of Clay Within the Polyelectrolyte Matrix," ACS Nano, 4(10), 5921-5929(2010). https://doi.org/10.1021/nn100700b
  34. Kang, S., Asatekin, A., Mayes, A. M. and Elimelech, M., "Protein Antifouling Mechanisms of PAN UF Membranes Incorporating PAN-g-PEO Additive," J. Membrane Sci., 296(1), 42-50(2007). https://doi.org/10.1016/j.memsci.2007.03.012
  35. Widjojo, N., Chung, T.-S., Weber, M., Maletzko, C. and Warzelhan, V., "The Role of Sulphonated Polymer and Macrovoid-free Structure in the Support Layer for Thin-film Composite (TFC) Forward Osmosis (FO) Membranes," J. Membrane Sci., 383(1), 214-223(2011). https://doi.org/10.1016/j.memsci.2011.08.041
  36. Tiraferri, A., Yip, N. Y., Phillip, W. A., Schiffman, J. D. and Elimelech, M., "Relating Performance of Thin-film Composite Forward Osmosis Membranes to Support Layer Formation and Structure," J. Membrane Sci., 367(1), 340-352(2011). https://doi.org/10.1016/j.memsci.2010.11.014
  37. Cath, T. Y., Childress, A. E. and Elimelech, M., "Forward Osmosis: Principles, Applications, and Recent Developments, " J. Membrane Sci., 281(1), 70-87(2006). https://doi.org/10.1016/j.memsci.2006.05.048
  38. Yasukawa, M., Mishima, S., Shibuya, M., Saeki, D., Takahashi, T., Miyoshi, T. and Matsuyama, H., "Preparation of a Forward Osmosis Membrane Using a Highly Porous Polyketone Microfiltration Membrane as a Novel Support," J. Membrane Sci., 487, 51-59(2015). https://doi.org/10.1016/j.memsci.2015.03.043