Journal of Membrane Science 209 (2002) 283292

TFC polyamide membranes modied by grafting of hydrophilic polymers: an FT-IR/AFM/TEM study

Viatcheslav Freger , Jack Gilron, Soa Belfer
Institutes for Applied Research, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel Received 7 May 2002; received in revised form 3 July 2002; accepted 16 July 2002

Abstract Surface modication using grafting of a hydrophilic polymer onto the membrane surface is a possible route to improving the fouling properties of polyamide thin-lm composite membranes. The structure of nanoltration (NF) and reverse osmosis (RO) membranes modied using graft polymerization of acrylic (AA) monomers was visualized and analyzed using attenuated total reectionFourier transform infrared spectroscopy, atomic force microscopy and transmission electron microscopy. The results show that a layer of AA polymer is indeed formed on the polyamide surface, which could be accompanied by a change of the surface morphology. It was observed that for the NF membranes studied polymerization could also take place inside the pores of the support as a result of penetration of the monomer through the active layer, particularly for high degrees of grafting. It suggests that the modication procedures should be optimized so that the latter effect is minimized. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Thin-lm composite membranes; Reverse osmosis; Nanoltration; Membrane modication; Grafting; TEM; AFM; FT-IR

1. Introduction Over the last three decades following the pioneering development by Cadotte and co-workers the thin-lm composite (TFC) polyamide (PA) membranes have become the main type of membranes used for reverse osmosis (RO) and nanoltration (NF) [1]. Due to the excellent performance and superior economics the TFC-based technology is taking the leading place in water treatment, particularly, in desalination. However, their most serious drawback is the proneness to organic fouling. The problem seems to have no easy solution and necessitates the use of expensive pretreatment and cleaning systems. The propensity
Corresponding author. Tel.: +972-8-6479316; fax: +972-6472960. E-mail address: vfreger@bgumail.bgu.ac.il (V. Freger).

of TFC to undergo fouling arises primarily from the hydrophobicity of the polyamide active layer, onto which many natural organic compounds easily adsorb, eventually leading to irreversible deterioration of the performance. Periodic cleaning does not solve the problem completely and the membranes eventually have to be replaced. Unfortunately, as far as the performance is concerned, no substitute to polyamides has been found so far. A potential way to circumvent the problem is modication, whereby one grafts a hydrophilic polymer onto the polyamide surface making it more hydrophilic and decreasing or weakening the adherence of the organic matter. This approach could be particularly attractive, if one could modify the existing commercial membranes in situ, e.g. inside a module using an inexpensive procedure. It has been shown that the fouling resistance of membranes could be improved

0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 6 - 7 3 8 8 ( 0 2 ) 0 0 3 5 6 - 3

284

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

without signicantly affecting the retentive properties [27]. Such a technique has been developed in our group [2,3]. The method is based on a redox-initiated graft polymerization of acrylic (AA) and other hydrophilic monomers onto the membrane surface and has been applied earlier to increase the hydrophilicity and fouling resistance of asymmetric UF membranes [7]. Preliminary tests on surface modied TFC membranes showed that, though we could not eliminate gradual decrease of the ux, this kind of antifouling modication resulted in a decrease of protein sorption by the TFC membranes and a better and more reversible restoration of the ux after cleaning [810]. The modied membranes also showed in some cases a moderate increase in rejection of organic solutes (by up to 25%) and some reduction of ux (typically by 2030%) [10]. However, these small changes, if undesired, were more than offset by improving the fouling resistance properties. The purpose of this paper is to present visual evidence and analysis of the structural and morphological changes in the active and supporting layers of the RO and NF membranes caused by in situ modication. Out of several monomers employed for grafting we focused on the AA acids, as it easily binds heavy metal cations to provide contrast in electron microscopy. Apart from the chemical changes due to modication, we also tried to assess the effect of modication on the surface roughness. In the latter case, the incentive is its known effect on the colloidal fouling [11,12].

2.2. Modication (grafting) The grafting procedure was similar to that described in [2,3]. A redox system, composed of potassium persulfate and potassium metabisulte, was used to generate radicals. These attack the polymer backbone, thus initiating the graft polymerization by attachment of monomers to the membrane surface. The polymer then grows by propagation. A cross-linker was added to the reaction solution. The coverage of the surface increases with modication time, monomer concentration and initiator concentration [2,3]. The list of monomers included AA, methacrylic acid, polyethylene glycol methacrylate (PEGMA), sulfopropyl methacrylate (SPM) and others. The extent of grafting of the membrane surface was measured by attenuated total reectionFourier transform infrared (ATRFT-IR) spectroscopy. The changes in the absorption peaks that are associated with the grafted polymer were monitored. The concentrations used were 0.1 to 1 M for monomer and 0.01 M for ethyleneglycol dimethacrylate (EGDMA) used as cross-linker. A mixture of redox initiators, 0.01 M K2 S2 O8 and 0.01 M K2 S2 O5 (0.025 M for RO membranes), was added at the end, and after adding to the monomer, the mixture was immediately used to ll a cell containing a membrane. Typically, the cells were the same ones used in permeation experiments. Several types of cells differing in area and cell (channel) height were used. In all cells a membrane was placed at the bottom of a cell sealed in such a way that the solution could contact only the active surface of the membrane. After appropriate intervals of time the membranes were removed from the vessel, conditioned in dilute NaOH (pH 10) and HCl (pH 4) solutions for several hours, washed, kept in water at 40 C overnight to remove loosely bound homopolymer. The degree of grafting on such samples was estimated from ATRFT-IR data. Before taking FT-IR spectra, the membranes (stored wet) were dried in vacuum at 3040 C. 2.3. ATRFT-IR The spectra were recorded on a Nicolet spectrometer using a ZnSe crystal (25 mm 5 mm 2 mm) at a nominal incident angle of 24 yielding about 12 internal reections at the sample surface. All spectra (100

2. Experimental 2.1. Membranes All TFC membranes were commercial samples kindly supplied by the manufacturer. As indicated by the manufacturer, the NF-200 and NF-270 NF membranes (DowFilmtec) are composed of an semiaromatic piperazine-based polyamide layer on top of a polysulfone (PSf) microporous support reinforced with a polyester non-woven backing layer. According to the manufacturers information, the RO membranes of different manufacturers all have fully aromatic polyamide active layer on top of microporous polysulfone reinforced with a polyester backing.

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

285

scans at a resolution of at least 4 cm1 ) were recorded at 25 C. The instrument was purged with dry nitrogen to prevent interference of atmospheric moisture with the spectra. 2.4. AFM The AFM images of dry modied and non-modied NF membranes were taken on an AFM/SPM instrument (Park Scientic) of the Minerva center at Ben-Gurion University. The samples of modied and unmodied RO membranes were measured in a liquid cell under water on the atomic force microscope (Nanoscope III) located in the surface science laboratory at Weizmann Institute. No signicant morphological differences were found between membranes scanned in dry state and under liquid. The tapping and contact modes were primary employed. Because of the sensitivity of the membrane to damage by the AFM tip probe, it was found that tapping mode was preferable. 2.5. TEM The membranes were stained by treating them with dilute NaOH solution (to facilitate the subsequent ion exchange) followed by immersion in an excess of uranyl nitrate for about 15 min, thorough washing of the membrane with deionized water in an ultrasonic bath and drying in vacuum at 40 C. For TEM observations dry uranyl-treated samples were mechanically separated from the non-woven polyester backing, so that only the porous polysulfone together with the active layer remained, and small pieces were embedded in an Araldite resin. The embedded samples were then cut into slices 60100 nm thick using an ultramicrotome, collected and placed on a carbon/collodion covered copper grid. The images were taken on a Phillips CM-12 instrument at an accelerating voltage of 120 kV located at Weizmann Institute.

the outmost part of a TFC membrane. The depth of penetration of the reected IR beam in the ATR technique is typically somewhat below 1 m [3,7]. The spectrum observed represents therefore, the average composition of this layer. Since the thickness of the active layer in TFC membranes is far below 1 m, the method proves highly suitable for analyzing the active layer of modied and non-modied TFC membranes. The relative amounts of the polymers are determined by analyzing the IR adsorption bands specic for each polymer. This specicity renders the method sensitive even to relatively small amounts of the polymers attached to the surface. Fig. 1 presents typical spectra of non-modied polyamide TFC membranes (Filmtecs NF-200B and NF-270 NF membranes and Hydranautics SWC-1 and high-ux ESPA1 RO membranes). The polyamides of the NF and RO membranes are different, which is clearly seen from the absence of Amide II peak in NF membranes prepared from piperazine (a secondary amine) as compared to the RO polyamides based on m-phenylene diamine (a primary amine).

3. Results and discussion 3.1. Infrared ATR spectroscopy The ATRFT-IR spectroscopy provides an easy and convenient way for determination of the relative amounts of different polymeric species present in
Fig. 1. ATRFT-IR spectra of several unmodied TFC polyamide membranes. The spectra are shifted by 0.2 absorbance units relative to each other. Note the different positions of the Amide I peaks for nanoltration (NF-200B and NF-270, DowFilmtec) and reverse osmosis (SWC-1 and ESPA-1, Hydranautics) membranes and absence of the Amide II peak for NF membranes. The peaks marked PSf correspond to polysulfone support.

286

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

The Amide I and II peaks of the active layers at 1650 and 1541 cm1 are clearly separable from the group of peaks apparently corresponding to the polysulfone support (e.g. at 1487, 1503 and 1584 cm1 ). A peak at 1584 cm1 belonging to the polysulfone group was chosen for the purpose of quantifying the amide peak relative to the support. While the two RO membranes appear to have about the same amounts of polyamide in the active layer (despite the almost 10-fold difference in permeability!), a comparison of the two NF membranes shows that the polyamide content of the two membranes differs signicantly. The height ratios, I1650 /I1584, differ by a factor of about 2 for NF-200B and NF-270, respectively. Assuming that the permeability of the membranes is determined by the resistance of polyamide, which might not be entirely correct, this suggests that the latter contains about half the amount of polyamide of the former, which agrees well with the fact that NF-270 is about twice as permeable (in terms of pure water ux) as NF-200B. The spectra of modied membranes are shown in Fig. 2. Since the grafted polymers contain carboxylic groups practically absent in the support and active layer, the degree of modication is most conveniently characterized by the ratio of the heights of the characteristic polysulfone (1584 cm1 ) and carbonyl (17001720 cm1 ) peaks. The spectra of the three membranes shown (samples 13) correspond to various degrees of modications. As the IR spectra indicate, the grafting is largest for sample 3 and lowest for sample 1. However, one cannot infer from the IR spectra whether the grafted polymer, as intended, is deposited onto the polyamide layer as an additional layer or lls the pores of the active or adjacent support layer. Obviously, the desired morphology is a thin layer of the grafted polymer, ideally, a dense polymer brush, attached to the outer surface without penetration into the support. Such structure could change the adsorptive properties of the surface, while retaining the high permeability of the polyamide layer, since the hydrophilic brush should be highly swollen. In fact, a substantial reduction of the ux (down to 25% of the ux of an unmodied membrane) was found for samples with high modication and we could suspect some blocking of the pores of the support by the grafted polymer. In attempt to elucidate the resulting structure we conducted an AFM and TEM study with membranes of various degrees of modication.

Fig. 2. ATRFT-IR spectra of modied NF-270 nanoltration membrane (DowFilmtec). The 1720 and 1584 cm1 peaks correspond to PAA and PSf, respectively. The curve 0 is for unmodied membrane. The curves 13 correspond to low (I1720 /I1584 < 0.01), moderate (I1720 /I1584 = 0.057) and heavy (I1720 /I1584 = 0.37) modication, respectively. Reaction time 1 h. The AA concentrations 0.1 M for curve 1, 1 M for curves 2 and 3. The spectra are normalized to the height of the PSf peak and shifted by 0.1 absorbance units relative to each other.

3.2. AFM AFM was chosen for morphological characterization of the surface of modied membranes. SEM that often complements AFM seemed less suitable since the skin of the piperazine-based polyamide NF membranes, which were at the focus of the present study, is so thin that the polysulfone background in the SEM images largely overwhelms it. The surface of unmodied RO membranes shows a typical nodular (hills and valleys) morphology [1113]. AFM measurements showed that this is also true for unmodied NF membranes under study, the hill to hill distance being, however, much smaller, which correlates well with the much lower thickness of the active later (1540 nm for NF against 200300 nm for RO). This morphology seems to be inherent to the interfacial polymerization used to manufacture the membranes, although the possible

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

287

Fig. 3. AFM images of modied NF-270 membranes of low (a), moderate (b) and heavy (c and d) modication. The size of the images is approximately 1 m 1 m. The Z (grey) scale is in . The average roughness (in nm) is: (a) 1.3; (b) 1.9; (c) 9.9 ; (d) 4.9.

inuence of the underlying support also should not be neglected, and may be viewed as a ngerprint of the TFC polyamide composites. We could thus expect to distinguish between the morphologies of covered and bare surfaces. AFM images of three modied NF-270 samples are shown in Fig. 3. The images of low or moderately modied membranes (Fig. 3a and b) are practically identical to that of an unmodied membrane, which is not shown, yet Fig. 3a can be taken as a very faith-

ful representation of it. Apart from occasional white spots (see Fig. 3b), which could be small patches of a polymer but might well be dust particles (in either case they should have no signicant effect on the performance), the nodular surface morphology remained virtually intact up to the highest extent of grafting where changes in surface morphology accompanied by increase in roughness become apparent (Fig. 3c and d). Statistical analysis shows that the average roughness of NF membranes (a few nanometers, see Fig. 3) slightly

288

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

Fig. 4. AFM images of BW-30 RO membranes (DowFilmtec): original (a) and modied with PEGMA (b) and SPM (c). The reaction time 120 min. The average roughness (in nm) is: (a) 93; (b) 30; (c) 28.

increases with modication, though the change is rather insignicant, except for the most heavily modied samples (up to 10 nm). Interestingly, modied RO membranes showed some reduction of roughness compared to the virgin membrane (Fig. 4) irrespective of the type of monomer used. We do not see any contradiction in this fact since the initial roughness of RO membranes (tens of nanometers) is much larger than in the case of NF membranes. We could conclude

therefore that grafting used in the present study is unlikely to improve the resistance to colloidal fouling. The information provided by AFM sheds no light on resistance to the organic fouling as it says nothing about the chemical and adsorptive properties of the surface. However, some AFM experiments are potentially capable of providing this information by directly measuring intermolecular forces as reported recently [14,15].

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

289

3.3. TEM TEM seems to be the most suitable technique to visualize the internal structure of the non-modied and modied active layer of TFC membranes due to its high resolution and possibility to achieve contrast between the areas having different chemical structure. The latter is most easily realized through selective incorporation of heavy elements, i.e., staining. Since most of the monomers used for grafting in this study had free carboxylic groups, the grafted polymer was rendered highly contrasting by ion exchange of the carboxylic groups with uranyl ions. TEM images of modied membranes are shown in Figs. 5 and 6. The porous polysulfone support having a signicant proportion of sulfur atoms is substantially darker than the intact polyamide layer (Fig. 5). The bright pores in PSf of various sizes (open or lled with much brighter Araldite) are clearly seen (Fig. 5a and b). TEM micrographs of the original membrane (not shown) clearly reveal heterogeneity of the active layer with certain amount of uranyl-stained carboxylic groups in the thin outmost part of the active layer (c-PA) and a brighter and thicker carboxyl-free layer, presumably, amine-dominated (a-PA), adjacent to the support. It may be seen from the micrographs that the a-PA interlayer (Fig. 5a and b) lls the cavities of the polysulfone support and largely varies in thickness.

As a result the upper surface of the polyamide layer is smoother than the PAPSf interface. The double-layer structure of the skin (c-PA over a-PA) agrees well with recent simulations of the interfacial polymerization process used to manufacture these membranes [16] and explains many experimental facts, such as the apparent discrepancies between ESCA [17], NMR [13,17] and FT-IR [9] chemical composition analyses of the skin layer. The probing beam in ESCA penetrates to a very low depth (ca. 1 nm) and detects signicant amounts of free carboxylic groups in the thin outmost fraction of the non-modied skin (c-PA in Fig. 5a), this fact is also reected in the negative surface charge of most TFC composites, as indicated by streaming potential measurements [10]. In contrast, FT-IR and NMR actually probe the average composition of the polyamide, thereby the fraction of carboxylic groups (absent in the a-PA layer) becomes very low or undetectable. Many other results also agree well with this picture, e.g. the simultaneous presence of negative and positive xed charges in the skin layer [18] and trends in separation of various electrolytes [19,20]. In Fig. 5ac (see next), the c-PA layer should therefore be intermixed with the grafted polyacrylic acid (PAA). A cross-sectional image of the sample having the lowest degree of modication (Fig. 5a) shows little difference with the unmodied membrane. The darker

Fig. 5. TEM cross-sectional images of modied NF-270 membranes of low and moderate degrees of modication: (a) very low modication (1720 cm1 peak undetectable, I1720 /I1584 < 0.01), magnication 45 K; (b) moderate modication (I1720 /I1584 = 0.057), magnication 45 K; (c) Same as (b), magnication 320 K.

290

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

Fig. 6. TEM cross-sectional images of a heavily modied NF-270 membrane (I1720 /I1584 = 0.37): (a) magnication 60 K, (b) magnication 200 K.

carboxyl-rich part of the skin is almost as thin as in the original membrane and no penetration of the pores of the support by the polymer is observed. A moderately grafted sample shown in Fig. 5b is more different from the non-modied sample. It is seen that in this case the grafted polymer was capable of forming a dense layer about 20 nm thick above the polyamide layer leaving the pores of the support intact. Higher magnication of the same sample (see Fig. 5c) shows the thickness of the grafted layer to be about 20 nm, which is comparable to the thickness of the thinnest parts of the active layer itself (c-PA+a-PA). This structure is presumably most desired since due to the high hydrophilicity and swelling of PAA it should minimally reduce the ux yet positively affect the surface properties (hence fouling) and, possibly, rejection (by sealing the defects). Fig. 6a and b shows the cross-section of a heavily modied sample at different magnication. We can see a thick layer of grafted polymer covering the surface of the membrane. The boundary between the graft polymer and the polyamide layer is very diffuse. This indicates that both polymers appear to be strongly

interpenetrated. Another striking difference with the previous samples is the absence of open pores in the support. The dark color acquired by the pores making them almost indistinguishable from polysulfone suggests that a signicant portion of PAA was formed in the pores of the support due to penetration of the small monomer molecules through the active layer. This conclusion was also conrmed by the ATRFT-IR analysis of the backside of the polysulfone layer of samples having the highest amount of grafted polymer, where some grafted polymer was also found. Clearly, this modication route is not particularly desirable since it signicantly reduces the ux (by as much as 75% in some experiments) by increasing the hydraulic resistance of the support and has little impact on the fouling properties. 3.4. Penetration of monomers to the support We should note that sometimes even in cases of low modication some penetration of monomers was indicated by FT-IR and TEM. This serves to emphasize that conclusions from the TEM results must be drawn

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292

291

with care. In a few cases, no grafted layer was found on the NF surface but rather all polymer was located inside the pores. This fact should not be surprising, as even provided the skin is defect free, the NF could not completely stop penetration of small monomer molecules through the skin. This is seen by the fact that the rejection of lactic acid having a size similar to these monomers in NF tests with these membranes was about 60% at pH 3, close to the native pH of monomer solutions used in this study [21]. Penetration of the reactants through the active layer could be related to the morphological pattern observed at the active surface. This hypothesis is supported by the results obtained with RO membranes, which are far less permeable to the reactants and thus a buildup of the grafted layer at the interface accompanied by a reduction in roughness was consistently achieved with both large (PEGMA) and small (SPM) monomers (Fig. 4b and c, respectively). In addition, it has been found over many modication experiments that the cell, in which the synthesis is carried out, also affects the extent of grafting of NF membranes as measured by ATR-FT-IR. Cells with higher liquid levels tend to give higher grafting. The difference between curves 2 and 3 is due to this effect. We might suggest that small differences in the static head developed in different cells at the bottom of solution might have some effect on the penetration of the reaction mixture through the active layer of NF membranes into the support. Indeed, for a layer of liquid 1 cm high (a typical value) over the membrane, a static pressure of 103 bar will develop at the membrane surface. Though it seems insignicant, this pressure will cause a convective ow through the membrane at a rate of about 109 m/s or 103 m/s, as may be deduced from known hydraulic permeability (105 m/s at 10 bar or 1 m/(s bar)) [21,22]. It means that over a typical reaction time (103 s) the liquid contacting the membrane will penetrate into the membrane to a depth of roughly 103 1 103 = 1 m. This depth of penetration clearly exceeds the thickness of the polyamide skin and could be further increased by capillary effects and diffusion. In the case of low rejection, this can convectively bring a signicant amount of the monomers into the pore space. It partly explains the observed polymerization patterns found for various cells, monomer solutions and reaction times and suggests that a proper control of penetration of the

monomer through the skin layer should play a signicant role in the optimization of the grafting procedures.

4. Conclusions Analysis of the structure of polymer layers grafted onto the surface of TFC polyamide membranes revealed the following facts: 1. AFM shows that attachment of the grafted layer onto the active surface does not lead to signicant changes of the surface morphology. While a certain reduction of roughness could be obtained, with RO membranes, the characteristic hills and valleys morphological pattern does not undergo a qualitative change, even for very high degrees of grafting. Therefore, if a substantial reduction of the surface roughness is required, e.g. to prevent colloidal fouling, the described grafting procedure requires further improvement. In case of organic fouling the modication as is may be adequate to impart fouling resistance. 2. TEM microscopy of cross-sections of modied membranes reveals a reasonable correlation with the extent of grafting as determined by ATRFT-IR. TEM shows that a thin layer of hydrophilic polymer may indeed be formed on the surface of the active layer. 3. Filling of the pores of the support by the grafted polymer occurs in some cases, particularly for high degrees of grafting. This phenomenon is undesirable and should be avoided by optimizing conditions so that grafting takes place only at the active surface. The optimization must include both chemical factors and hydrodynamic conditions employed in the modication procedures.

Acknowledgements This part of the work was supported by the EU Grant #BRPR-CT98-8001. The authors wish to thank Mrs. R. Fainshtein and Dr. Y. Purinson for kind help in preparation of the membrane samples and FT-IR analysis. The assistance of the Minerva Center for Nanoscience at BGU and Mrs. R. Golan (BGU) and Dr. S. Matlis (Weizmann Institute) in

292

V. Freger et al. / Journal of Membrane Science 209 (2002) 283292 Prevention, Second Annual Scientic Progress Report, EU Project Contract BRPR-CT98-8001, November 1999October 2000 (Chapter 1). M. Elimelech, X. Zhu, A.E. Childress, S. Hong, Role of membrane surface morphology in colloidal fouling of cellulose acetate and composite aromatic polyamide reverse osmosis membranes, J. Membr. Sci. 127 (1997) 101. E.M. Vrijenhoek, S. Hongb, M. Elimelech, Inuence of membrane surface properties on initial rate of colloidal fouling of reverse osmosis and nanoltration membranes, J. Membr. Sci. 188 (2001) 115128. S.Y. Kwak, D.W. Ihm, Use of atomic force microscopy and solid state NMR to characterize structure-propertyperformance correlations in high-ux reverse osmosis membranes, J. Membr. Sci. 158 (1999) 143. W.R. Bowen, T.A. Doneva, Atomic force microscopy studies of nanoltration membranes: surface morphology, pore size distribution and adhesion, Desalination 129 (2000) 163. J.A. Koehler, M. Ulbricht, G. Belfort, Intermolecular forces between proteins and polymer lms with relevance to ltration, Langmuir 13 (1997) 4162. V. Freger, S. Srebnik, Mathematical model of charge and density distributions in interfacial polymerization of thin lms, J. Appl. Polym. Sci., in press. J.-Y. Koo, R.J. Petersen, J.E. Cadotte, ESCA characterization of chlorine-damaged polyamide reverse osmosis membrane, Pol. Preprints, Div. Pol. Chem. ACS 27 (1986) 391. J. Schaep, C. Vandecasteele, Evaluating the charge of nanoltration membranes, J. Membr. Sci. 188 (2001) 129. M. Nystrm, L. Kaipia, S. Luque, Fouling and retention of nanoltration membranes, J. Membr. Sci. 98 (1995) 249. A.E. Yaroshchuk, Non-steric mechanisms of nanoltration: superposition of Donnan and dielectric exclusion, Separation Purif. Technol. 22/23 (2001) 143158. V. Freger, T.C. Arnot, J.A. Howell, Separation of concentrated organic/inorganic salt mixtures by nanoltration, J. Membr. Sci. 178 (2000) 185193. V. Freger, T.C. Arnot, J.A. Howell, Flux and rejection in nanoltration of concentrated organic/inorganic salt mixtures, in: Proceedings of the Euromembrane 2000, Maale Hachamisha, 2000.

AFM measurements and of Dr. R. Popovich-Biro (Weizmann Institute) and Mrs. R. Yegger (BGU) in TEM analysis is gratefully acknowledged. References

[11]

[12] [1] R.J. Petersen, Composite reverse osmosis and nanoltration membranes, J. Membr. Sci. 83 (1993) 81150. [2] S. Belfer, Y. Purinson, R. Fainshtein, Y. Radchenko, O. Kedem, Surface modication of commercial composite polyamide reverse osmosis membranes, J. Membr. Sci. 139 (1998) 175. [3] S. Belfer, Y. Purinson, O. Kedem, Surface modication of commercial polyamide reverse osmosis membranes by radical grafting: an ATRFT-IR study, Acta Polym. 49 (1998) 574. [4] M. Nystrm, P. Visnen, Contact angle measurements of protein adsorption onto membrane polymer lms, Acta Polytech. Scand., Chem. Technol. Ser. N273 (2000) 5. [5] M. Nystrm, Fouling of unmodied and modied polysulfone ultraltration membranes by ovalbumin, J. Membr. Sci. 44 (1989) 183. [6] A. Nabe, E. Staude, G. Belfort, Surface modication of polysulfone ultraltration membranes and fouling by BSA solutions, J. Membr. Sci. 133 (1997) 57. [7] S. Belfer, R. Fainshtain, Y. Purinson, O. Kedem, Surface characterization by FT-IR-ATR spectroscopy of polyethersulfone membranes-unmodied, modied and protein fouled, J. Membr. Sci. 172 (2000) 113. [8] J. Gilron, S. Belfer, P. Visnen, M. Nystrm, Modication of RO membranes for antifouling resistance, Desalination 140 (2001) 167. [9] S. Belfer, J. Gilron, Y. Purinson, R. Fainshtain, N. Daltrophe, M. Priel, B. Tenzer, A. Toma, Effect of surface modication in preventing fouling of commercial SWRO membrane at Eilat seawater desalination plant, Desalination 139 (2001) 169. [10] M. Mnttri, in: J. Gilron (Ed.), Increased Water Recovery from Organic-Laden Process Streams (OLAPS) by Combining NF with Selected Downstream Processes and Fouling

[13]

[14]

[15]

[16]

[17]

[18] [19] [20]

[21]

[22]