VIEWPOINT

The Role of Polymers in Breakthrough Technologies for Water Purification

BENJAMIN CHU, BENJAMIN S. HSIAO Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400

Received 18 May 2009; revised 25 June 2009; accepted 29 June 2009 DOI: 10.1002/polb.21854 Published online in Wiley InterScience (www.interscience.wiley.com).

Keywords: bers; purication

membranes;

nanober;

nanotechnology;

separation

techniques;

water

BACKGROUND The term, polymers, in its broader interpretation as macromolecules, is one of the essential elements of modern materials, not to mention the basic components of life, as revealed in our knowledge on bio-macromolecules. In the current state of water purication, polymers play many roles, some critical but mostly supporting, in this extremely fragmented industry, which includes ltration and water treatment. In the latter case, the industrial development involves infrastructure, automation, engineering, pumps, valves, testing, and etc. For water purication by ltration, which has been proven as the most energy efcient method, the critical component is the membrane technology, in which polymer membranes have emerged as the preferred choice over its inorganic counterparts due to low cost and diverse functionality.1,2 In this viewpoint deliberation, we describe some pathways that can signicantly improve the ux performance of polymer membranes when maintaining the same rejection ratio and selectivity. As the elements in the membrane can dene the performance of the ltration system, the enhanced membrane performance has the potential to revolutionize the current water purication technology by offering cheaper, simpler, and smaller systems with less energy and less maintenance needs. Perhaps the scenario is somewhat similar to the computer industry, where faster
Correspondence to: B. Chu (E-mail: bchu@notes.cc. sunysb.edu) or B. S. Hsiao (E-mail: bhsiao@notes.cc.sunysb. edu)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 47, 24312435 (2009)
C V 2009 Wiley Periodicals, Inc.

CPU has drastically reduced the system and infrastructure needs, leading to more mobile devices of greater efciency and functionality. Our viewpoints on the role of polymers in upcoming breakthrough technologies developed for water purication are as follows. WHY IS WATER IMPORTANT? Water has been known to be important from ancient times, especially in the orient, as one of the ve fundamental elements (re, water, wood, metal, and earth, or ), in which re, or in modern terms, energy, has already been publicized as a challenge that requires immediate attention. We believe that the importance of water will soon follow as one of the new challenges of the 21st century. With global warming and a population reaching about 9 billion by 2050, (vs. $2.5 billion and $6 billion, respectively, in 1950 and 2000),3 there is simply not enough usable water for many parts of the world, especially for people to lead a standard of living that one aspires to. This is because the distribution of usable water on earth is extremely uneven and most people do not live only in regions where there is plenty of accessible usable water. Of course, there is plenty of water on earth ($1.3 109 km3). However, $97% of water on earth is in the oceans and, of the remaining 3%, $99% is ground water and relatively inaccessible glaciers and ice caps, whereas surface water in rivers and lakes can account for only $0.01% of water on earth, with $98% of the 0.01% in lakes and swamps.4 Thus, the key sources of water, aside from rivers and lakes, are from oceans ($97%) and from ground water ($1%), although the rate of 2431

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replenishment for ground water needs to be taken into account, if we were to increase its usage substantially. We are used to getting usable water at low cost, because our civilization originated largely near rivers where water is replenished naturally by precipitation using solar energy. Although we can change our habits on water consumption and emphasize on conservation, we still need access to usable water at an affordable cost in order to sustain life and to maintain a reasonable standard of living. The scale of the project and the need to adhere to cost effectiveness that depends on specic requirements and targets are of primary importance. In a 1961 press conference, the late President John F. Kennedy stated, We have made some scientic advances in the last decade, and some of them are not as spectacular as the man in space, or as the rst sputnik, but they are important. I have said that I thought that if we could ever competitively, at a cheap rate, get fresh water from salt water, that it would be in the long-range interests of humanity which would really dwarf any other scientic accomplishments. President Kennedy has a point, that is, we need to simulate nature, which is often a very tough challenge, and to drastically decrease the cost of desalination. It is an inspiring and worthy goal. CAN WE BREAK THROUGH THE CURRENT TECHNOLOGY BARRIER TO ACHIEVE THE ABOVE GOAL? We are optimistic in our current technology development and suggest that the goal can be reached in the near future. To achieve this goal, it is important that we start with a broad perspective, because water purication has many facets and the problem is complex. Therefore, due to the requirements of cost effectiveness and large scales, we must rst take into account what modern science and technology can bring to the table, not to be limited by basic disciplines, such as, biology, chemistry, physics, and engineering. For example, there are differences in the forms of impurities in water; for example, impurities can be in the form of bacteria, organic or inorganic particulates, or dissolved species, such as, metal ions. To remove the impurities, fundamental knowledge based on biology and chemistry can play a primary role. One should be interested to know whether the impurity is hydrophobic or hydrophilic or/ and whether the separation membrane can survive in basic or acidic environments. For particulates, what are the sizes and the shapes? Engineering becomes essential when we deal with large scales. One can think of a beautiful concept but there is a substantial gap between a laboratory demonstration and a large scale operation, especially when cost is of primary importance. The combination of a multidisciplinary approach, involving biology, chemistry, engineering, materials, and physics, and a realization on using polymers as the promising mate-

rials, forms the basis of this breakthrough technology. It is important to recognize that we are dealing with water, which is intimately connected with our life. Thus, the proper materials that have the appropriate morphology and structure, as well as mechanical and surface properties are likely to come from macromolecules. SOME EXAMPLE BREAKTHROUGHS IN THE MEMBRANE TECHNOLOGY Recently, there are several publications indicating that breakthroughs in the membrane technology are within our reach. For example, one research team demonstrated that if water molecules can be injected into the inner cavity of a single-walled carbon nanotube,5 the transportation rate of the water molecules is 23 orders of magnitude higher than that in the bulk state. Based on this technology, an energy efcient reverse osmosis (RO) system may be obtainable. However, this technology is facing some practical challenges: it is difcult to nd a substrate that can (1) be mechanically strong to support the vertically aligned nanotubes, (2) seal off the entrance to the space between the nanotubes, allowing only the passage of water within the tube, and (3) be able to generate cost effective systems. Similarly, another research team demonstrated that water transport efciency in the bacterial water-channel (Aquaporin Z protein) is 80 times higher than that in conventional RO membranes.6 However, this technology also has some similar practical challenges: (1) the channel density may not be high in such polymer membranes (e.g., triblock-polymer vesicles as the base materials) containing Aquaporin Z protein, and (2) the mechanical strength and durability of these membranes are relatively weak. The above ndings challenge the conventional viewpoint as to how the RO membrane really works. The current belief is that water transport in the RO membrane is through the dissolution and the subsequent diffusion of water molecules in the swollen barrier layer, not through the pores or molecular channels in the layer. Clearly the presence of well-dened water channels can greatly facilitate the transport of water. However, the nature of an ideal water channel is not yet known precisely (e.g., whether the channel surface should be hydrophobic or hydrophilic). We are condent that this will be an active research area in the future. There are also other interesting technologies, such as, the inclusion of zeolite nanoparticles in the barrier layers for RO membranes,7 which may improve the total transport efciency of water. Although the above technologies are all in their infancy and many technical challenges have yet to be overcome, we are condent that more breakthroughs based on these or other technologies will be forthcoming in the near future. As an example, we wish to share our own experience and demonstrate a different pathway to reach the goal of purifying water at low cost and low energy Journal of Polymer Science: Part B: Polymer Physics DOI 10.1002/polb

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consumption. Our technology takes advantage of the nanobrous structure in a nonwoven format to fabricate polymer membranes that can signicantly improve the ux of water transport without losing the selectivity.812 We termed this membrane system as thin-lm nanobrous composite (TFNC) membrane, which is a platform technology suitable for all segments of water ltration, including microltration (MF), ultraltration (UF), nanoltration (NF), reverse osmosis (RO), forward osmosis (FO), and osmosis energy generation. Current Status of Polymer Membrane Technology To understand the breakthroughs, we briey summarize the current polymer membrane technology for water purication (e.g., MF, UF, NF, RO, and FO), depending roughly on the effective pore size of the lter. Typically, the separation membrane has a multilayered composite structure. For MF and UF applications, the structure usually contains two different layers: a nonwoven microbrous support for mechanical strength and a porous layer with asymmetric pore size distribution, often made by the phase inversion method,13 for separation function (e.g., particulates and oil). The pore size distribution in the asymmetric porous membrane layer is broad. The conventional surface of the membrane possesses low surface porosity (ca. 520%), causing low diffusive ux and high fouling potentials. The symptom of fouling is an unavoidable consequence of gradual blockage of permeation in the membrane during ltration. The fouling rate is a function of many variables, such as, the surface characteristics of the membrane, the surface-to-volume ratio of the membrane, the ow rate, the permeant concentration, the ltration temperature, the characteristics of the feed, and the retentate streams. For NF, RO, and FO applications, where the impurities (e.g., multivalent and monovalent ions) are of small sizes, the asymmetric porous layer is not sufcient for separation and it becomes a support to bear a thin top barrier (or selective) layer, which is responsible for the separation function and for reducing the membrane fouling. The thin top coating layer can be made by chemical means (e.g., interfacial polymerization) or physical means (e.g., surface casting). With chemical means, the barrier layer usually consists of tightly crosslinked polymer chains. Without question, this crosslinked structure leads to nondirected torturous channels (with dimensions of the order of several Angstroms) that would not be ideal for high ux water transport, if the channel transportation is the dominant factor for separation of water and ions. Such a membrane system with the three-layered structure is often termed thin-lm composite (TFC) membrane. The key component for separation of impurity is the top barrier layer. To increase the throughput and to decrease the rate of fouling, the top layer should generally be made very thin and use materials that like Journal of Polymer Science: Part B: Polymer Physics DOI 10.1002/polb Figure 1. Two new breakthroughs: High-ux lowfouling membranes.

water (hydrophilic) and dislike the impurities, that is, to reject the impurities. We have made no reference for polymers versus inorganic materials or composites in making the top barrier layer, so long as the material properties can meet the requirements for effective separation of impurities, chemical and mechanical stability, and cost effectiveness. The conventional polymers chosen for the asymmetric porous layer include, for examples, polyvinylidene uoride (PVDF), polysulfone/polyether sulfone, polyacrylonitrile (PAN), and etc., depending on the environmental requirements. For NF and RO applications, the top barrier layer, made by interfacial polymerization, usually consists of highly crosslinked polyamides. Can the materials for porous layer or the top barrier layer be improved? Of course, and this is one of the problems that researchers in the separations eld are interested in. What are the Breakthroughs in Nanobrous Membranes? The breakthroughs we now discuss are beyond the conceptual stage. However, it should be noted that there is a substantial gap between a laboratory demonstration and a product on an industrial scale, not to mention the nal system development that can take full advantage of the new breakthroughs. The two major breakthroughs developed in our laboratory,812,14,15 as shown in Figure 1, can be described as follows.
Breakthrough 1. We recognize the need for a support in

order to achieve a very thin top barrier layer and yet be able to maintain a desired applied pressure. The phase inversion method takes advantage of phase transitions that normally require a comparable amount of components participating in the phase separation phenomena, resulting in the range of porosity that such a membrane can achieve. In other words, the amount of void volume is limited (e.g., the bulk porosity is usually in the range of 50%), especially in the surface pore density

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(e.g., the surface porosity is usually in the range of about 20%). On the other hand, the nonwoven nanober morphology can produce interconnected pores with void volume to materials ratio in the 4:1 range, that is, the bulk porosity is in the 80% range with the surface porosity being about the same as the bulk porosity). This higher porosity effectively increases the ltration speed in nanobrous membranes. The thinner nanober diameter results in an effective pore size decrease, given the same porosity. The interconnected pores suggest less susceptibility to fouling. More importantly, the nanobers can be soldered together, for example, by chemical (e.g., crosslinking) or physical (e.g., melting and dissolving) means, to produce threedimensional structures that simulate trusses in the submicron length scale range, making the nonwoven support stronger mechanically. Thus, a thinner midlayer support can be achieved. In this respect, during the processing step, we can vary the ber diameter, making asymmetric layers with the larger diameter bers toward the bottom and thinner ones toward the top barrier layer. We believe this breakthrough will have a far-reaching impact on MF and UF applications, where the dominant water transport mechanism is through pores or cavities.
Breakthrough 2. There are two important points related

tions, some promising evidence of ux increase through the presence of nanobrous infrastructure was also seen, which could be attributed to the introduction of more water channels.15 CONCLUDING REMARKS In this viewpoint, we foresee the needs of technology breakthrough in water purication, which will be one of the most urgent tasks in research and development of this century. We have demonstrated our unique pathway of using polymer nanobers to devise a more cost effective and energy saving membrane system and expect many new similar developments will be materialized in the near future. The major benets that nanobers can bring to membranes are two: (1) the reduction of substructure resistance to water transport, which is particularly evident for MF and UF, and (2) the possible introduction of water channels through embedment of nanobrous infrastructure in the barrier layer (also become more robust), which will be the key to improve performance for NF, RO, and FO. We note that there are hurdles for translating the laboratory demonstration to industrial products. To achieve the translation of polymer nanobrous membranes from bench to commercialization, we continue to need (1) the chemistry to synthesize stronger and more stable materials, to modify surfaces to produce uid channels with proper dimensions, and to introduce desired functions that can adsorb, exclude, and let the desired uid to slip by; (2) the physics to characterize the structure and the morphology of composite complex structures; (3) the engineering processes to fabricate the membrane on an industrial scale; and (4) the biology to determine interactions with living systems. The nal word is cost effectiveness with respect to the demand. With improvements approaching a factor of 10100, there will be many far-reaching impacts on different facets of applications in water purication that will benet mankind. The authors wish to acknowledge partial support of this work by the Ofce of Naval Research (ONRN000140310932). REFERENCES AND NOTES 1. Pinnau, I.; Freeman, B. D. In Advanced Materials for Membrane Separations, ACS Symposium Series, Washington, DC, 2004. 2. Cheremisinoff, N. P. Handbook of Water and Wastewater Treatment Technology; ButterworthHeinemann: Boston, 2002. 3. World Population to 2300, United Nations Department of Economic and Social Affairs Population Division. Available at: (http://www.un.org/esa/population/publications/longrange2/WorldPop2300nal. pdf). Accessed on March 15, 2009. Journal of Polymer Science: Part B: Polymer Physics DOI 10.1002/polb

to this breakthrough. Point 1 refers to the integration of nanobers with the top barrier layer, thereby forming a nanocomposite layer. Depending on the mechanical strength of nanobers used, this process can increase the mechanical strength of the top layer, and can decrease the thickness of the top barrier layer under the same applied pressure, resulting in a corresponding increase in throughput. Furthermore, the integration of the top barrier layer with the mid-layer support should yield a stronger membrane that can withstand physical back ushing (to reduce the membrane fouling). Point 2 is more interesting and important, because we can take advantage of the existing (interconnected) nanobers (or introduce additional nanobers) in the top barrier layer by modifying the nanober surface to become water channels. This concept is similar to using the interior of carbon nanotubes or Aquaporin Z protein for water transportation in RO. Here, we deal with surface modications to produce water channels that are interconnected in the presented morphology, as shown in Figure 1. It should be noted that the thickness of the modied ber surface that can act as the uid channel depends on the nature of uid that one wishes to pass through. For example, for water as a uid, the thickness will be in the few Angstroms length scale. The directed and interconnected channels can permit the ow of water, instead of owing through more tortuous paths as in molecular cavities, increases the throughput substantially. We have demonstrated the ux increases by a factor of 2 10 in UF applications.812,14 For NF and RO applica-

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4. Water Science for Schools, U.S. Geological Survey. Available at: (http://ga.water.usgs.gov/edu/waterdistribution.html). Accessed on March 15, 2009. 5. Holt, J. K.; Park, H. G.; Wang, Y. M.; Stadermann, M.; Artyukhin, A. B.; Grigoropoulos, C. P.; Noy, A.; Bakajin, O. Science 2006, 312, 10341037. 6. Kumar, M.; Grzelakowski, M.; Zilles, J.; Clark, M.; Meier, W. Proc Natl Acad Sci 2007, 104, 2071920724. 7. Jeong, B. H.; Hoek, E. M. V.; Yan, Y.; Huang, X.; Subramani, A.; Hurwitz, G.; Ghosh, A. K.; Jawor, A. J Membr Sci 2007, 294, 17. 8. Wang, X.; Chen, X.; Yoon, K.; Fang, D.; Hsiao, B.S.; Chu, B. Environ Sci Technol 2005, 39, 7684 7691.

9. Yoon, K.; Wang, X.; Fang, D.; Hsiao, B. S.; Chu, B. Polymer 2006, 47, 24342441. 10. Wang, X.; Fang, D.; Yoon, K.; Hsiao, B. S.; Chu, B. J Membr Sci 2006, 278, 261268. 11. Burger, C.; Hsiao, B. S.; Chu, B. Annu Rev Mater Res 2006, 36, 333368. 12. Yoon, K.; Hsiao, B. S.; Chu, B. J Mater Chem 2008, 18, 53265334. 13. Kesting, R. E. Synthetic Polymeric Membranes; McGraw-Hill: New York, 1971. 14. Tang, Z.; Wei, J.; Yung, L.; Ji, B.; Ma, H.; Qiu, C.; Yoon, K.; Wan, F.; Fang, D.; Hsiao, B. S.; Chu, B. J Membr Sci 2009, 328, 15. 15. Yoon, K.; Hsiao, B. S.; Chu, B. J Membr Sci 2008, 326, 484492.

Journal of Polymer Science: Part B: Polymer Physics DOI 10.1002/polb