Desalination 275 (2011) 252–259

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Surface modification of a commercial thin film composite polyamide reverse osmosis

membrane by carbodiimide-induced grafting with poly(ethylene glycol) derivatives
Guodong Kang a, Haijun Yu a, Zhongnan Liu a,b, Yiming Cao a,⁎
a
Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China
b
Graduate University of Chinese Academy of Science, Beijing 100049, China

a r t i c l e i n f o a b s t r a c t

Article history: Based on the existing carboxylic acid groups on surface of used commercial thin film composite polyamide
Received 24 January 2011 reverse osmosis membrane, two kinds of poly(ethylene glycol) derivatives with different chains were grafted
Received in revised form 1 March 2011 by carbodiimide-induced method to improve the antifouling property. The membranes before and after
Accepted 2 March 2011
modification were characterized by attenuated total reflectance Fourier transform infrared spectroscopy,
Available online 4 May 2011
scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and static contact
Keywords:
angle measurement. Moreover, the water flux, NaCl rejection and fouling experiments were also conducted.
Polyamide reverse osmosis membrane The changes of chemical composition and morphology on membrane surfaces indicated the successful
Surface modification grafting of poly(ethylene glycol) derivatives. Compared to unmodified membrane, the modified membranes
Carboxylic acid groups were more resistant to fouling in protein and cationic surfactant feeding solutions. The method in this study
Carbodiimide-induced grafting provided a new way for surface modification of commercial polyamide reverse osmosis membranes.
Antifouling © 2011 Elsevier B.V. All rights reserved.

1. Introduction comprehensively studied due to their extraordinary antifouling abilities.

In recent years, reverse osmosis (RO) membrane technology has
been widely used in industrial water treatment and desalination [1,2].
At present, most commercially available RO membranes are of thin
film composite type, where a dense aromatic polyamide barrier layer
is formed on a microporous support such as polysulfone by an
interfacial polymerization process [3]. These membranes exhibit
excellent performance and superior economics. However, one of the
issues limiting their use is the proneness of fouling [4,5]. Therefore, a
number of studies have been conducted to mitigate this problem
including pretreatment processes, designing special modules and
development of antifouling membranes. Meanwhile, the surface
modification of commercial RO membrane is considered as an
effective and relatively economic route [6,7]. So far, the reports
about the surface modification methods of RO membranes ranged
from physical adsorption [8], coating [9,10], in-situ redox initiated
grafting [11,12], free-radical graft polymerization [13], plasma
polymerization [14] and chemical coupling [15]. In general, the
purpose of these methods is to introduce hydrophilic layer or
hydrophilic molecular chains onto RO membrane surface to improve
the antifouling properties.
Among the hydrophilic monomers applied for surface modification,
poly(ethylene glycol) (PEG) and its derivates have already been
⁎ Corresponding author. Tel.: + 86 411 84379053; fax: + 86 411 84379906.
E-mail address: ymcao@dicp.ac.cn (Y. Cao).
PEG is an uncharged water-soluble polymer having good hydrophilicity,
flexible long chains, large exclusion volume and unique coordination
with surrounding water molecules in an aqueous medium. It is found
that the surface-bounded PEG molecules can be very effective in
preventing adsorption of hydrophobic or large molecules from
membrane surface, which was advantageous to reducing membrane
fouling [16]. In recent years, the surface modification of membranes by
the immobilization of PEG chains or protective layer has been used in
ultrafiltration [17,18], nanofiltration [19] and RO [11,12,15,20–23]. For
example, Belfer and Freger et al. studied redox-initiated radical grafting
method of poly(ethylene glycol) methacrylate (PEGMA) onto commer-
cial polyamide RO membrane surfaces to improve fouling resistance
[11,12]. Van Wagner et al. modified polyamide RO (XLE) and
nanofiltration (NF90) membranes by grafting poly(ethylene glycol)
diglycidyl ether (PEGDE) to their top surfaces from aqueous solution
[20]. In the previous study, we also developed a novel surface
modification method of nascent polyamide RO membrane by grafting
aminopoly(ethylene glycol) monomethylether [15]. In general, the
modified membranes exhibited improved fouling resistance and an
improved ability to be cleaned after fouling compared to unmodified
membranes.
As we know, some commercial thin film composite polyamide RO
membranes prepared from 1,3,5-benze-netricarbonyl trichloride
(TMC) and m-phenylene-diamine (MPD) such as FT-30 contain
carboxylic acid groups on the surface [24]. These reactive groups
provide the possibility of surface modification of these RO membranes
to improve the antifouling properties. On the other hand, the
activation of carboxylic acid groups by coupling reagent such as 1-

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.03.007
 G. Kang et al. / Desalination 275 (2011) 252–259
ethy-3-(3-dimethyl amidopropyl) carbodiimide (EDC) has been used
in organic synthesis [25] and chemical grafting [26,27]. Combining
with these two aspects, a surface modification method of commercial
thin film composite polyamide RO membrane by EDC-induced
grafting with hydrophilic PEG derivatives was developed in this
study. The chemical composition and morphology of membrane
surface before and after modification were investigated using
attenuated total reflectance Fourier transform infrared spectroscopy
(ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning elec-
tron microscopy (SEM) and atomic force microscopy (AFM). The
performance and fouling resistance of modified and unmodified
membranes were also compared.
2. Experimental
2.1. Membranes and reagents
The RO membranes used in this work were kindly supplied by
Hangzhou Beidouxing Membrane Co., Ltd., China, which were
fabricated by interfacial polymerization using TMC and MPD on
polysulfone support. 1-Ethy-3-(3-dimethyl amidopropyl) carbodii-
mide (EDC) was purchased from Shanghai Medpep Co., Ltd. The PEG
derivates with end amine groups called Jeffamine ED600 and
Jeffamine ED2001 (abbreviated to ED600 and ED2001) were pur-
chased from Hunstman Company Limited and used for surface
modification. The chemical structures of EDC, ED600 and ED2001
were illustrated in Fig. 1. All reagents used in this work were of
analytical grade.
2.2. Surface modification of polyamide RO membrane
200 mg of EDC was dissolved in 200 mL of sodium citrate buffer
solution (pH 4.7) to prepare a 0.1 wt.% EDC aqueous solution. The
thoroughly washed RO membrane (6 cm × 6 cm) was immersed in the
EDC solution at 4 °C for 3 h to activate the carboxylic acid groups on
membrane surface. The membrane was gently washed twice with
deionized water and then incubated in an aqueous solution contain-
ing an excessive amount of ED600 or ED2001 at 4 °C for 24 h. Finally,
the modified membrane was thoroughly washed with deionized
water to remove the residual adsorbed PEG derivative, and then
stored in deionized water for use. The schematic diagram showing
surface modification of polyamide RO membrane by EDC-induced
grafting with PEG derivates was represented in Fig. 2.
2.3. Surface characterization
2.3.1. ATR-FTIR analysis
The Fourier transform infrared spectroscopy (Equinox 55) with an
ATR unit (ZnSe crystal, 45°) was employed to investigate the change
of chemical composition between unmodified and modified mem-
(a) EDC
H3C
N CH2CH2CH2 N C NCH2CH3 . HCl
H3C
(b) ED600 and ED2001
H2N O to determine the composition of outmost part in a thin film composite
O RO membrane. It was performed in this study to confirm the successful
O
x y
CH3 CH3 CH3
Fig. 1. Chemical structure of (a) 1-ethy-3-(3-dimethyl amidopropyl) carbodiimide
(EDC); (b) ED600 (x + z = 3.6, y = 9.0) and ED2001 (x + z = 6.0, y = 39.0).
253
branes and confirm the grafting of PEG derivatives onto RO membrane
surface. The membrane samples were dried in vacuum oven before
analysis. IR spectra of the membranes were recorded in the range of
wavenumber 800–4000 cm− 1 at 25 °C.
2.3.2. SEM and AFM analyses
The surface morphology of unmodified and modified RO mem-
branes was observed by SEM (Philips XL30E) and AFM (Digital
Instruments Inc., Santa Barbara) using a Nanoscope III equipped with
1553D scanner. The tapping mode in air was preferable and used to
take AFM images [12]. The AFM images of 10 μm scans were acquired
by scanning the sample in air under ambient laboratory conditions at
a scan rate of 2 Hz. The roughness of the membrane surface was
assessed by measuring roughness parameters.
2.3.3. XPS analysis
XPS spectra were recorded on a Leybold LHS-12 ESCA unit
employing Mg Kα excitation radiation (1253.6 eV). The X-ray source
was run at a power of 200 W (10.0 kV, 20 mA). The surface elemental
stoichiometries were determined from peak area ratios after correct-
ing with experimentally determined instrumental sensitivity factors.
2.3.4. Static contact angle measurement
The static contact angle of membranes was measured using a
contact angle goniometer (JC2000C Contact Angle Meter, Powereach
Co., Shanghai, China) by the sessile drop method as described in
literatures [28]. An average value of five measurements was taken.
2.4. Performance measurement and fouling experiment
The performance measurement and fouling experiment of un-
modified and modified RO membranes were tested with a laboratory-
scale crossflow test unit. The salt rejection (R) and permeation flux (F)
of the membrane were calculated as Eqs. (1) and (2):
 
R = 1−Cp = Cf × 100% ð1Þ
F = V = At ð2Þ
where Cp and Cf were the salt concentration of permeate solution and
feed solution, V was the volume of permeate solution during the test
time, A was the effective membrane area, and t was the test time,
respectively.
In fouling experiment, each membrane was compacted with
deionized water until the permeate flux became constant. The pure
water flux was recorded. Then, the reservoir was emptied and the
contaminant solution was poured. The time-varying permeate flux
was measured. After 160 min, the membrane was rinsed with
deionized water and the flux recovery was measured. Data in fouling
experiment were normalized to make the comparison more straight-
forward. The value of relative flux (%) was calculated by comparing
the water flux before and after fouling or cleaning.
3. Results and discussion
3.1. ATR-FTIR spectroscopy
ATR-FTIR spectroscopy can provide a convenient and effective way
NH2
z grafting reaction of PEG chains onto membrane surface. Since the
thickness of polyamide barrier layer was about 0.2–0.3 μm [24], which
was thinner than the penetration depth of ATR-FTIR (about 0.5–1.0 μm)
[12,29], the spectra of composite membranes showed characteristic
peaks of both polyamide layer (such as 1660 cm− 1 and 1544 cm− 1) and
254 G. Kang et al. / Desalination 275 (2011) 252–259
Fig. 2. Schematic diagram showing surface modification of polyamide RO membrane by EDC-induced grafting with PEG derivates.
polysulfone support membrane (such as 1584 cm− 1 and 1243 cm− 1).
By comparing the IR spectrum between unmodified and modified
membranes in Fig. 3, the latter showed some new or intensity increased
peaks at 943 cm− 1, 1080 cm− 1 and 2875 cm− 1, which were ascribed to
CH2 rock and C―C stretch, C―O and C―C stretch, and the CH2
symmetric stretch of PEG, respectively [30]. These results suggested that
the PEG derivatives were successfully immobilized onto the surface of
commercial RO membrane by carbodiimide-induced grafting method.
3.2. SEM and AFM analyses
In order to examine the morphological changes of RO membranes
before and after surface modification, the SEM observations were
conducted with a magnification of 2500 and 10,000. The images in
Fig. 4(a)–(f) presented the surface structure of unmodified mem-
brane, ED600 modified membrane and ED2001 modified membrane
with different magnifications, respectively. It could be seen that some
new regular nodules appeared on modified membranes compared to
the control membrane. Moreover, this phenomenon was more
distinct for long-chain ED2001 than that of short-chain ED600. This
was probably due to the connection or aggregation of grafted PEG
chains in dry state. In order to more intuitively observe the stereo
structure of membrane surface, the AFM images were also performed.
Fig. 5 showed the images of three-dimensional 10 μm scans for
unmodified and PEG-modified RO membranes. As shown in Fig. 5(a),
the unmodified membrane exhibited a unique and characteristic
ridge-and-valley structure consistent with that in Ref. [24]. After
surface grafting with PEG chains, some regions were covered with
new nodules. The similar morphological changes were also observed
when PEG-like monomers were grafted onto RO membranes by
plasma polymerization [14]. Meanwhile, the results showed an
increase in the roughness of membrane surface after modification,
ED2001 modified
ED600 modified
Unmodified
1080cm-1
Absorbance
2873cm -1
943cm-1
3600 3200 2800 1600 1400 1200 1000 800
Wavenumber / cm-1
Fig. 3. ATR-FTIR spectra of unmodified and modified polyamide RO membranes.
from 78 nm to 100 nm and 111 nm, respectively. The results were in
agreement with those conducted by some other researchers. For
example, Van Wagner et al. observed a 19–33% increase in surface
roughness upon modification with PEGDE [20]. Zou et al. grafted a
PEG-like hydrophilic polymer (trimethylene glycol dimethyl ether)
onto RO membrane by plasma polymerization and found that, the
roughness increased to 89.3 nm after 60 s treatment from 61.9 nm of
the unmodified membrane [14].
The analytical results of SEM and AFM confirmed again that the
PEG chains were successfully grafted onto the surface of commercial
thin film polyamide RO membrane.
3.3. XPS analysis
XPS is particularly well suited for examining the chemical
composition of skin layer in RO composite membranes, and the
quantitative elemental composition of the top-most layer of mem-
brane sample can be calculated from XPS scanning spectrum. Table 1
presented the atomic concentration data of unmodified membrane,
ED600, ED600 modified membrane, ED2001 and ED2001 modified
membrane. Since ED600 and ED2001 contained higher oxygen and
lower nitrogen, the increases in oxygen content and decreases in
nitrogen content after modification were observed. Meanwhile, the
carbon content in ED600 and ED2001 was lower than that in
unmodified membrane, so the carbon content in modified mem-
branes decreased. Consequently, the ratio of O/C also increased. These
trends have also been observed in our previous study [15] and by Van
Wagner et al. [20].
According to the membrane manufactures, the RO membrane
sample used in this study was fully aromatic polyamide composite
membrane. The polyamide was formed by an interfacial polymeriza-
tion process based on TMC and MPD as shown in Fig. 6. Where, when
n = 1, the resulting polymer is fully crosslinked, giving a molecular
formula of C18H12N3O3. When n = 0, the resulting polymer is linear
with pendant COOH, giving a molecular formula of C15H10N2O4 [3,29].
Therefore, the value of n in unmodified RO membrane could be
obtained based on the data in Table 1 using Eqs. (3), (4) and (5):
Oð%Þ 3n + 4ð1−nÞ 17:0
= = ð3Þ
C ð%Þ 18n + 15ð1−nÞ 72:5
Oð%Þ 3n + 4ð1−nÞ 17:0
= = ð4Þ
Nð%Þ 3n + 2ð1−nÞ 10:5
Nð%Þ 3n + 2ð1−nÞ 10:5
= = : ð5Þ
C ð%Þ 18n + 15ð1−nÞ 72:5
It could be calculated that n1 = 0.283, n2 = 0.291, and n3 = 0.305.
Therefore, the average n = 0.293 was obtained. In other words, the
top-most polyamide layer in used composite RO membrane contained
about 70.7% of linear structure with pendant COOH, which was
accordant with that mentioned above and Ref. [24].
 G. Kang et al. / Desalination 275 (2011) 252–259 255

Fig. 4. SEM micrographs of membranes before and after surface grafting.Unmodified: (a) × 2500, (b) × 10,000; ED600 modified: (c) × 2500, (d) × 10,000; ED2001 modified:
(e) × 2500, (f) × 10,000.

Meanwhile, the grafting rate of carboxylic acid (i.e., the proportion It could be calculated that x1 ≈ 0.74 and x2 ≈ 0.14. In other words,
of carboxylic acid reacted with PEG derivates) in modified membranes about 74% of carboxylic acid groups on RO membrane surface reacted
could be approximately estimated. The molecular formula of ED600 for ED600 modified membrane, but only about 14% for ED2001
and ED2001 were C31.8H67.6N2O12.6 and C99H202N2O45, respectively. If modified membrane. The significant difference of grafting rate for
x was the grafting rate of carboxylic acid, then 1 − x was the unreacted ED600 and ED2001 was probably due to their different chain lengths.
carboxylic acid groups. Based on the measured chemical composition Since the repulsion effect of initially grafted PEG chains in liquid
of modified membranes, the following equations could be obtained: surroundings would hinder the further grafting reaction around, the
ED600 modified membrane: ED2001 with longer molecular chain had more distinct steric effect,
resulting in lower grafting rate.
Oð%Þ 3 × 0:293 + 4 × 0:707 × ð1−xÞ + ð3 + 12:6Þ × 0:707 × x 21:2
= =
C ð%Þ 18 × 0:293 + 15 × 0:707 × ð1−xÞ + ð31:8 + 15Þ × 0:707 × x 70:5
3.4. Performance test
ð6Þ
The pure water flux and NaCl rejection of unmodified and PEG-
ED2001 modified membrane:
modified membranes were presented in Table 2. Similar to the
research results conducted by Belfer et al. [11] and Zou et al. [14], the
Oð%Þ 3 × 0:293 + 4 × 0:707 × ð1−xÞ + ð3 + 45Þ × 0:707 × x 22:0 surface modification by grafting in this study also caused decreases in
= = :
C ð %Þ 18 × 0:293 + 15 × 0:707 × ð1−xÞ + ð99 + 15Þ × 0:707 × x 70:3 water flux (decreased by about 35% in this study, and 36% in Ref. [11]
ð7Þ and 18% in Ref. [14] after modification for 60 min using methacrylic
256 G. Kang et al. / Desalination 275 (2011) 252–259

Fig. 5. Three-dimensional AFM images of unmodified and modified RO membranes: (a) unmodified; (b) ED600 modified; and (c) ED2001 modified. The size of images is
10 μm × 10 μm. The average roughnesses are: (a) 78 nm; (b) 100 nm; and (c) 111 nm.
 G. Kang et al. / Desalination 275 (2011) 252–259 257

Table 1 Table 2
Chemical composition of grafting PEG derivatives, unmodified membrane and modified Pure water flux, salt rejection and static contact angle of membranes before and after
membranes (mol%). modification.

Sample C (%) O (%) N (%) O/C Membrane Pure water fluxa, Salt rejectionb, Static contact
(L/m2h) (%) angle (°)
ED600 (theoretical value) 68.5 27.2 4.3 0.399
ED2001 (theoretical value) 67.8 30.8 1.4 0.454 Unmodified membrane 50 ± 4 96.7 ± 0.4 53 ± 2
Unmodified membrane 72.5 17.0 10.5 0.234 ED600 modified membrane 32 ± 3 96.4 ± 0.2 42 ± 2
ED600 modified membrane 70.5 21.2 8.3 0.302 ED2001 modified membrane 36 ± 3 96.5 ± 0.4 38 ± 3
ED2001 modified membrane 70.3 22.0 7.7 0.312 a
Testing condition of pure water flux: deionized water, 1.05 MPa, 25 °C.
Totally crosslinked 75.0 12.5 12.5 0.167 b
Testing condition of salt rejection: 1500 ppm of NaCl solution, 1.05 MPa, 25 °C.
Linear with pendant COOH 71.5 19.0 9.5 0.266

contaminants in antifouling tests of RO membranes [15,22,23,31].

acid and triglyme, respectively). The decrease of permeation flux was
due to the increased resistance of grafted layer which affected the
pressure drop of membrane. However, compared to some coating
processes [9,10], the surface grafting method often showed relatively
lower decrease in water flux.
On the other hand, since the grafting method in this study was
conducted in a very mild aqueous environment without any drying
process or damaging effect, the NaCl rejection of RO membrane had no
significant change after surface modification, which was also reported
by many researchers [11,14,23]. For example, NaCl rejection of RO
membrane changed from 98.5% to 98.0% in Ref. [14], and from 99.0 ±
0.3% to 99.3 ± 0.5% in Ref. [23] after surface modification using
triglyme and PEGDA, respectively. However, unlike some other
grafting methods such as UV-initiated polymerization or plasma
polymerization, this method needed no special equipments. More-
over, it was very simple and easily operated, providing a new way for
surface modification of commercial polyamide RO membranes.
3.5. Fouling experiments
In this study, 100 ppm of milk solution (for simulating protein
solution) and 100 ppm of dodecyltrimethylammonium bromide
(DTAB, a cationic surfactant) solution were used for fouling experi-
ments. Protein solution and DTAB solution were commonly used as
According to the experimental method, the fouling and cleaning
results were summarized in Fig. 7(a) and (b).
It could be clearly seen that, the modified membranes showed
relatively better antifouling properties than those of unmodified
membrane. Through surface modification, the membranes exhibited
smaller flux decrease after fouling and higher flux recovery after
cleaning. It could be explained as follows: (1) The grafting of
hydrophilic PEG derivatives enhanced the hydrophilicity of mem-
brane surface, which was in good agreement with the static contact
angle measurement in Table 2. The enhancement of surface hydro-
philicity was advantageous to improvement of antifouling perfor-
mance [17,18,32]. (2) The grafted PEG chains presented a good steric
repulsion effect in liquid surroundings, which was helpful to restrain
and prevent the adsorption of protein onto membrane surface. This
was also reported by Che et al. [26] and Wang et al. [33]. (3) The
modification process eliminated a portion of carboxylic acid groups by
reaction with ED600 and ED2001, thus the surface charge of modified
membrane was less negative, reducing the electrostatic attraction
with DTAB having positive charge. Similarly, Hachisuka et al. coated
electric neutral polyvinyl alcohol onto polyamide RO membrane to
create a neutral membrane surface, and the treated membrane
showed better tolerance to water containing a surfactant [9].
However, it should be mentioned here that the modified membranes
exhibited larger surface roughness, which may be disadvantageous to

COCl

H2N NH2
+

ClOC COCl

TMC MPD

O O O O

HN NH C C HN NH C C

C O C O

OH
NH n 1-n

NH

Fig. 6. Interfacial polymerization of commercial polyamide RO membrane dense layer based on TMC and MPD.
258 G. Kang et al. / Desalination 275 (2011) 252–259

a 120 References
ED2001 modifed
ED600 modifed [1] L.F. Greenlee, D.F. Lawler, B.D. Freeman, B. Marrot, P. Moulinc, Reverse osmosis
Unmodified desalination: water sources, technology, and today's challenges, Water Res. 43
100 (2009) 2317–2348.
[2] D. Li, H.T. Wang, Recent developments in reverse osmosis desalination
Relative Flux (%)

membranes, J. Mater. Chem. 20 (2010) 4551–4566.

80 [3] C.Y. Tang, Y.N. Kwon, J.O. Leckie, Probing the nano- and micro-scales of reverse
osmosis membranes — a comprehensive characterization of physiochemical
properties of uncoated and coated membranes by XPS, TEM, ATR-FTIR, and
streaming potential measures, J. Membr. Sci. 287 (2007) 146–156.
60 [4] A. Subramani, E.M.V. Hoek, Biofilm formation, cleaning, re-formation on
polyamide composite membranes, Desalination 257 (2010) 73–77.
[5] S.A. Creber, J.S. Vrouwenvelder, M.C.M. van Loosdrecht, M.L. Johns, Chemical
Water Milk solution Cleaning Water
40 cleaning of biofouling in reverse osmosis membranes evaluated using magnetic
resonance imaging, J. Membr. Sci. 362 (2010) 202–210.
[6] D. Rana, T. Matsuura, Surface modification for antifouling membranes, Chem. Rev.
110 (2010) 2448–2471.
20 [7] K.C. Khulbe, C. Feng, T. Matsuura, The art of surface modification of synthetic
0 50 100 150 200 250 300 polymeric membranes, J. Appl. Polym. Sci. 115 (2010) 855–895.
Time (min) [8] M.C. Wilbert, J. Pellegrino, A. Zydney, Bench-scale testing of surfactant-modified
reverse osmosis/nanofiltration membranes, Desalination 115 (1998) 15–32.
[9] H. Hachisuka, K. Ikeda. Composite reverse osmosis membrane having a separation
b 120 layer with polyvinyl alcohol coating and method of reverse osmosis treatment of
ED2001 modified water using the same, US Patent, 6,177,011 B1 (2001).
ED600 modified
[10] J.S. Louie, I. Pinnau, I. Ciobanu, K.P. Ishida, A. Ng, M. Reinhard, Effects of polyether–
Unmodified
100 polyamide block copolymer coating on performance and fouling of reverse
osmosis membranes, J. Membr. Sci. 280 (2006) 762–770.
[11] S. Belfer, Y. Purinson, R. Fainshtein, Y. Radchenko, O. Kedem, Surface modification
Relative Flux (%)

80 of commercial composite polyamide reverse osmosis membranes, J. Membr. Sci.

60
40
Water DTAB solution Cleaning
20
0 on thin-film composite reverse osmosis membrane by grafting poly(ethylenegly-
0 50 100 150 200 250
Time (min)
Fig. 7. Fouling and cleaning experiments of membranes before and after modification:
(a) milk solution; and (b) DTAB solution.
the improvement of colloidal fouling according to the research results
by Elimelech et al. [34].
4. Conclusion
A novel surface modification method of commercial thin film
composite polyamide RO membrane by EDC-induced grafting with
hydrophilic PEG derivatives was developed in this study. The FTIR-ATR,
SEM, AFM and XPS analyses confirmed the successful immobilization of
PEG chains onto polyamide RO membrane surface. The hydrophilicity
was relatively enhanced after modification. Surface modification in this
study caused acceptable decreases in pure water flux but no significant
change in NaCl rejection. Compared to unmodified membrane, the
modified membranes were more resistant to fouling in protein and
cationic surfactant feeding solutions. The surface modification method
in this study was conducted in a mild aqueous environment without any
drying process or damaging effect. Moreover, it was simple, easily
operated and needed no special equipments, which were all very
advantageous to industrial applications.
Acknowledgement
Financial support from the National Natural Science Foundation of
China (Grant No. 20906086) is gratefully acknowledged.
139 (1998) 175–181.
[12] V. Freger, J. Gilron, S. Belfer, TFC polyamide membranes modified by grafting of
hydrophilic polymers: an FT-IR/AFM/TEM study, J. Membr. Sci. 209 (2002)
283–292.
[13] X.Y. Wei, Z. Wang, Z. Zhang, J.X. Wang, S.C. Wang, Surface modification of
commercial aromatic polyamide reverse osmosis membranes by graft polymer-
ization of 3-allyl-5,5-dimethylhydantoin, J. Membr. Sci. 351 (2010) 222–233.
Water [14] L. Zou, I. Vidalis, D. Steele, A. Michelmore, S.P. Low, J.Q.J.C. Verberk, Surface
hydrophilic modification of RO membranes by plasma polymerization for low
organic fouling, J. Membr. Sci. (2010), doi:10.1016/j.memsci.2010.12.0238 12.023.
[15] G.D. Kang, M. Liu, B. Lin, Y.M. Cao, Q. Yuan, A novel method of surface modification
300 col), Polymer 48 (2007) 1165–1170.
[16] T. McPherson, A. Kidane, I. Szleifer, K. Park, Prevention of protein adsorption by
tethered poly(ethylene oxide) layers: experiments and single-chain mean-field
analysis, Langmuir 14 (1998) 176–186.
[17] W. Chinpa, D. Quémener, E. Bèche, R. Jiraratananon, A. Deratani, Preparation of
poly(etherimide) based ultrafiltration membrane with low fouling property by
surface modification with poly (ethylene glycol), J. Membr. Sci. 365 (2010) 89–97.
[18] S. Kang, A. Asatekin, A.M. Mayes, M. Elimelech, Protein antifouling mechanisms of
PAN UF membranes incorporating PAN-g-PEO additive, J. Membr. Sci. 296 (2007)
42–50.
[19] S. Belfer, R. Fainshtain, Y. Purinson, J. Gilron, M. Nyström, M. Mänttäri,
Modification of NF membrane properties by in situ redox initiated graft
polymerization with hydrophilic monomers, J. Membr. Sci. 239 (2004) 55–64.
[20] E.M. Van Wagner, A.C. Sagle, M.M. Sharma, Y.H. La, B.D. Freeman, Surface
modification of commercial polyamide desalination membranes using poly
(ethylene glycol) diglycidyl ether to enhance membrane fouling resistance,
J. Membr. Sci. 367 (2010) 273–287.
[21] J.Y. Koo, S.P. Hong, J.W Kang N. Kim. Selective membrane having a high fouling
resistance, US Patent, 6,913,694 B2 (2005).
[22] W.E. Mickols. Composite membrane with polyalkylene oxide modified polyamide
surface, US Patent 6,280,853 B1 (2001)
[23] A.C. Sagle, E.M. VanWagner, H. Ju, B.D. McCloskey, B.D. Freeman, M.M. Sharma,
PEG-coated reverse osmosis membranes: desalination properties and fouling
resistance, J. Membr. Sci. 340 (2009) 92–108.
[24] R.J. Petersen, Composite reverse osmosis and nanofiltration membranes, J. Membr.
Sci. 83 (1993) 81–150.
[25] A. Okamura, T. Hirai, M. Tanihara, T. Yamaoka, Synthesis and properties of novel
biodegradable polyamides containing α-amino acids, Polymer 43 (2002)
3549–3554.
[26] A.F. Che, F.Q. Nie, X.D. Huang, Z.K. Xu, K. Yao, Acrylonitrile-based copolymer
membranes containing reactive groups: surface modification by the immobiliza-
tion of biomacromolecules, Polymer 46 (2005) 11060–11065.
[27] Q. Shi, Y.L. Su, W.J. Chen, J.M. Peng, L.Y. Nie, L. Zhang, Z.Y. Jiang, Grafting short-
chain amino acids onto membrane surfaces to resist protein fouling, J. Membr. Sci.
366 (2011) 398–404.
[28] V. Gekas, K.M. Persson, M. Wahlgren, B. Sivik, Contact angles of ultrafiltration
membranes and their possible correlation to membrane performance, J. Membr.
Sci. 72 (1992) 293–302.
[29] A.P. Rao, S.V. Joshi, J.J. Trivedi, C.V. Devmurari, V.J. Shah, Structure-performance
correlation of polyamide thin film composite membranes: effect of coating
conditions on film formation, J. Membr. Sci. 211 (2003) 13–24.
[30] Y.S. Park, J. Won, Y.S. Kang, Preparation of poly(ethylene glycol) brushes on
polysulfone membranes for olefin/paraffin separation, Langmuir 16 (2000)
9662–9665.
 G. Kang et al. / Desalination 275 (2011) 252–259 259

[31] Q.F. Yang, Y.Q. Liu, Y.J. Li, Control of protein (BSA) fouling in RO system by
antiscalants, J. Membr. Sci. 364 (2010) 372–379.
[32] D. Rana, Y. Kim, T. Matsuura, H.A. Arafat, Development of antifouling thin-film-
composite membranes for seawater desalination, J. Membr. Sci. 367 (2010) 110–118.
[33] J. Wang, C.J. Pan, N. Huang, H. Sun, P. Yang, Y.X. Leng, J.Y. Chen, G.J. Wan, P.K.
Chu, Surface characterization and blood compatibility of poly(ethylene
terephthalate) modified by plasma surface grafting, Surf. Coat. Tech. 196 (2005)
307–311.
[34] M. Elimelech, X.H. 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) 101–109.