Desalination 316 (2013) 127–136

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Desalination
journal homepage: www.elsevier.com/locate/desal

The preparation of antifouling ultrafiltration membrane by surface grafting

zwitterionic polymer onto poly(arylene ether sulfone) containing hydroxyl
groups membrane
Yang Liu a, b, Shuling Zhang a, Guibin Wang a,⁎
a
College of Chemistry, Engineering Research Center of High Performance Plastics, Ministry of Education, Jilin University, Changchun 130012, China
b
College of Material Science and Engineering, Northeast Forestry University, Harbin 150040, China

H I G H L I G H T S

► Modification of the PES-OH membrane via redox graft polymerization.

► Poly(MPC) is immobilized by hydroxyl groups on the PES-OH membrane surface.
► The grafting process is facile and effective due to the presence of hydroxyl group.
► The zwitterionic membrane exhibits excellent protein antifouling property.

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

Article history: This work describes the polymerization of a zwitterionic polymer, poly(2-methacryloyloxyethyl
Received 1 October 2012 phosphorylcholine) [poly(MPC)] onto the poly(arylene ether sulfone) containing hydroxyl groups (PES-OH)
Received in revised form 9 February 2013 membrane via redox graft polymerization using ceric (IV) ammonium nitrate (CAN) as initiator. Due to the pres-
Accepted 11 February 2013
ence of the activated hydroxyl groups which were used for the immobilization of MPC monomer, the grafting
Available online 15 March 2013
process is facile and effective which avoid the complex and unfavorable pretreatment process and/or hydroxyl-
Keywords:
ated treatment. Attenuated total reflectance Fourier transform infrared spectrometer (FTIR-ATR), X-ray photo-
Antifouling electron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize the chemical
Surface modification compositions and surface morphologies of the unmodified (PES-OH) and modified membrane, respectively. Stat-
Redox graft polymerization ic water contact angle measurement indicated that the introduction of poly(MPC) promoted remarkably the sur-
Zwitterionic polymer face hydrophilicity of the PES-OH membrane. The cycle ultrafiltration experiments for protein solution revealed
Poly(arylene ether sulfone) containing that nonspecific protein adsorption, especially irreversible protein adsorption, for the zwitterionic membrane
hydroxyl groups was significantly reduced, suggesting superior antifouling performance. This work not only introduces a modifi-
cation approach to obtain a PES-OH membrane grafting hydrophilic poly(MPC) chains, but also gives the zwitter-
ionic membrane a long time life and excellent ultrafiltration performance.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction as polysulfone, polyethersulfone and polyphenylsulfone, etc.) are a

Ultrafiltration (UF) as an effective and powerful technique has been
found to be an alternative approach for macromolecules separation
such as proteins. It possesses a number of attractive features mainly
low energy consumption, mild operating conditions, no additive re-
quirements, no phase change and environmentally friendly [1], which
has been integrated into industrial processes as well as economical, eco-
logical and safety issues. The state-of-the-art materials used for man-
ufacturing of commercial ultrafiltration membrane are generally made
from polymers [2], such as cellulose [3], poly(vinylidene fluoride) [4],
polyetherimide [5], polysulfone [6] and polyethersulfone [7]. Among
all polymeric membrane materials, poly(arylene ether sulfone)s (such
⁎ Corresponding author. Tel./fax: +86 431 8516 8889.
E-mail address: wgb@jlu.edu.com (G. Wang).
class of especially useful materials which have been used to make ultra-
filtration membrane for over 25 years due to their specific characteris-
tics. These excellent high-heat plastics offer more toughness, strength,
rigidity and hydrolytic stability than other polymer materials, and
withstand prolonged exposure to water, chemicals and temperatures
[6,8–10]. However, their applications are often limited by the inherent
hydrophobic property of poly(arylene ether sulfone)s. The hydrophobic
interaction between poly(arylene ether sulfone)s membrane and pro-
tein molecules in feed solutions often causes nonspecific adsorption
and deposition of proteins on the membrane surface or in pores, and
results in serious membrane fouling [1,11–14], which will reduce per-
meate flux, increase production cost, alter membrane selectivity and
shorten membrane life. Therefore, increasing need for antifouling ultra-
filtration membranes has driven the widespread development of chem-
ical or physical modifications of the separation membranes.

0011-9164/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2013.02.004
128 Y. Liu et al. / Desalination 316 (2013) 127–136
In recent years, many researches have been reported and used suc-
cessfully to improve the membrane resistance toward fouling from aca-
demic and technological point. According to literatures, four different
modification strategies, including (I) synthesis of novel polymers with
well-defined structure as membrane materials (synthesis) [1,12], (II) di-
rect membrane material modification before membrane preparation
(pre-modification) [11,15], (III) blending of membrane material with
modifying additives in casting solutions during membrane preparation
(additive) [14,16], and (IV) advanced surface modification or func-
tionalization after membrane preparation (post-modification) [17,18]
have been proposed. For the synthesis method, the new materials are
not easy to synthesize and handle, and a large number of starting
materials are wasted. An ideal membrane should retain the excellent
mechanical properties of membrane bulk. However, for the pre-
modification method, the modified membrane materials could sacrifice
intrinsic properties of original materials. For example, a highly sulfonated
material is considerably beneficial to ultrafiltration membrane [19], but
it is difficult to obtain a membrane having sufficient mechanical strength
and dimensional stability [15,20]. It is generally accepted that surface
property holds a key factor on antifouling as it determines the interaction
between proteins and membrane [21]. For the additive method, the
modification membrane through a blending technique is simple, and
no additional step is needed during membrane preparation. But the
surface coverage of the modifying additives on membrane surface is
relative low, which resulted in poor antifouling property. For the
post-modification method, research efforts have focused on modifying
membrane surface using hydrophilic materials, which was regard as an
efficient way for improving antifouling property. Furthermore, consider-
able attention has been directed towards the development of surface
grafting for modifying membrane surface, which is apparently more re-
sistant to various membrane-washing processes than surface adsorption
and surface coating [17].
To data, zwitterionic substances, containing a representative
structure of both anionic and cationic units in the same molecule
have been attractive as a class of promising alternative materials
with excellent antifouling ability. Numerous significant works have
been made in preparing of zwitterionic surfaces were shown to
have the function of reducing protein adsorption, because their hy-
drophilic surfaces containing uniform chains with tailorable length
could bind a large amount of water, leading to a strong repulsive
force to protein at specific separation distances or making the protein
contact with the surface without conformation change [22,23]. The
2-methacryloyloxyethyl phosphorylcholine (MPC) with a zwitterion-
ic phosphorylcholine (PC) group has been synthesized and widely
used in the preparation of antifouling surfaces [24]. For example,
MPC has been grafted on polyethylene films by plasma induced at
low temperature [25] and photo induced graft polymerization [26].
Several surface modification techniques have been adopted for im-
proving the surface antifouling by grafting polymerization of monomers
on the membrane surface. However, the surface grafting modifications
usually require a pretreatment process, including UV-induced [18,21],
ozone surface activation [17], plasma induced [25] and γ-radiation
induced [27], which required somewhat expensive equipment and/or
cause significant surface aging of the base membrane [25]. Furthermore,
the surface modification techniques mentioned above are incapable of
modifying the sample with complex geometries [25]. Consequently, sur-
face modification by redox graft polymerization using ceric ammonium
nitrate (CAN) as initiator is a good choice and a well-known way for the
polymerization of vinyl monomers. The reaction method has a prime ad-
vantage of performing at moderate temperature, which would make the
side reaction minimized [28]. Many researches have been focused on the
surface modification of hydroxyl group polymers via redox graft poly-
merization by the conventional ceric ion technique [29–31]. To our
knowledge, the membranes were hydroxylated by treatment with the
peroxy compounds is unavoidable before redox graft polymerization,
especially poly(arylene ether sulfone) membranes.
The present study reports on a simple and efficient method to
graft zwitterionic monomer, MPC, onto the membrane surface by
redox graft polymerization using CAN as initiator, which only require
one step reaction and avoid the complex and unfavorable pretreat-
ment process and hydroxylated treatment. The poly(arylene ether
sulfone) containing hydroxyl groups (PES-OH) was synthesized as
our previous work [32], which was used to prepare the PES-OH ultra-
filtration membrane. Due to the appearance of the pendant activated
hydroxyl group in every unit of PES, an amount of hydroxyl groups
with tailorable distribution density on the surface of the PES-OH
membrane are achievable by immersion precipitation phase inver-
sion method, and the PES-OH membrane could be further grafted
with other functional groups. The chemical compositions, hydrophi-
licity and surface morphologies of the unmodified and modified
membrane were thoroughly investigated, and the antifouling perfor-
mance of the modified membrane was examined in detail. It was
expected that the modified membrane provides a good opportunity
to improve antifouling property.
2. Experimental
2.1. Materials
2-Methacryloyloxyethyl phosphorylcholine (MPC) was purchased
from Joy-Nature Technology Institute, Nanjing, China. The ceric (IV) am-
monium nitrate (CAN, AR grade) was purchased from Aldrich and used
without further purification. Polyethersulfone (PES, Ultrason E6020P)
was purchased from BASF which was used as polymer material in prepa-
ration of membrane casting solution. Poly(vinylpyrrolidone) (PVP 30 K),
which was used as pore-former, was purchased from Fluka Chemika,
Switzerland. Bovine serum albumin (BSA, pI=4.8, Mw =67,000) and
phosphate buffer solution (PBS, 0.1 mol/L, pH 7.4) were both purchased
from Dingguo Bio-technology Co., Ltd. (Beijing, China). Coomassie bril-
liant blue G250 was purchased from Aldrich. (3-Methoxy)aniline were
obtained from Tokyo Chemical Industry, Japan. Hydrochloric acid (36%),
sodium bicarbonate, 1,4-benzoquinone and N-methyl-2-pyrrolidinone
(NMP) were purchased from Beijing Chemical Reagent, China. Pyridine,
zinc powder and sodium nitrite were supplied by Shanghai Chemical Re-
agent, China. The polymerization solvents, sulfolane (TMS) and toluene
were purchased from Tiantai Chemical Reagent, China. Commercially
available 4,4′-dichlorodiphenylsulfone (DCDPS) was purchased from
Yanji Chemical Plant, China. Anhydrous potassium carbonate was dried
under vacuum at 110 °C for at least 24 h before use. All other chemicals
were obtained from commercial sources and used without further purifi-
cation. Deionized water was used throughout this study.
2.2. Synthesis of poly(arylene ether sulfone) containing hydroxyl groups
(PES-OH)
Obtained (3-methoxy)phenylhydroquinone was synthesized ac-
cording to previously reported procedure [32], and the synthetic route is
illustrated in Scheme 1. The synthesis of Poly(arylene ether sulfone)
containing hydroxyl groups (PES-OH) was achieved in two steps as our
previous work [32]. First of all, poly(arylene ether sulfone) containing
methoxyl groups (PES-OCH3) was synthesized by a characteristic nucle-
ophilic aromatic substitution (SNAr) reaction by treatment of 4,4′-
dichlorodiphenylsulfone with (3-methoxy)phenylhydroquinone. In the
second step, PES-OH was obtained by demethylation of PES-OCH3 in
molten pyridine hydrochloride. The synthetic route is outlined in
Scheme 2. The advantage of hydroxyl groups being that they can be read-
ily transformed into various other funtionalities owing to their good
reactivity. Therefore, the polymer could then be easily modified by reac-
tion with monomers or polymers containing proper functionalities to
give graft copolymers, allowing the careful tuning of the properties of
the PES-OH.
 Y. Liu et al. / Desalination 316 (2013) 127–136
Scheme 1. Synthetic procedure for (3-methoxy)phenylhydroquinone.
2.3. Preparation of PES-OH and PES membranes
The PES-OH membrane was prepared by the conventional immer-
sion precipitation phase inversion method. PES-OH was dried at 80 °C
under vacuum for at least 24 h before use. Homogeneous casting solu-
tion was prepared by dissolving PES-OH and PVP in NMP at 50 °C
under vacuum and filtered by a metal filter. The concentrations of
PES-OH and PVP in the casting solution were 17 wt.% and 8 wt.%, re-
spectively. After degassing, the casting solution was cast onto a polyes-
ter nonwoven fabric supported by a glass plate using a casting knife
with a nominal thickness of 200 μm, and then the glass plate was im-
mersed immediately into a coagulated bath of deionized water at
room temperature (about 18 °C). Finally, the membrane was kept in de-
ionized water for at least 48 h until all of solvent and water-soluble
polymer were removed. In this work, the PES membrane was used as
a benchmark reference for evaluating the membrane performance be-
cause it is a commercial ultrafiltration membrane material and its
chemical structure similarity to the PES-OH. The reference PES mem-
brane was prepared by the same procedure as the PES-OH membrane.
2.4. Ceric (IV) redox surface graft polymerization of MPC on the PES-OH
membrane
The PES-OH membrane was subjected to grafting reaction in an
aqueous solution using CAN as initiator [29,30], and the schematic il-
lustration is shown in Scheme 3. Firstly, the PES-OH membrane was
immersed in acetone at room temperature for 10 h, and then treated
by ultrasonication for 30 min to remove surface impurities and dried
under a vacuum oven at 50 °C for 12 h. Then the membrane was im-
mersed in an aqueous solution containing 5% (w/v) concentration of
MPC. After displacing oxygen by argon gas about 10 min, the CAN
initiator was added in the aqueous solution at a concentration of
2 × 10 −3 mol/L. The reaction was conducted at 50 °C and was allowed
to proceed for 4 h with continual degassing and stirring. Following
the modified membrane (PES-g-MPC) was washed with deionized
water and ethanol to remove ungrafted homopolymer from the sur-
face and the pores, and allowed to dry in a vacuum oven at 50 °C
for 12 h before carrying out ultrafiltration experiments.
Scheme 2. Synthetic procedure for poly(arylene ether sulfone) containing hydroxyl groups.
129
2.5. Membrane characterization
The characteristics of the membranes were investigated using the
following parameters: surface chemical structure, surface chemical
composition, contact angle, morphology, porosity and pore size. The
membranes used for characterization were dried under vacuum at
50 °C for 24 h.
Fourier transform infrared spectroscopy (FTIR, Bruker Vertex 80 V)
with an ATR unit (Attenuated Total Reflection, crystal, 45°) was used
to investigate the surface chemical structures of the membranes. Absor-
bance spectra were obtained in the region of 4000–400 cm−1 with res-
olution 4 cm−1 for 32 scans. All the spectra were baseline corrected.
The surface chemical compositions of the PES-OH and PES-g-MPC
membranes were performed by X-ray photoelectron spectroscopy
(XPS) on an ESCLAB MKII with Al/K (hν = 1486.6 eV) anode mono
X-ray source. The atomic compositions of the elements were calculated
by their corresponding peak areas.
The static water contact angles of the membranes were estimated
by sessile drop method with a contact angle goniometer from Drop
Shape Analysis (DSA 100 KRUSS GMBH, Hamburg) at room tempera-
ture. About 4 μL of deionized water was dropped onto the membrane
surface with a microsyringe, and the value of water contact angle was
recorded after 3 s. At least five measurements in different locations of
the membrane samples were carried out and averaged to yield the
contact angles. In addition, the surface free energy was also calculated
according to the following equation:
rffiffiffiffiffi
γs −βðγs −γl Þ2
cosθ ¼ −1 þ 2 e ð1Þ
γl
where γs and γl represent the solid and liquid surface free energy, re-
spectively. θ is the contact angle of the membrane sample. The value
of water surface free energy is 72.8 mJ/m 2. β is the constant coeffi-
cient related to a specific solid surface and the value of 0.0001247 is
adopted from previously reported literature [25].
The surface morphologies of the unmodified and modified mem-
branes were examined by a scanning electron microscope (SSX-550,
Shimadzu equipped with energy dispersive X-ray (EDX) spectroscopy).
130
Scheme 3. Schematic illustration of the preparation process of the PES-g-MPC membrane by graft polymerization.
The porosity of the membrane was measured by the dry-wet
weight method which was calculated according to Eq. (2) [33]:
m1 −m2
ε¼
ρw Al
where ε is the porosity (%), m1 is the weight of the wet membrane
(g), m2 is the weight of the dry membrane (g), ρw is the water density
(0.998 g/m 2), A is the effective area of the membrane (cm 2), and l is
the membrane thickness (μm).
Average pore size rm (m) was determined by the filtration velocity
method according to the Guerout–Elford–Ferry equation, which can
be calculated as follows [34–36]:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð2:9−1:75εÞ  8ηlQ t
rm ¼
ε  A  ΔP
where Qt is the volume of the permeate water per unit time (m 3/s),
ΔP is the operational pressure (0.1 MPa), and η is the viscosity of
water (8.9 × 10 −4 Pa.s) at 25 °C. In order to minimize experimental
error, each membrane was measured for three times and calculated
the average.
2.6. Protein adsorption experiments
The amount of proteins adsorbed on membrane is one of the most
important evidence in evaluating the fouling resistant ability of mem-
branes, and BSA was used as model protein to evaluate the anti-
protein adsorption performance of three investigated membranes in
phosphate buffered saline (PBS, pH 7.4). The membrane samples
were cut into a round shape with a diameter of about 30 mm, and
treated by ultrasonication for 30 min in 0.1 M PBS solution for clean-
liness. Then the pre-treated membranes were immersed into PBS so-
lution containing BSA (1.0 mg/mL) at 25 °C for 4 h. After adsorption,
each membrane was rinsed three times in the fresh PBS by gentle
shaking. Then these membranes were transferred into a well-plate
filled with PBS solution, and the protein adsorbed on the membrane
surface was completely desorbed by ultrasonic treatment at room
temperature for 3 min. The obtained PBS solution was dyed with
Coomassie Brilliant Blue and measured by a UV–vis spectrophotome-
ter (UV3600, Shimadzu) to determine the total amount of adsorbed
protein. The final results were averaged from triplicate specimens
for each membrane.
2.7. Ultrafiltration experiments
The membrane performances were tested using a stirred dead-
end filtration cell at room temperature, and the effective membrane
area is around 12.6 cm2. At first, each membrane was initially subjected
to pure water with pressure of 0.2 MPa for 1 h prior to performing the
Y. Liu et al. / Desalination 316 (2013) 127–136
ultrafiltration experiments. Then the pressure was lowered to 0.1 MPa
and all the ultrafiltration experiments were carried out at this pressure.
After compacted, deionized water was passed through the membrane
for 1 h to obtain the beginning pure water flux (Jw,0, L/m2h), and the
ð2Þ
flux was measured every 5 min. In this present study, three cycles of fil-
tration experiment was carried out for each membrane sample. In each
cycle, a BSA solution with a concentration of 1.0 mg/ml in PBS (pH 7.4)
was filtrated for 2 h. The flux during protein filtration was recorded
which called Jp,i (i means the ith cycle). After BSA solution filtration,
the membrane was washed thoroughly and passed through deionized
water for another 30 min (the washing time was not counted in the fil-
tration cycle). Thereafter, the pure water flux was measured again with-
in 1 h for the membrane, which was recorded as Jw,i. The flux (Jw and Jp)
of the membrane was determined by direct measurement of permeate
volume, which was calculated by the following equation:
ð3Þ
V
J¼ ð4Þ
At
where V was the volume of permeation, A was the effective membrane
area and t was the permeation time. In order to evaluate the recycling
property of these membranes, the flux recovery ratio (FRRi) during
the ith cycle is calculated using the following expression:
!
J w;i
FRRi ð% Þ ¼  100 ð5Þ
J w;i−1
The higher FRR value, the better the antifouling property of the
membrane. The membrane rejection ratio (R) was calculated by using
the following equation:
!
Cp
Rð% Þ ¼ 1−  100 ð6Þ
Cf
In which Cp (mg/L) is the permeate concentration and Cf (mg/L) is
the feed concentration. The solute concentration of permeation was
measured by a UV–vis spectrophotometer (UV3600, Shimadzu).
To study the antifouling property in more detail for the unmodified
and modified membranes, the degree of total flux loss caused by total
protein fouling in the ith cycle, Rt,i, was defined as
!
J w;i−1 −J p;i
Rt;i ð% Þ ¼  100 ð7Þ
J w;i−1
A high value of Rt,i corresponds to a large flux decay and serious
membrane fouling. The total flux loss was caused by both reversible
 Y. Liu et al. / Desalination 316 (2013) 127–136 131

and irreversible protein fouling in the ith cycle. Rr,i was calculated by membranes, and the SEM photographs are shown in Fig. 1. It is apparent
the following equation: that the top surfaces are much different between the unmodified and
! modified membranes. The PES-OH membrane showed a relatively
J w;i −J p;i smooth surface, and the surface of the PES-g-MPC membrane became
Rr;i ð% Þ ¼  100 ð8Þ
J w;i−1 much rougher after the graft polymerization. Therefore, it could be ten-
tatively concluded that the MPC monomer was grafted on the PES-OH
which was the reversible fouling ratio caused by reversible fouling, surface by using CAN as an initiator, and resulted in the formation of
and could be eliminated by hydraulic cleaning. And Rir,i was calculat- many small dot-like structures on the surface of the modified membrane.
ed by the following equation: The phenomenon of the formation of the “dot-like” structure has often
been reported in the surface-initiated atom transfer radical polymeriza-
!
J w;i−1 −J w;i tion (ATRP) method [40–42]. Furthermore, the energy-dispersive X-ray
Rir;i ð% Þ ¼  100 ¼ Rt;i −Rr;i ð9Þ (EDX) P mapping on the surfaces of the PES-OH and PES-g-MPC mem-
J w;i−1
branes is also shown in Fig. 1. It could be seen that elemental phosphorus
(the bright spots) is evenly distributed on the modified membrane
which was the irreversible fouling ratio caused by irreversible fouling,
surface, and there is no elemental P on the surface of the unmodified
and can only be eliminated by chemical cleaning or enzymatic degra-
membrane. Since MPC is the only source of elemental P, EDX measure-
dation [14,37–39]. Rt,i was the sum of Rr,i and Rir,i.
ment gave valuable information to confirm that the poly(MPC) was suc-
cessfully grafted on the PES-OH membrane surface.
3. Results and discussion

3.1. Membrane characterization 3.1.2. FTIR-ATR spectroscopy

To clearly understand, the chemical structures of the top surface of
3.1.1. Scanning electron microscopy the unmodified and modified membranes were thoroughly character-
The scanning electron microscopy (SEM) was employed to investi- ized by FTIR-ATR spectroscopy that plays an important role in surface
gate the surface morphology changes of the unmodified and modified or near-surface chemical composition analysis. Fig. 2 shows the FTIR-

Fig. 1. SEM images of the surface of the unmodified and modified membranes: (a) the PES-OH membrane and (b) the PES-g-MPC membrane. EDX P-mapping on the surface of the
unmodified and modified membranes: (c) the PES-OH membrane and (d) the PES-g-MPC membrane.
132 Y. Liu et al. / Desalination 316 (2013) 127–136

Fig. 2. FTIR-ATR spectrum of the unmodified and modified membranes: (a) the PES-OH
membrane and (b) the PES-g-MPC membrane.

Fig. 3. XPS spectrum of the unmodified and modified membranes: (a) the PES-OH
membrane and (b) the PES-g-MPC membrane.

ATR spectrum of the PES-OH and PES-g-MPC membranes. Two absorp-

tion peaks were clearly observed at 1149 cm−1 and 1231 cm−1 for
both the unmodified and modified membranes which could be attributed
mainly to O_S_O group and Ar\O\Ar group, and these characteristic
absorption peaks were almost unchanged after the graft polymerization.
This is because the thickness or the contents of poly(MPC) layer may be
below the detection limit of FTIR-ATR. Compared to the FTIR-ATR
spectrum of the PES-OH membrane, three new absorption peaks at
968 cm−1, 1072 cm−1 (−POCH2-) and 1244 cm−1 (P_O) were ob-
served only for the PES-g-MPC membrane which could be attributed to
the phosphate (P\O) group in the MPC unit. Additionally, the strong ad-
sorption peak at 1722 cm−1 only corresponds to the ketone group in the
MPC unit was also observed in the spectrum of the PES-g-MPC mem-
brane. The FTIR-ATR spectrum showed that the MPC was successfully
grafted on the surface of the PES-OH membrane.
poly(MPC) surface coverage (CPMPC) on the PES-OH membrane surface
was calculated as the following equation:
AmP
C PMPC ð% Þ ¼  100 ð10Þ
ApP
where AmP is the phosphorus atomic percentage on the PES-g-MPC
membrane surface measured by XPS, and ApP is the phosphorus atomic
percentage of poly(MPC) under the condition of membrane surface
completely covered with poly(MPC). According to the above equation,
the PES-g-MPC membrane presents CPMPC of 84.98%. A large number of
hydroxyl groups are well distributed on the surface of the PES-OH mem-
brane may be responsible for the high degree of poly(MPC) surface
coverage.

3.1.3. X-ray photoelectron spectroscopy 3.1.4. Contact angle

Since the penetration depth of FTIR-ATR spectroscopy is at the level Surface hydrophilicity is one of the most important factors in de-
of a micron, and the layer of graft polymerization of a zwitterionic poly- termining antifouling property and performance of ultrafiltration
mer is usually very thin. To further confirm successful graft polymeriza- membrane. The hydrophilicity and wettability of the unmodified
tion on the PES-OH membrane, XPS, a more surface-sensitive method and modified membranes in this study were evaluated by contact
(XPS only measures a depth of about 10 nm), was used to identify the angle measurement, which was also used to assess the surface (inter-
surface chemical changes. The comparison between the unmodified facial) free energies of substrate surfaces. It is commonly accepted
and modified membranes (Fig. 3) shows clearly that the chemical com- that the lower contact angle represents the greater tendency for
positions are markedly different. In the case of the PES-OH membrane, water to wet the membrane, the higher surface energy and the higher
two strong peaks at 285 (C1s) and 532 (O1s) eV were obviously ob- hydrophilicity. Table 2 lists the detailed water contact data from the
served, which corresponded to carbon and oxygen atoms. And two measurements on these different membranes.
small peaks at 168 (S2p) and 230 (S2s) eV were also found which were The PES membrane has the highest contact angle of 82.91°, indicat-
attributed to sulphur atom in the sulfone group. For the PES-g-MPC ing the lowest hydrophilicity. The PES-OH membrane has a more hydro-
membrane, the content of carbon (C1s) was slightly decreased while philic surface (67.81°) than the PES membrane, and this tendency was
the content of oxygen (O1s) was slightly increased after the graft poly- attributed to the hydrophilic nature of the hydroxyl groups. The de-
merization reaction, and the XPS peaks at 286.9 and 288.8 eV were crease of contact angle indicated that a highly hydrophilic surface was
attributed to carbon atoms of the ether bond (−C\O\C–) and carbonyl created. After the graft polymerization reaction occurred, the contact
group (C_O), respectively. Besides, two new XPS peaks at 134 (P2p) and
190 (P2s) eV were attributed to phosphorus atom, and the peak in the
Table 1
nitrogen atom region at 402.5 (N1s) eV attributed to the quaternary am- Surface chemical compositions of the PES-OH and PES-g-MPC membranes from XPS.
monium group was detected. These peaks were specific to the
Samples Compositions (%)
phosphorylcholine group in the MPC unit as compared with the survey
scan spectrum of the PES-OH membrane. It could be indicated that the C O S N P
poly(MPC) was successfully grafted on the PES-OH membrane surface. PES-OH 79.73 16.81 3.45 – –
The detailed analysis results of the surfaces of the unmodified and PES-g-MPC 62.14 28.29 0.46 4.62 4.47
modified membranes determined by XPS were shown in Table 1. Pure MPCa (57.89) (31.59) – (5.26) (5.26)
a
Based on the only source of elemental P in the MPC unit, the degree of The values of pure MPC are the theoretical atomic percentages.
 Y. Liu et al. / Desalination 316 (2013) 127–136 133

angle of the PES-g-MPC membrane was significantly decreased further

by immobilization of poly(MPC) onto the surface of the PES-OH mem-
brane. Comparing with the PES-OH membrane, obvious decrease of
water contact angle (46.43°) and dramatic increase of the surface energy
(55.97 mJ/m2) were observed for the PES-g-MPC membrane, the value
of water contact angle is comparable with those previously reported in
the literatures [24,43]. The zwitterionic groups could form a hydration
layer via electrostatic interaction in addition to the hydrogen bond
[23,44], therefore, the introduction of MPC unit on the membrane sur-
face could effectively enhance the hydrophilicity and improve antifoul-
ing property of ultrafiltration membrane.

3.2. Membrane performance

3.2.1. Protein adsorption

The static protein adsorption is one of the dominant factors in
determining the membrane fouling, and the reduction of protein
adsorption will enhance the antifouling property of membrane. Here-
in, BSA was used as the model protein to evaluate the static protein
adsorption on the surface of the unmodified and modified mem-
branes. The antifouling property of membrane is highly dependent
on the membrane surface chemistry, such as surface charge character,
surface free energy, surface chemical composition and surface mor-
phology. In many cases, the nonspecific protein adsorption on the
membrane surface due to the inherent hydrophobic characteristic
often causes serious membrane fouling. Therefore, the increment in
the surface hydrophilicity is a straightforward and effective method
to enhance the antifouling property of membrane.
As is shown in Fig. 4, the adsorption amount for measured protein
exhibited the following order: PES>PES-OH>PES-g-MPC. Interestingly,
this tendency is very similar to the tendency found in the static water con-
tact angle measurement. The PES membrane was found the highest pro-
tein adsorption due to its hydrophobic character. BSA adsorption amount
on the PES-OH membrane was lower than that on the PES membrane.
This may be attributed to the introduction of the hydrophilic hydroxyl
groups. The PES-g-MPC membrane exhibited the lowest adsorption
amount among the three investigated membranes. In general, the protein
resistant chemical structures are commonly hydrophilic, overall electri-
cally neutral, hydrogen-bond acceptors but not hydrogen-bond donors
[45], and the zwitterionic groups share all of these common characteris-
tics. It is commonly believed that zwitterions form a regular hydration
layer via electrostatic interaction in addition to hydrogen bond, and the
protein was excluded from the hydration layer to avoid the substantial
entropy loss caused by the entrance of large protein molecules into the
highly structural zwitterionic layer [46]. Our study indicated that the
grafting of poly(MPC) onto the surface of the PES-OH membrane de-
pressed the protein adsorption effectively. The experimental result was
consistent with the general antifouling mechanism for zwitterionic
membrane [17,23].
Fig. 4. BSA adsorption on the PES, PES-OH and PES-g-MPC membranes.
of the PES-OH membrane. The PES-g-MPC membrane exhibited the
lowest pure water flux among the three investigated membranes.
This result could be proved at quantitative degree by determining
the average pore size. The average pore sizes of the three investigated
membranes were calculated based on the Eq. (3). In this study, the
PES-OH membrane has the highest average pore size (11.76 nm),
whereas the PES-g-MPC membrane has the lowest value (7.23 nm),
which agree with the water flux measurement. The average pore
size of the PES membrane is 10.34 nm, which had inconspicuous dif-
ferent from the PES-OH membrane, also clearly had a slight small
pure water flux. Furthermore, the phenomenon could be also
explained as follows: the graft polymerization usually occurs in the
pores of the ultrafiltration membrane, which will cause these pores
become smaller or blocked and the surface becomes more dense,
meanwhile any defect on the surface is also repaired, and leading to
the pure water flux was seriously decreased as a result of low porosity
and reduced pore size.
As shown in Fig. 5, the flux decreased dramatically at the initial
operation of BSA solution ultrafiltration due to membrane fouling
caused by protein adsorption or deposition on the membrane surface.
When the adsorption and deposition of protein molecules may reach
equilibrium, a relatively steady flux (Jp) was retained in the final op-
eration of BSA solution ultrafiltration. The BSA rejection ratio (R) of
the PES membrane is 98.4%, and that of the PES-OH membrane is
95.7%. However, the PES-g-MPC membrane has an excellent BSA

3.2.2. Permeation properties of the unmodified and modified membrane

Ultrafiltration experiments were carried out to investigate the
separation performance of the unmodified and modified membranes.
Fig. 5 presented time-dependent flux during ultrafiltration operation.
The pure water flux (Jw,0) of the PES membrane is 156.3 L/m 2h, which
is lower than that of the PES-OH membrane. This result may be attrib-
uted to the increased hydrophilicity and surface morphology change

Table 2
Water contact angles and surface free energies of the PES, PES-OH and PES-g-MPC
membranes.

Samples

PES PES-OH PES-g-MPC

Contact angle (°) 82.90 ± 2.37 67.81 ± 1.44 46.43 ± 1.93

Fig. 5. Time-dependent fluxes of the PES, PES-OH and PES-g-MPC membranes during
Surface energy (mJ/m2) 33.71 ± 1.45 42.92 ± 0.88 55.97 ± 1.18
the protein ultrafiltration experiment.
134 Y. Liu et al. / Desalination 316 (2013) 127–136
rejection ratio of 99.9%. The decrease of pore size of the modified
membrane had a positive effect on BSA rejection.
After 2 h of BSA solution filtration, the membranes were washed
thoroughly and passed through deionized water for another 30 min,
and the water fluxes of the cleaned membranes (Jw,1) were measured
again. FRR is introduced to reflect the resistant fouling ability of the
membranes, and higher value of FRR means the higher resistant foul-
ing ability. The FRR values were calculated and presented in Fig. 6. The
FRR value is only 60.6% for the PES membrane, meaning the existence
of serious membrane fouling. The PES-OH membrane has a larger FRR
value (74.5%), suggesting that adsorbed and deposited protein on the
membrane surface could be easily washed away. The zwitterionic
PES-g-MPC membrane has the highest FRR value (87.1%), which is
consistent with the protein adsorption experiments. The zwitterionic
poly(MPC) chains can prevent direct contact of BSA molecules with
the membrane surface, and the protein fouling in the PES-g-MPC
membrane was suppressed significantly under the ultrafiltration
process.
3.2.3. Fouling analysis of the unmodified and modified membranes
During the ultrafiltration process, the rejected protein molecules
adsorbed or deposited on the surface and inside the membrane pores
causing membrane fouling, which could be further divided into revers-
ible and irreversible fouling. One part of fouling, recognized as revers-
ible fouling, was caused by reversible protein adsorption or deposition
and could be eliminated through hydraulic cleaning (hydrodynamic
method); while the other part of fouling, defined as irreversible fouling,
could not be eliminated only through hydraulic cleaning. More detailed
results of the total fouling ratio (Rt), the reversible fouling ratio (Rr) and
the irreversible fouling ratio (Rir) of the three investigated membranes
are given in Fig. 6. It can be seen that the Rt value of the PES membrane
is larger than that of other two types of membrane. The bigger Rt value
indicates higher total flux loss, corresponding to more protein adsorp-
tion and deposition on the membrane surface. Meanwhile, the Rir
value of the PES membrane is the largest among three types of mem-
brane. It can be concluded that the protein fouling on the PES mem-
brane is so serious that the fouling cannot be removed by hydraulic
cleaning. In addition, the zwitterionic PES-g-MPC membrane has not
only the lowest Rt value but also the lowest Rir value, which was already
confirmed in protein adsorption experiments. Generally speaking,
when protein molecules contacted with the membrane surface, water
molecules between protein and the membrane surface would be
Fig. 6. Summary of the flux recovery ratio (FRR), the total fouling ratio (Rt), the revers-
ible fouling ratio (Rr) and the irreversible fouling ratio (Rir) of the PES, PES-OH and
PES-g-MPC membranes during the protein ultrafiltration experiment.
replaced. The high surface coverage of poly(MPC) segments leads to a
spontaneous rearrangement of the polymer to form molecular brush
and strong hydration layer due to electrostatic interaction by the prox-
imity between phosphate group and quaternary ammonium group. The
zwitterionic poly(MPC) can take up large quantities of free water,
which possibly prevents protein molecules from close contact with
the membrane surface. These results indicated obviously that the intro-
duction of MPC units efficiently reduces total membrane fouling, espe-
cially irreversible membrane fouling.
3.2.4. Recycling properties of the unmodified and modified membranes
In the practical application, the ultrafiltration membrane should keep
long-term antifouling property which induced a decrease of production
cost by decreasing the energy consumption and the cleaning frequencies.
A long-term ultrafiltration experiment with three runs was carried out to
further investigate the recycling properties of the three investigated
membranes, and the results are shown in Fig. 7. After three times of
BSA ultrafiltration with a total operation time of 10 h and corresponding
three times of hydraulic cleaning, the pure water flux of the PES mem-
brane was decreased from 156.3 to 61.2 L/m2h and the flux of BSA
solution was only 40.3 L/m2h. However, the pure water flux of the
PES-g-MPC membrane can retain at 107.8 L/m2h, the flux of BSA solution
could keep at 64.5 L/m2h after three times of BSA solution ultrafiltration.
The performance of the PES-OH membrane was intermediacy between
the PES and PES-g-MPC membrane. The water flux recovery ratio during
each cycle could be calculated to indicate the extent of cleaning efficiency
or the effect of irreversible fouling resistance of the membranes, and the
results are presented in Fig. 8. For the PES membrane, the water flux re-
covery ratio was 60.6% in the first cycle, and the value increased to 76.6%
in the second cycle, and reached 84.4% in the third cycle. It reflected an
irreversible fouling that was 39.4% in the first cycle, 23.4% in the second
cycle, and 15.6% in the third cycle. The amount of newly formed irrevers-
ible adsorption of protein was still significant. For the PES-g-MPC mem-
brane, the water flux recovery ratio was 87.0% in the first cycle, 92.3% in
the second cycle, and 95.5% in the third cycle. The degree of irreversible
fouling was significantly reduced after each cycle, which ensured high
water flux recovery in each cycle. The excellent performance of the zwit-
terionic PES-g-MPC membrane showed that the modified membrane
could be reused for a longer time without compromising the water
flux. On the whole, the incorporation of zwitterionic poly(MPC) seg-
ments on the PES-OH membrane effectively reduced the total membrane
fouling especially irreversible membrane fouling, which is an appropri-
ate method for preparation of highly effective antifouling ultrafiltration
membrane.
Fig. 7. Time-dependent recycling fluxes of the PES, PES-OH and PES-g-MPC membranes
during the protein ultrafiltration experiment of three recycles.
 Y. Liu et al. / Desalination 316 (2013) 127–136
Fig. 8. The flux recovery ratio (FRR) of the PES, PES-OH and PES-g-MPC membranes
after different cycles of the protein ultrafiltration experiment.
4. Conclusions
It is well known that serious fouling of the ultrafiltration membrane
restricts its application, which could result from the excessively adsorp-
tion of protein through the hydrophobic interaction between the mem-
brane surface and protein molecules. The main advantage of the
introduction of hydrophilic zwitterionic groups is to modify the surface
chemical property and improve antifouling property of the ultrafiltra-
tion membrane. This was achieved in this present article by redox
graft polymerization using CAN as initiator to successfully graft zwitter-
ionic MPC monomer onto the surface of the PES-OH membrane. The
grafting process is straightforward and effective which avoid the com-
plex and unfavorable pretreatment process and/or hydroxylated treat-
ment because of the presence of the activated hydroxyl groups on the
surface of the PES-OH base membrane. Thus, the PES-OH membrane
could be easily modified by reaction with the zwitterionic monomers
to obtain the desired properties. FTIR-ATR and XPS studies confirmed
the graft polymerization performed on the surface of the PES-OH mem-
brane. Static water contact angle test showed that some extent of hy-
drophilic behavior was obtained for the PES-g-MPC membrane. The
modified membrane has higher flux recovery ratio and lower extent
of membrane fouling, as compared to those of the PES and PES-OH
membrane. The excellent antifouling property renders the zwitterionic
PES-g-MPC membrane longer operation life, which is quite beneficial
for practical application.
Acknowledgments
This work was supported by a grant from the National High Tech-
nology Research and Development Program of China (863 Program)
(No. 2012AA03A212).
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