Effects of Substrates on Nanofiltration Characteristics of Multilayer Polyelectrolyte Membranes

다층 고분자 전해질 막의 나노여과 특성에 미치는 지지체의 영향

  • Hong, Seong-Uk (Department of Chemical Engineering, Hanbat National University)
  • 홍성욱 (한밭대학교 공과대학 화학공학과)
  • Published : 2008.06.30

Abstract

In a previous study, we probed the potential of poly(styrene sulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) nanofiltration (NF) membranes for the separation of monovalent anions, with an emphasis on the selective rejection of $F^-$. Remarkably, deposition of $(PSS/PBADMAC)_4PSS$ films on porous alumina supports yielded membranes that exhibited $Cl^-/F^-$ selectivity > 3 with minimal $Cl^-$ rejection, and a solution flux of $3.5m^3/m^2$-day at 4.8 bar. When the number of PSS/PDADMAC bilayers was increased from 4.5 to 5.5, however, $F^-$ rejection decreased from 73% to 50% and $Cl^-/F^-$ selectivity dropped to 1.9. Addition of another bilayer to form $(PSS/PDADMAC)_6$ PSS films resulted in a significant increase in $Cl^-$ rejection to give essentially no $Cl^-/F^-$ selectivity. The decrease of selectivity with deposition of more than 4.5 bilayers was not expected and it was unclear whether this characteristic was substrate independent. In this study, to investigate the effect of substrates on NF performance of multilayer polyelectrolyte membranes, PSS/PDADMAC films were deposited on 50 kDa polyethersulfone (PES) ultrafiltration supports instead of porous alumina supports. The results indicate that, although fluoride rejection and the number of bilayers at which a maximum $F^-$ rejection occurs are different, the trend is similar for both types of substrates. Therefore, we can conclude that the M: characteristics of multilayer polyelectrolyte membranes may be substrate independent.

선행 연구에서 poly(styrene sulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) 나노 여과막을 사용하여 불소 이온을 포함한 1가 이온 혼합물을 분리하는 것이 가능함을 보였다. 예를 들면, 다공성 알루미나 지지체에 $(PSS/PBADMAC)_4PSS$ 필름을 코팅한 경우 염소/불소 이온의 선택도가 3 이상이었으며 4.8 bar에서 용액의 플럭스가 $3.5m^3/m^2$-day이었다. 그러나, PSS/PDADMAC 이층의 수가 4.5에서 5.5.로 증가하면 염소/불소 이온의 선택도가 1.9로 떨어졌으며, $(PSS/PDADMAC)_6PSS$ 필름의 경우에는 염소 이온의 배제율이 급속히 증가하면서 선택도가 1에 가까웠다. 이러한 선택도의 감소 현상은 예상치 못한 것으로서 다른 지지체를 사용하여도 같은 경향을 보이는지 여부는 불분명하였다. 따라서, 본 연구에서는 다공성 알루미나 대신에 분획 분자량이 50kDa인 다공성 polyethersulfone (PES)에 PSS/PDADMAC을 적층하고 불소/염소 이온 혼합물의 나노 여과 특성을 살펴보았다. 그 결과 다공성 알루미나의 경우와 비록 적층 수는 달랐으나 불소 이온의 배제율이 최대가 되는 최적 적층수가 존재하였으며 이로부터 이러한 현상이 지지체에 무관한 일반적인 사실임을 알 수 있었다.

Keywords

References

  1. N. Kim, 'Preparation and characterization of fouling resistant nanofiltration membranes', Membrane Journal, 17, 44 (2007)
  2. I. C. Kim and K. H. Lee, 'Preparation of poly(vinyl alcohol)-coated composite nanofiltration membranes on various support membranes', Membrane Journal, 15, 34 (2005)
  3. J. H. Choi, C. K. Yeom, J. M. Lee, and D. S. Suh, 'Nanofiltration of electrolytes with charged composite membranes', Membrane Journal, 13, 29 (2003)
  4. B. W. Stanton, J. J. Harris, M. D. Miller, and M. L. Bruening, 'Ultrathin, multilayered polyelectrolyte films as nanofiltration membranes', Langmuir, 19, 7038 (2003) https://doi.org/10.1021/la034603a
  5. A. M. Hollman and D. Bhattacharyya, 'Pore assembled multilayers of charged polypeptides in microporous membranes for ion separation', Langmuir, 20, 5418 (2004) https://doi.org/10.1021/la049688+
  6. A. M. Hollman and D. Bhattacharyya, 'Controlled permeability and ion exclusion in microporous membranes functionalized with poly(L-glutamic acid)', Langmuir, 18, 5946 (2002) https://doi.org/10.1021/la025662b
  7. A. M. Balachandra, J. Dai, and M. L., Bruening, 'Enhancing the anion-transport selectivity of multilayer polyelectrolyte membranes by templating with $Cu^{2+}$', Macromolecule, 35, 3171 (2002) https://doi.org/10.1021/ma0116349
  8. S. U. Hong, R. Malaisamy, and M. L. Bruening, 'Optimization of flux and selectivity in ${Cl-/SO_4}^{2-}$ separation with multilayer polyelectrolyte membranes', J. Membr. Sci., 283, 366 (2006) https://doi.org/10.1016/j.memsci.2006.07.007
  9. B. Tieke, A. Toutianoush, and W. Jin, 'Selective transport of ions and molecules across layer-by-layer assembled membranes of polyelectrolytes, p-sulfonato-calix n arenas and Prussian Blue-type complex salts', Adv. Colloid. Interf. Sci., 116, 12 (2005)
  10. L. Krasemann and B. Tieke, 'Selective ion transport across self-assembled alternating multilayers of cationic and anionic polyelectrolytes', Langmuir, 16, 287 (2000) https://doi.org/10.1021/la991240z
  11. W. Jin, A. Toutianoush, and B. Tieke, 'Use of polyelectrolyte layer-by-layer assemblies as nanofiltration and reverse osmosis membranes', Langmuir, 19, 2550 (2003) https://doi.org/10.1021/la020926f
  12. S. U. Hong, R. Malaisamy, and M. L. Bruening, 'Separation of fluoride from other monovalent anions using multilayer polyelectrolyte nanofiltration membranes', Langmuir, 23, 1716 (2007) https://doi.org/10.1021/la061701y
  13. R. Malaisamy and M. L. Bruening, 'High-flux nanofiltration membranes prepared by adsorption of multilayer polyelectrolyte membranes on polymeric supports', Langmuir, 21, 10587 (2005) https://doi.org/10.1021/la051669s
  14. M. Salomaki, T. Laiho, and J. Kankare, 'Counteranion-controlled properties of polyelectrolyte multilayers', Macromolecules, 37, 9585 (2004) https://doi.org/10.1021/ma048701u
  15. G. Ladam, P. Schaad, J. C. Voegel, P. Schaaf, G. Decher, and F. Cuisinier, 'In situ determination of the structural properties of initially deposited polyelectrolyte multilayers', Langmuir, 16, 1249 (2000) https://doi.org/10.1021/la990650k
  16. H. W. Jomaa and J. B. Schlenoff, 'Salt-induced polyelectrolyte interdiffusion in multilayered films: A neutron reflectivity study', Macromolecules, 38, 8473 (2005) https://doi.org/10.1021/ma050072g
  17. O. M. Tanchak, K. G. Yager, H. Fritzche, T. Harroun, J. Katsaras, and C. J. Barrett, 'Water distribution in multilayers of weak polyelectrolytes', Langmuir, 22, 5137 (2006) https://doi.org/10.1021/la0529613
  18. Handbook of Chemistry and Physics, CRC Press, Boca Raton, Florida, 2000, pp. 5-91
  19. R. Malaisamy, personal communication (2008)