Journal of Membrane Science 322 (2008) 32–38

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Preparation and pervaporation performance of surface crosslinked PVA/PES

composite membrane
Ruili Guo, Xin Fang, Hong Wu, Zhongyi Jiang ∗
Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, 92# Road Wijin, Tianjin University, District Nankai, Tianjin 300072, China

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

Article history: This study describes the facile preparation of poly(vinyl alcohol) (PVA)/polyethersulfone (PES) composite
Received 10 December 2007 membranes by interfacial reaction technique, aiming at acquiring the improved structural and operational
Received in revised form 28 April 2008 stability of the resulting membranes. The effect of interfacial crosslinking agent and hydrophilicity of sup-
Accepted 2 May 2008
port layer on the interfacial adhesive strength and pervaporation performance of composite membranes
Available online 18 May 2008
were investigated. The optimal recipe for PVA/PES composite membrane preparation was as follows: PES
support layer was treated with 0.1 wt.% borax aqueous solution, fully dried and then immersed into 2 wt.%
Keywords:
PVA aqueous solution. The resulting PVA active layer was 1–1.5 ␮m thick after twice dip-coating. The as-
Poly(vinyl alcohol)
Polyethersulfone
prepared PVA/PES composite membrane exhibited high separation factor of over 438, high permeation
Composite membrane flux of 427 g m−2 h−1 for 80 wt.% EG in the feed at 70 ◦ C and desirable structural stability. It could be
Ethylene glycol derived that adoption of interfacial reaction would be an effective method for preparing the composite
Pervaporation membranes suitable for large-scale dehydration of ethylene glycol/water mixture.
Dehydration © 2008 Published by Elsevier B.V.

1. Introduction
For the purpose of improving the pervaporation performance
of polymeric membranes, especially for permeation flux, much
effort has been devoted to fabricate the well-structured compos-
ite membrane composed of support layer and active layer [1]. For
water-permselective composite membrane, in order to increase the
swelling resistance, the support layer bulk should be hydrophobic
enough; on the other hand, in order to increase the permeability
and selectivity, the active layer should be hydrophilic enough. A
challenge will be often occurred that the active layer is difficult to
be tightly coated on the support layer because of the great surface
tension and weak interfacial interaction between these two layers.
There exist two common methods for decreasing the surface
tension and increasing the interfacial interaction between active
layer and support layer (or substrate): (1) increasing the surface
energy of support layer by hydrophilic modification of the bulk
or the surface of the support layer [2–7] and (2) applying a cou-
pling agent or a surfactant which has moderate affinity toward
both the hydrophilic active layer and hydrophobic support layer [8].
Hydrophilic modification of the support layer surface seems a more
attractive and facile approach. Huang et al. [9] modified polysul-
fone porous support layer through hydrophilic polymer adsorption,
∗ Corresponding author. Tel.: +86 22 27892143; fax: +86 22 27892143.
E-mail address: zhyijiang@tju.edu.cn (Z. Jiang).
which considerably increased the affinity between the thin chi-
tosan layer and polysulfone support layer. The resulting composite
membranes showed an increase of the structural stability. However,
if the modification of support layer was carried out through sim-
ple physical adsorption, the interaction between the hydrophilic
active layer and hydrophobic support layer was often rather weak
[10,11], which caused the adsorbed polymer to easily fall off from
the support layer or dissolve into aqueous solution. Yeom et al.
[12] fabricated the thin film of sodium alginate (SA) on the polysul-
fone reverse osmosis (RO) membrane by combining adsorption and
crosslinking techniques. In this case, the crosslinking agent of SA,
CaCl2 was homogeneously dispersed into the polysulfone substrate.
The hydrophilic SA polymer chain reacted with the crosslinking
agent molecules and stuck onto the support layer, which endowed
a strong adhesive strength between the SA layer and polysulfone
substrate.
In this study, composite membranes consisting of a hydrophobic
polyethersulfone (PES) support layer and a hydrophilic poly(vinyl
alcohol) (PVA) active layer were prepared and their pervaporation
performance for the separation of aqueous ethylene glycol solution
mixtures were investigated. In order to decrease the surface ten-
sion and enhance the interfacial interaction between the PVA active
layer and support layer, the PES support layer was first modified
with interfacial crosslinking agent. The effects of crosslinking agent
and concentration of casting solution on the pervaporaiton perfor-
mance of the resulting composite membranes were investigated in
detail.

0376-7388/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.memsci.2008.05.015
 R. Guo et al. / Journal of Membrane Science 322 (2008) 32–38 33

2. Experimental 2.3. Membrane characterization

2.1. Materials Fourier transform infrared (FT-IR) spectra were obtained by a

PVA (the degree of polymerization and saponification were
1750 ± 50 and 99%, respectively), ethylene glycol, borax and glu-
taraldehyde (50 wt.%) were purchased from Tianjin Guangfu Fine
Chemical Research Institute (Tianjin, China). PES ultrafiltration
membranes were purchased from Shanghai MegaVision Membrane
Engineering & Technology Co., Ltd. (Shanghai, China). The PES ultra-
filtration membranes (molecular weight cutoff of 25,000) are of
asymmetric structure supported by nonwoven polyester fabric. The
microporous support layers are approximately 75–85 ␮m thick and
exhibit a pure water flux of 610 kg/m2 h, at a cross-membrane pres-
sure difference of 0.2 MPa. All the chemicals were of analytical grade
and used without further purification. Double distilled water was
used throughout the study.
2.2. Membrane preparation
PVA was dissolved in double distilled water at 90 ◦ C to make
a homogeneous PVA solution. The solution was filtered and
deposited to remove all the bubbles. The PES ultrafiltration mem-
branes (the area of 10 cm × 10 cm) were soaked in double distilled
water for 2 days to remove glycerin and then fully dried. The dried
PES support layer was dipped in interfacial crosslinking agent aque-
ous solution, 0.1–0.5 wt.% borax or 0.1–5 wt.% glutaraldehyde, for
12 h and then fully dried again.
Hydrophilic modification of support layer: the dried PES support
layer pretreated by borax was mounted on a glass plate, sealing its
edge with masking tape, and dipped into 0.5 and 2 wt.% PVA aque-
ous solution for 5 min, respectively, to enhance the hydrophilicity
of the PES support layer and then fully dried. The contact angle of
the modified support layers was measured.
Fabrication of composite membrane: the modified support layer
were dipped into 1.5–7 wt.% PVA casting solution for 5 min and then
taken out to dry. Twice dip-coating processes should be carried out
in order to obtain a full coverage of the support layer and to min-
imize morphological defects. The PVA/PES composite membrane
was then dried overnight and brought into contact from the PVA
layer side with a crosslinking solution for 1.5 h. The crosslinking
solution used was acetone solution containing 15 vol.% of GA as
crosslinking agent and 0.12 vol.% HCl as catalyst. Finally, the surface
crosslinked PVA/PES composite membrane was washed thoroughly
with an excess amount of water to remove the remaining GA on the
membrane surface. There was not heat treatment involved to dry
the substrate and the membranes, all the membranes are dried at
room temperature.
Nicolet, 5DX instrument equipped with both horizontal attenu-
ated total reflectance (HATR) accessories. Thirty-two scans were
accumulated with a resolution of 4 cm−1 for each spectrum. Con-
tact angle of support layer was measured at 20 ◦ C by contact angle
goniometer (JC2000C, Powereach Co., Shanghai, China). Each mea-
surement was repeated six times and then averaged as the final
result. The errors were within ±5%. The morphology of composite
membranes was examined by Philips XL-30M scanning electron
microscope (SEM) instrument.
2.4. Pervaporation experiments
Pervaporation experiments were performed on the membrane
module (CM-Celfa AG Company, Switzerland). The effective mem-
brane area was 25.6 cm2 . The vacuum in the downstream side was
maintained (0.67 kPa) using a vacuum pump, and permeate was
collected in liquid nitrogen-cold traps. The compositions of the
feed and permeate were measured using Agilent 6890 gas chro-
matography equipped with a thermal conductivity detector (TCD)
and a column packed with GDX102 (Tianjin Chemical Reagent Co.,
China). The results for pervaporation separation of ethylene gly-
col/water mixtures were reproducible, and the errors inherent in
the pervaporation measurements were less than 1.0%. Separation
performance of the membranes can be evaluated on the basis of
total flux (J) and separation factor (˛):
Q
J= (1)
A t
YW /YE
˛= (2)
XW /XE
where Q is the weight of permeate collected in time t, and A is the
effective membrane area, X and Y represent the weight fractions in
the feed and permeate, respectively, and the subscripts W and E
represent water and ethylene glycol, respectively.
3. Results and discussion
3.1. Hydrophilic modification on PES support layer and
pervaporation performance of the resultant composite membranes
During EG production, excess water is added to ethylene oxide in
order to increase EG yield and to inhibit the formation of diethylene
glycol and triethylene glycol byproducts. Conventionally, the pro-
duced EG concentration is 14–16 wt.%, and multi-effect evaporation
is utilized to concentrate EG solution to 70–80 wt.%. After that the

Table 1
Modification of PES support layer and pervaporation performance of PVA/PES composite membranes for 80 wt.% EG aqueous solution in the feed at 70 ◦ C

Interfacial crosslinking agent Modified material Contact angle of modified Casting solution of Permeation flux Separation factor
PES support layer (◦ ) active layer (g m−2 h−1 ) (˛)

0.1 wt.% GA – 85.1

0.1 wt.% GA 2.0 wt.% PVA 80.1 2.0 wt.% PVA 563 73

5.0 wt.% GA – 85.7

5.0 wt.% GA 2.0 wt.% PVA 75.2 2.0 wt.% PVA 493 83

0.1 wt.% borax – 84.3

0.1 wt.% borax 0.5 wt.% PVA 63.9 2.0 wt.% PVA 542 175
0.1 wt.% borax 2.0 wt.% PVA 21.5 2.0 wt.% PVA 427 438

0.5 wt.% borax – 83.3

0.5 wt.% borax 0.5 wt.% PVA 41.1 2.0 wt.% PVA 323 272
0.5 wt.% borax 2.0 wt.% PVA 20.5 2.0 wt.% PVA 306 352
34 R. Guo et al. / Journal of Membrane Science 322 (2008) 32–38

Fig. 1. Schematic illustration of reaction between PVA and borax.

concentrated EG solution is transported in membrane modules to the fact that increasing borax content exerted no effect on the water
remove the residual water. In this study, borax and glutaraldehyde contact angle of PES support layer modified by 2 wt.% PVA aqueous
were selected as interfacial crosslinking agent for pretreatment of solution.
PES support layer. The effects of interfacial crosslinking agent on The pervaporation performance of composite membranes for
the properties of PES support layer and pervaporation performance water and EG mixtures showed that with the increase of the
of PVA/PES composite membranes for dehydration of 80 wt.% EG concentration of borax and/or PVA casting solution, the resul-
aqueous solution at 70 ◦ C were listed in Table 1. It was found that the tant composite membranes all showed increased selectivity for
introduction of interfacial crosslinking agent did not cause consid- water/EG. But the high borax content could lead to the thick cov-
erable change of the hydrophilicity of PES support layer. However, ering of PVA layer on the surface of PES support layer, which has
the modified PES support layer using borax as interfacial crosslink- negative influence on the permeation flux and even selectivity of
ing agent showed lower contact angle, as a result, the obtained composite membrane. Finally, in order to obtain thin PVA active
PVA/PES composite membranes displayed higher separation factor layer, 0.1 wt.% borax aqueous solution was used to treat PES support
than those using glutaraldehyde as interfacial crosslinking agent. layer in the subsequent study.
The reason might be that borax exhibited higher reactivity towards
PVA than glutaraldehyde at room temperature. The reaction of PVA 3.2. Effect of PVA concentration on pervaporation performance of
and borax allowed PVA to be uniformly adsorbed on the PES sup- the composite membranes
port layer (see Fig. 1) [13]. In addition, the fast reaction of PVA and
borax could promptly lead to the formation of gel network struc- PES support layer was treated with 0.1 wt.% borax solution, and
ture for PVA and effectively inhibited the penetration of PVA into then the PVA/PES composite membranes were prepared by twice
the underneath support layer. Consequently, the homogeneous PVA dip-coating in casting solution with different PVA content. The
active layer was readily acquired after the PES support layer was obtained PVA/PES composite membranes were characterized by
treated with borax aqueous solution. SEM photographs shown in Fig. 3. It can be observed that the thick-
It could be observed from above results that the hydrophilic ness of formed PVA active layer increased from 1 to 7 ␮m when the
modification of the PES support layer led to a remarkable reduc- PVA concentration increased from 1.5 to 7 wt.% and intact adhesion
tion in the water contact angle, and increased the wettability and between PVA active layer and PES support layer has been achieved.
adhesion of PES surface. Obviously, this was advantageous for eas- The PVA concentration exerts a direct influence on the thick-
ier coating of the hydrophilic PVA active layer onto the PES support ness of active layer, and the thickness of PVA active layer plays an
layer. The effects of borax and PVA concentration on the contact important role in pervaporation performance of the membranes.
angle of PES support layer and pervaporation performance were In this study, the pervaporation performance of surface crosslinked
extensively investigated and listed in Table 1. It was found that PVA/PES composite membranes for 80 wt.% EG aqueous solution
the contact angles of the modified PES support layer decreased by
increasing borax or PVA concentration, which indicated that the
increase of crosslinking agent concentration and PVA concentration
were all beneficial for hydrophilic modification of PES support layer.
However, when the PVA content increased up to 2 wt.%, the contact
angle of PVA modified PES support layer dramatically decreased
to 20◦ and was not considerably changed with the variation of
borax content. It may be explained that when the PVA content was
increased to 2.0 wt.%, its adsorption amount had reached a satu-
rated value, and a thin PVA layer would fully cover PES support layer
(this could be supported by FT-IR result). Consequently, more borax
exerted only little influence on the contact angle of PVA modified
PES support layer.
The occurrence of crosslinking between PVA and borax could be
demonstrated by the disappearance of –OH peak in “0.5 PVA–PES
(0.1 B)” spectrum. As shown in Fig. 2, no evident absorption peak
had been detected around 3300 cm−1 in the spectrum of “0.5
PVA–PES (0.1 B)”, which indicated that the reaction between PVA
and borax had substantially happened. Meanwhile, it was observed
that the spectra of the PES support layer modified with 2 wt.% PVA
Fig. 2. FTIR spectra of PES support layer modified by PVA aqueous solution (0.5
showed the characteristic peak of PVA, which meant that the sup- PVA–PES (0.1 B) means that 0.5 wt.% PVA modified PES support layer was treated
port layer was completely covered by PVA. This could account for with 0.1 wt.% borax aqueous solution).
 R. Guo et al. / Journal of Membrane Science 322 (2008) 32–38
Fig. 3. SEM photographs of the cross-sections of PVA/PES composite membranes.
at 70 ◦ C was investigated by varying the casting solution concen-
tration. As shown in Fig. 4, the permeation flux monotonously
decreased as the PVA casting solution concentration increased,
which was arised from the increase of the active layer thickness. The
separation factor increased with the increase of PVA casting solu-
tion concentration firstly and reached maximum value when the
PVA content was 2 wt.%, and then began to decrease. This changing
trend can be explained as follows: when the PVA casting solution
concentration was too low, it was difficult to form the homoge-
neous and defect-free active. Therefore, when the casting solution
concentration was 1.5 wt.%, the as-prepared composite membrane
had the highest permeation flux (756) but the lowest separation
factor (44). With the PVA content increasing, the coverage of PVA
on the PES support layer was increased, which showed higher sep-
Fig. 4. Effect of casting solution concentration on the pervaporation performance
for 80 wt.% EG aqueous solution in the feed at 70 ◦ C.
35
aration factor for water/EG. However, the swelling degree of the
active layer also increased with the increase of PVA active layer
thickness because of the limited degree of crosslinking. It is well
known that the PES materials can be easily dissolved in acetone.
Hence, when the PVA active layer is very thin, the PES support
layer can be easily destroyed due to the acetone intrusion during
the crosslinking period. As a result, the crosslinking time of 1.5 h
was determined as the optimum crosslinking time in this study.
With the increase of the PVA concentration in casting solution, the
PVA active layer would become unstable in EG aqueous solution
because of the distinct difference in swelling characteristics, which
led to the dramatic decrease in separation factor of the composite
membranes.
3.3. Effect of feed composition on pervaporation performance of
the surface crosslinked composite membranes
The effect of feed concentration on the pervaporaiton perfor-
mance of EG aqueous solution through the surface crosslinked
PVA/PES composite membranes was shown in Fig. 5. The perme-
ation flux increased with the increase of water content in the feed
because of the increased plasticization action of water molecules
in the membrane. The separation factor of composite membranes
reached a maximum value at 20 wt.% water content in the feed, at
higher water content in the feed the separation factor decreased
until 60 wt.% water content, the separation factor increased again
when water content in the feed was greater than 60 wt.%. The
separation factor and flux of the composite membranes did not
follow the typical trade-off phenomenon found in most poly-
meric pervaporation membranes [14]. This might be attributed
to the synergistic influence of plasticization effect between per-
meates and membrane, coupling effect between EG and water.
As described in our previous study [15], there was pronounced
coupling effect between EG and water which was demonstrated
36 R. Guo et al. / Journal of Membrane Science 322 (2008) 32–38

Fig. 5. Effect of feed concentration on the pervaporation performance of surface Fig. 7. Effect of feed temperature on the separation factor through surface
crosslinked PVA/PES composite membranes at 70 ◦ C. crosslinked PVA/PES composite membranes.

through swelling and sorption experiments and calculations by The activation energy for water and EG permeation can be cal-
Flory–Huggins and UNIQUAC model. The coupling effect influenced culated from an Arrhenius-type expression as Eq. (3):
not only the permeation flux but also the separation factor; as a  −E 
p
result, the separation factor changed without a consistent trend. Jp = Jpo exp (3)
RT
where Ep is the apparent activation energy of penetration, Jp and
3.4. Effect of operating temperature on pervaporation
Jpo are the permeation flux and permeation rate constant, respec-
performance of the surface crosslinked PVA/PES composite
tively, R is the gas constant, and T is Kelvin temperature. Arrhenius
membranes
plots of ln Jp flux versus to 1/T for water and EG at different feed
concentrations were shown in Figs. 8 and 9. It acquired a distinct
The composite membrane showed excellent thermal stability
linearity in the given temperature range for water and EG flux and
when pervaporation tests were carried out from 30 to 80 ◦ C. The
follows the typical Arrhenius trend.
effect of temperature on the permeation flux and separation fac-
The permeation activation energy of water and EG through the
tor of the composite membrane were depicted in Figs. 6 and 7,
PVA/PES composite membrane can be estimated by measuring the
the permeation flux increased significantly and separation fac-
slope of the straight lines in Figs. 8 and 9. The dependence of the
tor decreased with the temperature increasing from 313 to 353 K.
permeation activation energy versus the EG content in the feed
When operating temperature increased, the saturated vapor pres-
was illustrated in Fig. 10. It could be observed that the perme-
sure of permeating components in the upstream increased, but the
ation activation energy of water and EG through the composite
pressure in the downstream was maintained constant, therefore
membrane decreased as the water content in the feed increased.
the increased pressure difference between the upstream and down-
The reason was that higher water content in the feed led to a
stream sides enhanced the transport driving force. In addition, high
higher degree of swelling and thus resulted in lowered perme-
temperature facilitated the mobility of PVA chains and increased
ation activation energy. In addition, comparison of the surface
the swelling degree of PVA layer. All these factors led to the increase
crosslinked PVA composite membranes with surface crosslinked
of the permeation flux and the decrease of the separation factor of
PVA homogeneous membrane [15], it could be found that the acti-
surface crosslinked PVA/PES composite membranes.
vation energy of water and EG transporting through the surfaced

Fig. 6. Effect of feed temperature on the permeation flux through surface

crosslinked PVA/PES composite membranes. Fig. 8. Arrhenius relationship between water permeation flux and temperature.
 R. Guo et al. / Journal of Membrane Science 322 (2008) 32–38
Fig. 9. Arrhenius relationship between EG permeation flux and temperature.
crosslinked PVA/PES composite membranes were lower than that of
water and EG transporting through surface crosslinked PVA homo-
geneous membrane (Ep, water = 52.69 kJ/mol, Ep, EG = 73.24 kJ/mol).
This change indicated that the decrease of separation layer thick-
ness could remarkably reduce the energy barrier of water and
EG through the membrane. Moreover, it was observed that the
impact of feed temperature on the permeation of EG through sur-
face crosslinked PVA composite membranes was not so remarkable
in comparison with those of surface crosslinked PVA homogeneous
membranes. The EG permeability could be affected by the con-
centration gradient resulting from the difference in partial vapor
pressure between the feed and the permeate. However, according
to the solution–diffusion model [16], the diffusion process due to
the concentration gradient was not the only factor which deter-
mined the permeability in the dynamic permeation process. The
diffusion path of the membrane also played an important role.
In other words, under the low feed temperature, the EG perme-
ability through the composite membranes significantly increased
due to the considerably shortened diffusion path whereas the
concentration gradient was low. This may constitute the major
reason that the effect of feed temperature on the EG perme-
ability was not so pronounced for surface crosslinked composite
membranes.
Fig. 10. Activation energy for permeation through surface crosslinked composite
membrane.
37
Fig. 11. Effect of feed flow rate on the pervaporation performance of surface
crosslinked PVA/PES composite membranes for 80 wt.% EG aqueous solution in the
feed at 70 ◦ C.
3.5. Effect of feed flow rate on pervaporation performance of the
surface crosslinked PVA/PES composite membranes
For industrial application, the production capacity is always a
major concern, it is necessary to examine the influence of dif-
ferent feed flow rates on process performance. The effect of the
feed flow rate on the pervaporation performance of surfaced
crosslinked PVA/PES composite membranes was shown in Fig. 11.
With the increase of the feed flow rate, the turbulence of feed solu-
tion increased, which subtly reduced the temperature polarization
between the membrane surface and the bulk phase and increased
the operating pressure in the feed side. Both factors increased the
permeation flux slightly but had little effect on the separation fac-
tor. This could be explained as follows: when the feed flow rates
were in the range of 60–120 L/h in experiments, the concentration
polarization effect was not pronounced, accordingly the pervapo-
ration performance of the membranes did not change obviously.
The process conditions investigated above took 60 h, and no
remarkable decrease in the permeation flux and separation fac-
tor were found. The undesirable peeling of active layer was not
observed after the composite membrane was taken out from the
membrane chamber. These results indicated that the sufficient
interfacial interaction between PVA active layer and PES support
layer was ensured by interfacial reaction technique, which sig-
nificantly enhanced the comprehensive stability of the composite
membranes.
4. Conclusions
The PVA/PES composite membranes using PVA as active layer
and PES as support layer were successfully fabricated by interfa-
cial reaction technique. The treatment of the support layer using
the interfacial crosslinking agent borax enhanced the spreading of
hydrophilic PVA on the PES support layer and strengthened the
interface interaction between PVA active layer and PES support
layers. The optimal recipe for PVA/PES composite membrane was
that PES support layer was treated with 0.1 wt.% borax aqueous
solution, fully dried and then immersed into 2 wt.% PVA aque-
ous solution. The resulting surface crosslinked PVA/PES composite
membrane showed a highest separation factor of 427 with a perme-
ation flux of 438 g m−2 h−1 for 80 wt.% EG in the feed at 70 ◦ C. The
long-term investigation of process conditions showed that the com-
posite membranes displayed the desirable operating and structural
stability.
38 R. Guo et al. / Journal of Membrane Science 322 (2008) 32–38
Acknowledgements
The authors are grateful for the financial support from the Cross-
Century Talent Raising Program of Ministry of Education of China,
the Program for Changjiang Scholars and Innovative Research Team
in University from the Ministry of Education of China, the Pro-
grammer of Introducing Talents of Discipline to Universities (No.
B06006) and Petrochina Research Program (No. W050509-02-02).
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