by Prof. Volodymyr V. Tarabara
The last two decades have seen membrane-based separation established as a family of broadly accepted technologies that complement and often replace traditional water treatment unit processes such as granular media filtration, chemical precipitation and softening. Membranes processes such as microfiltration, ultrafiltration, nanofiltration, and reverse osmosis, can be used to remove a diverse range of pollutants from a variety of source waters. As of 2008, the membrane industry in U.S. alone is $2.9 billion and growing.
The commercial success of membrane technologies is grounded in the continuous innovation in the areas of membrane materials and processes. Recent developments in the materials science of membranes have been fueled in large part by advances in nanotechnology. Membranes with improved permeability, selectivity, and resistance to fouling have been developed using newly available nanomaterials.
Functional nanomaterials have been used to synergistically combine separation and additional functions and prepare more efficient membranes with a smaller environmental footprint. Examples of nanomaterial-enabled membranes include:
i) membranes prepared from nanomaterials (e.g., ceramic membranes that have been traditionally prepared from inorganic materials such as TiO2, ZrO2, Al2O3, etc.1 but also the novel class of membranes prepared from carbon nanomaterials such as carbon nanotubes2-4);
ii) membranes prepared by nanomaterial templating5;
iii) polymer nanocomposite membranes (e.g., using TiO26-8, Ag09-11, Al2O312,13, and SiO214-16, NaA zeolite17 as inorganic fillers);
iv) membrane reactors with functional nanoparticles (e.g., Fe/Ni18-20, Fe/Pd20,21, Ag022, gold23, zero-valent iron24).
Our NSF-sponsored research project “Partnership for International Research and Education: New generation synthetic membranes - Nanotechnology for drinking water safety” is an example of a large interdisciplinary of effort focused on the development of new nanotechnology-enabled membrane processes and technologies. The Partnership is on the design of nanostructured membranes and addresses fundamental nanomaterials chemistry and materials science as applied to water quality technologies. The project is a joint effort between a number of research groups in the United States and abroad. An example PIRE project is our recent study on the design of biofouling resistant silver-polysulfone composite membranes. In this work, the nanocomposite membranes were synthesized by incorporating silver nanoparticles into the polymer matrix of a membrane.
Inhibition of biofilm growth on the surface of Ag nanoparticle-filled membranes
The particles were either synthesized ex-situ and then added to the casting solution as organosol or produced in the casting solution via in-situ reduction of ionic silver by the polymer solvent. We have shown that the antibacterial capacity due to the gradual release of ionic silver by the prepared nanocomposites can be effective in reducing intrapore biofouling in nanocomposite membranes of a wide range of porosities. Such nanocomposites could also be used as materials for macroporous membrane spacers to inhibit the biofilm growth on downstream membrane surfaces11.
Casting nanocomposite membranes using controlled temperature/humidity chamber. From left to right: Julian Taurozzi (now at NIST), Volodymyr Tarabara, Alex Wang (now with Pentair, Inc.), Adam Rogensues (now with Severn Trent)
Another example of how functional nanoparticle can be used to improve membrane performance is the hybrid ozonation-ultrafiltration hybrid process. This process is at the focus of the NSF-funded research project at Michigan State University. The combination of nanoparticle-based functionalities with membrane separation in one hybrid unit improves the overall process efficiency and remove excessive redundancy25-31.
In the hybrid system, ozonation is effective in mitigating membrane fouling due to the oxidation of foulants by ozone and/or hydroxyl radicals. By introducing nanoparticles such as Fe2O3 and MnO2 at the membrane surface, the efficiency of the hybrid process can be significantly enhanced due to both the catalytic effect of the nanoparticles and more targeted oxidation of the NOM portion that is concentrated at or near the membrane surface contributing to membrane fouling.
A unique aspect of this hybrid process is that due to the effect of catalytic ozonation at the membrane surface, the surface remains relatively foulant-free; therefore, in the absence of the fouling layer, foulant-membrane interactions remain important for extended periods of membrane operation. This, in turn, increases the relevance of membrane surface engineering for longer term membrane operation.
1. Li, K., Ceramic Membranes for Separation and Reaction. 2007: J. Wiley & Sons.
2. Fornasiero, F., Park, H. G., Holt, J. K., Stademann, M., Grigoropoulos, C. P., Noy, A. and Bakajin, O. Ion exclusion by sub-2-nm carbon nanotube pores, PNAS 105 (2008) 17250-17255.
3. Hinds, B. J., Chopra, N., Rantell, T., Andrews, R., Gavalas, V. and Bachas, L. G. Aligned multiwalled carbon nanotube membranes, Science 303 (2004) 62-65.
4. Holt, J. K., Park, H. G., Wang, Y., Stademann, M., Artyukhin, A. B., Grigoropoulos, C. P., Noy, A. and Bakajin, O. Fast mass transport through sub-2-nnaometer carbon nanotubes, Science 312 (2006) 1034-1037.
5. Velev, O. D. and Lenhoff, A. M. Colloidal crystals as templates for porous materials, Curr. Opinion Colloid Interface Sci. 5 (2000) 56-63.
6. Ebert, K., Fritsch, D., Koll, J. and Tjahjawiguna, C. Influence of inorganic fillers on the compaction behaviour of porous polymer based membranes, J. Membr. Sci. 233 (2004) 71-78.
7. Li, J. B., Zhu, J. W. and Zheng, M. S. Morphologies and properties of poly(phthalazinone ether sulfone ketone) matrix ultrafiltration membranes with entrapped TiO2 nanoparticles, J. Appl. Polym. Sci. 103 (2006) 3623-3629.
8. Yang, Y., Zhang, H., Wang, P., Zheng, Q. and Li, J. The influence of nano-sized TiO2 fillers on the morphologies and properties of PSF UF membrane, J. Membr. Sci. 288 (2007) 231-238.
9. Chou, W. L., Yu, D. G. and Yang, M. C. The preparation and characterization of silver-loading cellulose acetate hollow fiber membrane for water treatment, Polym. Adv. Technol. 16 (2005) 600 - 607.
10. Son, W. K., Youk, J. H., Lee, T. S. and Park, W. H. Preparation of antimicrobial ultrafine cellulose acetate fibers with silver nanoparticles, Macromol. Rapid Commun. 25 (2004) 1632-1637.
11. Taurozzi, J. S., Arul, H., Bosak, V. Z., Burban, A. F., Voice, T. C., Bruening, M. L. and Tarabara, V. V. Effect of filler incorporation route on the properties of polysulfone-silver nanocomposite membranes of different porosities, J. Membr. Sci. 325 (2008) 58-68.
12. Wara, N. M., Francis, L. F. and Velamakanni, B. V. Addition of alumina to cellulose acetate membranes, J. Membr. Sci. 104 (1995) 43-49.
13. Yan, L., Li, Y. S., Xiang, C. B. and Xianda, S. Effect of nano-sized Al2O3-particle addition on PVDF ultrafiltration membrane performance, J. Membr. Sci. 276 (2006) 162-167.
14. Aerts, P., Genne, I., Kuypers, S., Leysen, R., Vankelecom, I. F. J. and Jacobs, P. A. Polysulfone-aerosil composite membranes: Part 2. The influence of the addition of aerosil on the skin characteristics and membrane properties, J. Membr. Sci. 178 (2000) 1-11.
15. Aerts, P., Van Hoof, E., Leysen, R., Vankelecom, I. F. J. and Jacobs, P. A. Polysulfone-aerosil composite membranes: Part 1. The influence of the addition of Aerosil on the formation process and membrane morphology, J. Membr. Sci. 176 (2000) 63-73.
16. Nunes, S. P., Peinemann, K. V., Ohlrogge, K., Alpers, A., Keller, M. and Pires, A. T. N. Membranes of poly(ether imide) and nanodispersed silica, J. Membr. Sci. 157 (1999) 219-226.
17. Jeong, B.H., Hoek, E. M. V., Yan, Y., Huang, X., Subramani, A., Hurwitz, G., Ghosh, A. K. and Jawor, A. Interfacial polymerization of thin film nanocomposites: A new concept for reverse osmosis membranes, J. Membr. Sci. 294 (2007) 1-7.
18. Meyer, D. E., Wood, K., Bachas, L. G. and Bhattacharyya, D. Degradation of chlorinated organics by membrane-immobilized nanosized metals, Environ. Prog. 23 (2004) 232-242.
19. Wu, L. and Ritchie, S. M. C. Removal of trichloroethylene from water by cellulose acetate supported bimetallic Ni/Fe nanoparticles, Chemosphere 63 (2006) 285.
20. Xu, J., Dozier, A. and Bhattacharyya, D. Synthesis of nanoscale bimetallic particles in polyelectrolyte membrane matrix for reductive transformation of halogenated organic compounds, J. Nanopart. Res. 7 (2005) 449-467.
21. Xu, J. and Bhattacharyya, D. Fe/Pd nanoparticle immobilization in microfiltration membrane pores: Synthesis, characterization, and application in the dechlorination of polychlorinated biphenyls, Ind. Eng. Chem. Res. 46 (2007) 2348-2359.
22. Dai, J. and Bruening, M. L. Catalytic nanoparticles formed by reduction of metal Ions in multilayered polyelectrolyte films, Nanoletters 2 (2002) 497 - 501.
23. Dotzauer, D. M., Dai, J., Sun, L. and Bruening, M. L. Catalytic membranes prepared using layer-by-layer adsorption of polyelectrolyte/metal nanoparticle films in porous supports, Nano Lett. (2006) 2268-2272.
24. Wu, L.F., Shamsuzzoha, M. and Ritchie, S.M.C. Preparation of cellulose acetate supported zero-valent iron nanoparticles for the dechlorination of trichloroethylene in water, J. Nanopart. Res. 7 (2005) 469-476.
25. Karnik, B. S., Baumann, M. J., Masten, S. J. and Davies, S. H. AFM and SEM characterization of iron oxide coated ceramic membranes, J. Membr. Sci. 41 (2006) 6861-6870.
26. Karnik, B. S., Davies, S. H., Baumann, M. J. and Masten, S. J. Fabrication of catalytic membranes for the treatment of drinking water using combined ozonation and ultrafiltration, Environ. Sci. Technol. 39 (2005) 7656-7661.
27. Karnik, B. S., Davies, S. H., Baumann, M. J. and Masten, S. J. The effects of combined ozonation and filtration on disinfection by-product formation, Water Res. 39 (2005) 2839-2850.
28. Karnik, B. S., Davies, S. H. R., Chen, K. C., Jaglowski, D. R., Baumann, M. J. and Masten, S. J. Effects of ozonation on the permeate flux of nanocrystalline ceramic membranes, Water Res. 39 (2005) 728-734.
29. Schlichter, B., Mavrov, V. and H., Chmiel Study of a hybrid process combining ozonation and microfiltration/ultrafiltration for drinking water production from surface water, Desalination 168 (2004) 307-317.
30. Kim, J., Davies, S. H. R., Baumann, M. J., Tarabara, V. V. and Masten, S. J. Effect of ozone dosage and hydrodynamic conditions on the permeate flux in a hybrid ozonation-ceramic ultrafiltration system treating natural waters, J. Membr. Sci. 311 (2008) 165-172.
31. Kim, J., Shan, W. Q., Davies, S. H. R., Baumann, M. J., Masten, S. J. and Tarabara, V. V. Interactions of Aqueous NOM with Nanoscale TiO2: Implications for Ceramic Membrane Filtration-Ozonation Hybrid Process, Environ. Sci. Technol. 43 (2009) 5488-5494.
Copyright AZoNano.com, Professor Volodymyr Tarabara (Michigan State University)
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