Journal of Membrane Science 534 (2017) 83–91

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Journal of Membrane Science

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High-flux thin-film composite polyelectrolyte hydrogel membranes for MARK

ethanol dehydration by pervaporation
⁎
Jinpeng Liu, Roy Bernstein
Department of Desalination and Water Treatment, Zuckerberg Institute for Water Research, Jacob Blaustein Institutes for Desert Research, Ben-Gurion University of the
Negev, Sede Boqer Campus, 8499000, Israel

A B S T R A C T

A thin-film composite (TFC) membrane for ethanol dehydration by pervaporation with a very high flux and a
moderately high separation factor was fabricated using a strong polyelectrolyte hydrogel as an active layer. The
thin-film hydrogel was graft-polymerized with vinyl sulfonic acid (VSA) as the polymer monomer and N, N′-
methylenbisacrylamide (MBAA) as the cross-linker monomer, employing the UV photo-initiation method on a
polyethersulfone ultrafiltration support. The successful grafting was confirmed by ATR-FTIR, and AFM and SEM
studies showed that TFC membranes with an active layer of 100–300 nm were fabricated. The IEC of the active
layer increased up to ca. 3 meq/g when the cross-linker fraction was changed from 1% to 5% MBAA and then
decreased at 10% MBAA, probably due to the high cross-linker fraction in the active layer. The degree of
swelling decreased with the cross-linker concentration and with the duration of the UV irradiation.
The pervaporation performance of the TFC membranes was studied with a 90% ethanol solution at 50 °C. The
separation factor coincided with the increase in the IEC, which is attributed to the higher sorption of water
molecules to the active layer. The degree of swelling had a lesser influence on the membrane performance than
the IEC, but greater swelling decreased the performance for similar IEC values. The optimal membrane with a
7.5 kg m−2 h−1 flux and a separation factor of 313 was obtained at the highest IEC and a limited degree of
swelling, making it one of the membranes with the highest pervaporation separation index reported to date.
However, the stability of the membrane should be improved, as its high performance decreased after 24–48 h
and reached a plateau after a few days of operation.

1. Introduction [10–13], mixed-matrix membranes with graphene oxide [14], carbon

Pervaporation is one of the most effective techniques for separating
miscible liquids due to its low cost and the ability to separate azeotropic
mixtures and liquids with close boiling points [1]. In addition, it is
environmentally friendly and does not discharge hazardous chemicals
or generate heat [2]. The three main applications of pervaporation are
solvent dehydration, organic–organic solvent separation, and removal
of solvents (e.g., volatile organic carbon) from aqueous solutions; of
these, solvent dehydration is the most developed application, and it is
being employed today on an industrial scale [3].
Pervaporation was commercialized for the dehydration of organic
solvents in 1983. This was accomplished with a composite membrane
with polyvinyl alcohol as the active layer [4]. Since then, numerous
attempts have been made to improve the efficiency of the process and
many other polymer-based membranes have been investigated [4],
including membranes made of modified poly(vinyl alcohol) [5,6],
polyimides [7], polyamides [8], polysaccharides [9], polyelectrolytes
nanotube [6,15], zeolites [16], metal organic frameworks [17], and
inorganic–organic hybrid membranes [18]. Nevertheless, improving
the performance of the membrane, namely, its separation factor and
permeability, is still a major challenge [3].
The accepted mechanism underlying the transport in pervaporation
is solution-diffusing- evaporation [4]. Therefore, an adequate mem-
brane performance for dehydration requires (a) a high solution of water
to the active layer; (b) preferable diffusion of the water molecules –
relative to the molecules of the organic solvent – through the membrane
to the permeate side through the fractional free volume (FFV) of the
swollen active layer, although the swelling should be restricted to
prevent high permeation of the organic solvent; and (c) a thin active
layer, which will allow high permeability [1,4].
One type of material that can be used for fabricating such thin-film
membranes and combine high water sorption and limited swelling is
polyelectrolytes. As polyelectrolytes have dissociated (negatively or
positively) charged groups on the polymer backbone, their water

⁎
Corresponding author.

http://dx.doi.org/10.1016/j.memsci.2017.04.018
Received 17 February 2017; Received in revised form 17 March 2017; Accepted 11 April 2017
Available online 13 April 2017
0376-7388/ © 2017 Elsevier B.V. All rights reserved.
J. Liu, R. Bernstein
sorption is relatively high [11,19]. Although polyelectrolytes usually
swell to a high degree in water solutions, which could reduce the
membrane performance [20], such swelling can be controlled by
fabricating a cross-linked polyelectrolyte, multilayer polyelectrolyte
membranes, or complex polyelectrolyte membranes. Several methods
can be used for this process, including chemical crosslinking by adding
a monomeric cross-linker, physical crosslinking through a thermal
treatment, ionic crosslinking, layer-by-layer deposition, and more
[14,21–23]. Finally, polyelectrolytes can be produced as very thin
layers to increase membrane permeability [24].
As mentioned above, the preferential solution of water over ethanol
to a polyelectrolyte active layer is due to the charge moiety of the
polyelectrolyte (also known as the active center); thus, an increase in
the ion-charge density can increase the membrane separation factor.
Furthermore, it was found that both the chemical nature of the charged
group and the counter ion influence the water sorption [1]. For
example, the use of strong sulfonate groups as an effective active
center has attracted much attention due to the high hydrophilicity and
hydration capabilities of these groups [11,25–27].
Composite membranes with various polyelectrolytes as the active
layer, which were either grafted or coated, have been investigated for
solvent dehydration by pervaporation [1]. However, the separation
factor of these membranes was usually insufficient, and most polyelec-
trolytes were not cross-linked. In the current study, a cross-linked
polyvinyl sulfonic acid (pVSA) was used as the thin-film active layer of
a composite membrane, which was assessed for dehydration of ethanol
by pervaporation. pVSA has a very high ion exchange capacity and is a
highly hydrophilic polyelectrolyte, and the cross-linking was used to
limit its swelling. The polymer was grafted onto a polyethersulfone
(PES) ultrafiltration (UF) membrane by UV–photo-irradiation and the
degree of grafting, ion exchange capacity (IEC), degree of swelling, and
morphological characteristics of the composite membrane were mea-
sured. The performance of the composite membrane in dehydrating a
90% ethanol solution was then evaluated and correlated with the
membrane characteristics.
2. Experimental
2.1. Materials
Commercial UF PES membranes (150 kDa, as reported by the
manufacturer) were supplied by Microdyn-Nadir (Wiesbaden,
Germany). Prior to the modification, the membranes were washed in
a 50% ethanol/water solution for at least 12 h, then thoroughly washed
again with Milli-Q water (Millipore, USA) and left in double distilled
water (DDW) until used. Vinyl sulfonic acid sodium salt (VSA; 25%,
Tokyo Chemical Industry Co., Ltd) was used as the polymer monomer
and N,N′-methylenbisacrylamide (MBAA, Sigma-Aldrich, Israel) was
used as the cross-linker monomer. To obtain a monomer solution with
42% VSA, the 25% VSA solution was concentrated under reduced
pressure (42 mbar) at 50 °C. The monomer concentration was 42%
when the solution density was 1.37 g/L. Ethanol was purchased from
Bio-Lab Ltd. (Jerusalem, Israel). All reagents were of analytical grade
and were used as received. All experiments were conducted using
purified water from a Milli-Q system.
2.2. Modification procedure
The modification solution was prepared by dissolving the cross-
linker (0–10% mole, relative to the VSA concentrations) in the aqueous
VSA solution. For the 5% and 10% fractions, a high concentration of
MBAA was dissolved in 50% ethanol and then a small volume was
added to the VSA solution.
A water-wet membrane (9×4 cm) was placed in a holder, leaving
only the outer surface of the membrane in contact with the solution.
The water was wiped off with a tissue paper and the surface of the
84
Journal of Membrane Science 534 (2017) 83–91
membrane was covered with 12 mL of the modification solution (which
was first degassed with nitrogen for 1 min). The sample was immedi-
ately placed inside a UV system (Intelli-Ray 400, Uvitron International
Inc., USA) and irradiated at an intensity of I =65 mW/cm2 (measured
with a UV power puck II radiometer, EIT, Sterling, VA), for various
durations (2.5–15 min) at 30–35 °C. The UV wavelength was narrowed
to λ > 315 nm by using a filter glass to avoid membrane degradation
[28]. At the end of the modification process, the membrane was washed
with a 50% ethanol/water solution for at least 12 h at 45 °C to remove
any ungrafted polymers, and it was left in DDW until tested.
2.3. Degree of grafting
The degree of grafting (DG) was calculated using the gravimetric
method. Pristine and modified membranes were cut with a punch-hole
(24 mm diameter), dried for 24 h at 40 °C in a vacuum oven, and left in
a desiccator for 1 h before weighing. For each condition, the weight of
six different samples was measured with a microbalance (XP6, Mettler
Toledo). The DG was calculated by using the following equation:
mmodified − mPES
DG =
A (1)
where mmodified is the weight of the modified membrane, mPES is the
weight of the membrane before modification, and A is the surface area
of the membrane.
2.4. Membrane characterization
2.4.1. Ion-Exchange Capacity (IEC)
Modified membranes with known DG values and pristine mem-
branes were submerged in a 1 M H2SO4 solution for 24 h, during which
time the solution was replaced twice to ensure complete conversion of
the sulfonic group to its acid form. The membranes were then washed
with Milli-Q water until a neutral pH was obtained, and, afterwards,
immersed for 24 h in 10 mL of a 2 M NaCl solution to convert the
sulfonic acid to its Na+ form. The solution was replaced five times, such
that a total of 50 mL of solution was collected. The solution was then
titrated with 0.001 N NaOH by using a T90 titrator (Mettler Toledo).
The IEC [meq g−1] was calculated by using:
(V−V0)*C
IEC =
w (2)
where V [mL] is the volume of NaOH required for the back-titration, V0
[mL] is the average volume required for the titration of five PES control
samples, C [M] is the NaOH concentration, and w (g) is the weight of
the modification layer, measured as the difference between the weight
of the modified and pristine PES membranes following the DG experi-
ments.
2.4.2. Degree of swelling
The membranes were dried for 24 h at 40 °C in a vacuum oven to
remove any absorbed moisture, weighted (Wdry), and then immersed in
Milli-Q water for 48 h at 30 °C. The fully swollen membranes were
carefully wiped with tissue paper to remove the excess solution and
immediately weighted (Wwet). The degree of swelling was calculated as:
Wwet − Wdry
Swelling degree(%) = *100
Wdry (3)
2.4.3. Scanning electron microscopy (SEM)
The cross-sectional images of the membranes were observed with a
field-emission scanning electron microscope (FESEM). Prior to photo-
graphing, all samples were fractured in liquid nitrogen and then
sputtered with gold. To better differentiate the newly grafted active
layers from the pristine membranes, the membranes were stained with
Ag nanoparticles by soaking them in a 100 mM AgNO3 solution for 24 h
J. Liu, R. Bernstein
to exchange Na+ to Ag+, washing them with a diluted (10:1 and then
100:1) AgNO3:Milli-Q water solution, then with Milli-Q water to
remove the residual Ag+, and, finally, soaking them in a 10 mM
NaBH4 solution in an ice bath for 10 min to convert Ag+ to Ag
nanoparticles [29]. The silver element distribution in the cross section
of the composite membrane was recorded by energy-dispersive X-ray
spectroscopy (EDX) equipped on the FESEM.
2.4.4. Atomic force microscopy (AFM)
The thickness of the dry active layer was also evaluated by using
AFM. First, the PES UF membranes were cast by using the non-solvent
phase inversion method. PES (15% w/w, Ultrason E3010P, kindly
provided by BASF) was dissolved in N-Methyl-2-pyrrolidone (NMP) and
cast on a polypropylene non-woven surface by using an automatic
casting device (Braive Instruments, Belgium) at a 200 µm wet thickness.
The polymer film was then immersed in deionized water at 20 °C and
kept in the water until used. The membranes were modified as
described in Section 2.2. The polypropylene support of both a pristine
and a modified membrane was then removed (the non-woven support
could not be separated from the commercial membranes, hence the in-
house membrane casting) and PES-grafted layer films were soaked with
NMP in a glass Petri dish until the PES completely dissolved, leaving
only the grafted layer floating in the NMP. The floating hydrogel layer
was carefully mounted on a clean silicon wafer and the solvent was
evaporated to leave a dry hydrogel film on the wafer. Finally, the
sample was left for 12 h at 60 °C and 100% humidity to allow the film to
swell and expand, and the dry film thickness was measured by AFM
using MFP-3D-Bio (Asylum Research, Oxford Instruments) with a
AC160TS probe (Olympus) in AC mode.
2.5. Pervaporation experiments
The ability of the membranes to separate water from ethanol was
characterized by using 90:10 (g/g) ethanol/water mixtures. The
pervaporation measurements were performed using a lab-made appa-
ratus, shown in Fig. 1. The membrane cell dimensions were
8×3×0.5 cm (L×W×H), with 24 cm2 as the membrane effective area.
The feed was circulated at 80 L/h and the temperature was controlled
by an electronic control thermometer. The vacuum at the downstream
pressure was maintained using a vacuum pump (Edwards E2M5). First,
the system was operated for a duration of 1 h for equilibration. Then,
the liquid was collected twice, using a liquid nitrogen trap, for
approximately 2 h each time (a total of 5 h for each sample); the
difference between the two successive measurements was always lower
than 5%. The total permeate flux was determined by measuring the
Fig. 1. Experimental apparatus for pervaporation.
85
Journal of Membrane Science 534 (2017) 83–91
weight of the collected liquid membrane, and the permeate composition
of the collected permeate was determined by the refractive index (ATR-
W2, Schmidt+Haensch, Germany).
The permeation flux (J), separation factor (α) [30,31], and perva-
poration separation index (PSI) [32] were calculated by using the
following equations:
Q
J=
At (4)
PW /PE
α=
FW/FE (5)
PSI = J (α −1) (6)
where Q (kg) is the weight of permeate in the operation duration t (h),
A (m2) is the effective membrane area, and P and F represent the mass
fractions of water (W) and ethanol (E) in the permeate solution and feed
solution, respectively.
3. Results and discussion
3.1. FTIR
The ATR-FTIR spectra of the pristine and modified membranes with
25 wt% VSA as the monomer and with different MBAA fractions as the
cross-linker (% mole, relative to the VSA concentrations) are shown in
Fig. 2. A new peak emerged for the modified membranes at 1040 cm−1,
corresponding to the stretching vibration of the sulfone acid group and
confirms the successful grafting of the pVSA [33]. As expected, the
intensity of the sulfonic peak increased with increasing cross-linker
concentration [33]. The other two new peaks shown in Fig. 2 are the
absorption peak of the amide I (C˭O) and the amide II (N-H), at
1662 cm−1 and at 1543 cm−1, respectively, which indicate that the
cross-linker fraction in the grafting (active) layer increases with
increasing MBAA fraction in the monomer solution.
3.2. Degree of grafting
The DG was evaluated at various cross linker–monomer ratios
(Fig. 3a) and for different durations of irradiation (Fig. 3b) by using
either 25% or 42% VSA, at otherwise constant polymerization condi-
tions. We investigated a similar system in previous studies [33,34], but
the cross linker fraction in the current study was much higher (up to
10% MBAA) than that used in our previous work (up to 2.5% MBAA).
Without a cross-linker, no grafting was detected under any of the
examined conditions. However, a monotonic increase in DG was
Absorbance
1800 1600 1400 1200 1000 800
Wave number (cm-1)
Fig. 2. ATR-FTIR spectrum of the pristine and modified membranes prepared with
various cross-linker concentrations. Grafting polymerization conditions were 25% VSA,
t=7.5 min, I =65 mW/cm2.
J. Liu, R. Bernstein Journal of Membrane Science 534 (2017) 83–91

500 800
(a) (b)
400
600

DG (µg/cm2)

DG (µg/cm2)
300
400
200

200
100
25%VSA 5%MBAA
42%VSA 10%MBAA
0 0
0.0 2.5 5.0 7.5 10.0 12.5 0 5 10 15 20
MBAA concentration (mole%) Irradiation time (min)
Fig. 3. (a) Degree of grafting (DG) at different cross-linker fractions (mole %) with 25% and 42% VSA, t=7.5 min (b) Effect of the UV irradiation duration on the DG at two cross-linker
fractions (5% and 10% MBAA) with 25% VSA. Grafting polymerization conditions were I =65 mW/cm2. n ≥5.

observed when the cross linker fraction was increased up to the
maximum concentration of 10 mol% (Fig. 3a), which was the maximum
solubility of the cross-linker in the ethanol–VSA solution (without a
significant change in the VSA concentration). The DG was higher when
42% VSA was used than when 25% VSA was used at the same cross-
linker concentration. Only two cross-linker-to-monomer ratios were
studied due to the low solubility of the cross-linker in the 42% VSA.
The DG also increased almost linearly with irradiation time for the
two cross-linker fractions (Fig. 3b). The increase in the DG with the
cross-linker fraction and with irradiation time was also reported in our
previous studies [33,34] and by others [35]. Although the cross-linker
fraction in the current study was much higher than the one used in our
previous studies, the general trends of the DG are similar.
3.3. Ion Exchange Capacity (IEC) and degree of swelling
The effect of the different graft polymerization conditions on the IEC
– a key parameter in the pervaporation-mediated dehydration – is
shown in Fig. 4. Fig. 4a shows that the IEC values (for 25% VSA)
reached a maximum of 2.99 at 5% MBAA and dropped to 1.66 at 10%
MBAA. This finding can be attributed to the adverse effect of the cross-
linker fraction in the monomer solution on the ratio between the VSA
(and, thus, the IEC) and the cross-linker fraction in the grafted layer. In
our previous work, we showed that an increase in the cross-linker
fraction in the monomer solution increases the VSA grafting [33,34].
This phenomenon was attributed to the low reactivity of the VSA as
compared with the cross-linker monomer during the co-polymerization,
as was reported by others [36,37]. However, the cross-linker fraction in
the grafted layer also increases. It seems that, at high cross-linker
fractions (10% for 25% VSA and 2.5% for 42% VSA), the increase in the
cross-linker fraction in the grafting layer exceeds the increased grafting
of the VSA.
This phenomenon was also observed in the change of the IEC with
the duration of irradiation for the 5% cross-linker fractions (Fig. 4b).
The IEC reaches its maximum value at 7.5 min for both cross-linker
fractions and drops at longer irradiation durations. Fig. 4b also shows
that the IEC values were lower at all durations of irradiation for the
10% cross-linker fraction than for the 5% cross-linker fraction, indicat-
ing that the cross-linker fraction in the grafted layer is higher for the
10% MBAA fraction. Furthermore, the change in the IEC with increas-
ing durations of irradiation was very small when the 10% cross-linker
fraction was used (except a small increase from 5 to 10 min), implying
that the 10% MBAA fraction is probably too high for an effective
pervaporation separation. Notably, although the IEC values are lower
than the theoretical value of pVSA (9.2 meq/g) in all conditions, and
due to the high crosslinking fraction in the active layer [34,38], the IEC
values are much higher than those of composite membranes that were
fabricated by using other polyelectrolytes as the active layer [39–42].
The degree of swelling of the active layer under various polymer-
ization conditions is presented in Fig. 5. The degree of swelling
decreased with increasing MBAA fraction (Fig. 5a) and duration of
irradiation (Fig. 5b). A decrease in swelling with increasing cross-linker
fractions due to an increase in the mechanical strength of the matrix is a
well-known phenomenon [43]. However, the decrease in swelling with
increasing irradiation duration was somewhat unexpected and can be
explained based on the swelling of a thin-film hydrogel tethered to a
surface. The swelling of a thin film is one-dimensional normal to the
substrate plane [44]; as the duration of irradiation increases, the film
becomes thicker (Fig. 3b), while the volumetric expansion increases to
a lesser extent because it is one-dimensional. Therefore, the ratio

4.0 4.0

3.5 (a) 3.5 (b)

3.0 3.0
IEC (mequiv g-1)

IEC (mequiv g-1)

2.5 2.5

2.0 2.0

1.5 1.5

1.0 1.0
25%VSA 5%MBAA
0.5 0.5
42%VSA 10%MBAA
0.0 0.0
0.0 2.5 5.0 7.5 10.0 12.5 0 5 10 15 20
MBAA concentration (mole%) Irradiation time (min)
Fig. 4. (a) Ion exchange capacity (IEC) of modified membranes prepared at different cross-linker fractions (mole %) with 25% and 42% VSA, t=7.5 min (b) Effect of the irradiation
duration on IEC values at two cross-linker fractions (5% and 10% MBAA) with 25% VSA. Grafting polymerization conditions were I =65 mW/cm2, n ≥5.

86
J. Liu, R. Bernstein
60
(a) 25%VSA
42%VSA
Swelling degree (g/g)
40
20
0 0
0.0 2.5 5.0 7.5 10.0
MBAA concentration (mole%)
Fig. 5. (a) Degree of swelling of modified membranes prepared at different cross-linker fractions (mole %) with 25% and 42% VSA, t=7.5 min (b) Effect of the duration of irradiation on
the degree of swelling at 5% MBAA. Grafting polymerization conditions were 25% VSA, I =65 mW/cm2, n ≥5.
between the dry and swollen volumes, i.e., the degree of swelling,
decreases with increasing irradiation duration.
3.4. Thickness of the active layer
In previous research, we demonstrated that, following the functio-
nalization of a PES membrane with 25% VSA and at a high cross-linker
fraction (2.5% MBAA), the surface of the membrane is covered
completely and a composite membrane is fabricated [33,34]. In the
current study, the cross-section morphology of the composite polyelec-
trolyte membrane was characterized by FESEM to evaluate the thick-
ness of its active layer, which has a considerable influence on
membrane performance [45]. The images in Fig. 6a-d demonstrate that
the thickness of the active layer of the membrane slightly increases with
the increase in cross-linker fraction, namely, from ca. 90 nm in the
pristine membrane (Fig. 6a) up to 208 nm (i.e., ca. 118 nm grafted
layer) for the 10% MBAA membrane (Fig. 6d).
Because it is very difficult to distinguish between the grafted
hydrogel (the active layer) on top of the supporting PES membrane in
the SEM images, both a pristine membrane and a modified membrane
(25% VSA, 5% MBAA, 7.5 min irradiation) were stained with Ag and
were then detected by using EDX measurements, which were taken
from the active layer and from the middle of the cross section. Figure
SI1 (Supporting Information) shows the exact positions on the pristine
and modified membranes that were measured with EDX. Table SI1
(Supporting Information) demonstrates that Ag could be detected only
at the active layer of the modified membrane, where the Ag+ ions were
successfully exchanged with the grafted sulfone groups, while no
measurable Ag was found at the other points, including at the ‘active
layer’ of the pristine PES membrane. These findings confirm that the
dense layer is, indeed, the newly grafted layer.
The dry thickness of the hydrogel layer with 5% MBAA (25% VSA,
7.5 min irradiation) was also measured by AFM. The complete dissolu-
tion of the PES membrane and the presence of the isolated pVSA
hydrogel layer on the silicone surface were confirmed by measuring the
FTIR spectra, using the reflection mode (FT-IR Microscope Bruker
HYPERION 1000); no peaks of the PES membrane were observed (data
not shown). The bright areas in the image of the height profile of the
isolated film (Fig. 7) represent the highest points of the hydrogel layer,
while the dark regions indicate the surface of the silicon wafer.
As shown in Fig. 7, the average thickness of the membrane that was
fabricated by using 5% MBAA is approximately 270 nm. This thickness
is somewhat higher than the thickness measured by using SEM (ca.
90 nm), which may indicate some intrusion of the hydrogel to the
membrane pores. Nevertheless, the active layer can still be considered a
thin-film hydrogel.
Journal of Membrane Science 534 (2017) 83–91
25
(b)
20
Swelling degree (g/g)
15
10
5%MBAA
12.5 0 5 10 15 20
Irradiation time (min)
3.5. Pervaporation performance
3.5.1. Effect of cross-linker concentration and irradiation duration
The effect of the cross linker-to-monomer ratio for 25% VSA
(7.5 min irradiation) and of the irradiation duration (for 25% VSA
and a 5% cross–linker fraction) on the membrane pervaporation
performance (separation factor and total flux) are presented in
Fig. 8a-b.
Fig. 8a demonstrates that the pervaporation separation factor
increases significantly with increasing cross-linker concentration of up
to a 5% fraction, and then drops; in contrast, the total flux gradually
decreases with increasing cross-linker fraction. A similar trend was
observed for the effect of irradiation duration (Fig. 8b), but with a small
variation: the total permeate flux slightly increased at a long duration of
irradiation (15 min).
The changes in the pervaporation separation factor with increasing
cross-linker concentrations and irradiation durations correlate with the
changes observed in the IEC (compare Fig. 4 and Fig. 8), probably due
to the higher sorption of water molecules to the active layer [46]. The
separation factor increases from 24 to 303 when the IEC increases from
2.27 to 2.99 meq/gr, and then decreases to 94 as the IEC is reduced to
1.66 meq/gr. The increased swelling with increasing cross-linker frac-
tion can also enhance the separation factor due to faster diffusion of the
water molecules to the permeate side. The high swelling also increases
the total flux, but it can lower the separation factor due to the
enlargement of the free volume in the hydrogel, which enables the
penetration of ethanol molecules [16]. Therefore, as seen in Fig. 8a-b,
there is an optimum performance that occurs at the optimal swellin-
g–IEC value corresponding to a high IEC value and a limited degree of
swelling. Furthermore, the changes in the trade-off between the
separation factor and permeability can also result from a thicker active
layer, which is expected to improve membrane separation factor but to
reduce total flux [47].
The separation factor of a composite membrane, fabricated by using
42% VSA and 1% MBAA, was only 114 (and a total flux of 6.1 kg/m2h)
– lower than a membrane with similar IEC values that was fabricated by
using 25% VSA and 5% MBAA (IEC ≈3 meq/gr, Fig. 4a). This is
probably due to the much greater water swelling of the former (Fig. 5a).
3.5.2. Effect of feed temperature
It is well-known that the feed temperature is a key parameter that
influences the permeation of water molecules through the membrane
[11]. The effect of temperature (ranging from 303 K to 333 K) on the
water and ethanol fluxes was studied for the membranes that presented
the optimal performance (25% VSA, 5% MBAA, and 7.5 min irradiation
duration; see Fig. SI3, Supporting information). The trend of permea-
tion flux versus temperature and the apparent activation energy can be
87
J. Liu, R. Bernstein Journal of Membrane Science 534 (2017) 83–91

Fig. 6. Cross-section morphology of polyelectrolyte hydrogel PES membrane, observed by FESEM. The thickness of the active layer (an average of ten different points) is shown for (a)
pristine membrane and (b-d) membranes modified with (b) 2.5% (c) 5%, and (d) 10% cross-linker fractions (mole %). Polymerization conditions were 25% VSA, t=7.5 min, I =65 mW/
cm2.

described by the Arrhenius equation: has a higher temperature sensitivity than ethanol, resulting in an
increase of the separation factor [49,50].
JP = AP * exp(−EP / RT ) (7)

where AP, JP, EP, R, and T represent the pre-exponential factor,
permeation flux (kg/m2h), apparent activation energy (kJ/mol), gas
constant, and feed temperature (K), respectively.
Fig. 9 shows that the ln(Jp) versus 1000/T curve is linear, indicating
that the permeability followed the Arrhenius relation. The calculated
apparent activation energy of water (29.93 KJ/mol) was higher than
that of ethanol (6.31 KJ/mol), which is similar to the other sulfone-
based composite membranes [48], indicating that the water permeation
3.6. Long-term operational stability
To investigate their long-term stability, modified polyelectrolyte
membranes were continuously operated with a 90 wt% ethanol aqu-
eous solution at 323 K for up to 120 h. However, since the flux was very
high, it was impossible to operate the system continuously under
filtration mode. Therefore, the system was operated constantly in a
cross-flow mode (without filtration) and two samples were taken daily,

Fig. 7. AFM images of a VSA film on a silicon surface (grafting conditions were 25% VSA, 5% MBAA, and 7.5 min of UV irradiation).

88
J. Liu, R. Bernstein Journal of Membrane Science 534 (2017) 83–91

Separation factor-25%VSA Permeate-25%VSA Separation factor-5%MBAA Permeate-5%MBAA

400 14 500 16
(a) (b)
12 14

Permeation flux (kg/m 2h)

Permeation flux (kg/m 2h)
400
Separation factor 300 12

Separation factor
10
300 10
8
200 8
6 200 6
4
100 4
100
2 2

0 0 0 0
0.0 2.5 5.0 7.5 10.0 12.5 0 5 10 15 20
MBAA concentration (mole%) Irradiation time (min)
Fig. 8. (a) The effect of cross-linker concentration on membrane pervaporation performance (separation factor and flux). (b) The effect of irradiation duration on membrane
pervaporation performance for 5%. Graft polymerization conditions were t=7.5 min, I =65 mW/cm2, n ≥3.

10 reduction in performance is due to the aging of the hydrogel, as is

Water usually observed when ethanol is removed from aqueous solutions by
9 Ethanol pervaporation using PTMS membranes [51]. Nevertheless, the long-
term stability can be improved by using various approaches, such as
EP,W =29.93kJ/mol
8 adding nanoparticles [52] or coating the membrane with a thin-film of
protective layer [53]; both are currently being explored.
In J P

7
3.7. Comparison of pervaporation performance of various membranes
6 EP,E =6.31kJ/mol
Fig. 11 summarizes the pervaporation performance of various types
5 of polymeric membranes for the dehydration of an ethanol solution, as
reported in the literature (see Table SI2, Supporting information). The
VSA hydrogel composite membrane demonstrates a moderately high
4
2.9 3.0 3.1 3.2 3.3 3.4 separation factor, but has the highest permeation flux of all examined
-1
membranes. Furthermore, as compared with the other polyelectrolyte
1000/T (K ) composite membranes, a very high separation factor was obtained. The
Fig. 9. Arrhenius plots of permeation flux for separating an ethanol/water mixture. pervaporation separation index (Eq. (6)), which enables a comparison
Grafting polymerization conditions were 25% VSA, 5% MBAA, t=7.5 min, I =65 mW/ between the performance of membranes with different separation
cm2. factors and permeability [54], is very high, as compared with other
polymeric membranes [7,10–13,24,39,50,55–64] (Table SI2,
8 100 Supporting information).
Water content in permeate (wt%)

80 4. Conclusions
6
Flux (kg/m2h)

60 A composite membrane with a polyvinyl sulfonic acid hydrogel as

4 the active layer on a PES membrane was successfully fabricated by
using the UV grafting polymerization method. The degree of grafting
40
monotonically increased with increasing cross-linker concentration
2 (1–10%) and the duration of UV irradiation (2.5–15 min). The IEC also
20
Flux increased with increasing cross-linker concentration and the duration of
Water content irradiation until it reached a maximum value, after which it decreased
0 0 with increasing cross-linker concentrations (10% for 25% VSA and
0 24 48 72 96 120 144
2.5% for 42% VSA) and irradiation durations (15 min). This behavior
Operation time (h) was attributed to the increase in the cross-linked fraction in the
Fig. 10. Pervaporation performance stability of a polyelectrolyte hydrogel membrane in hydrogel. The degree of swelling decreased with increasing cross
dehydrating 10 wt% water/ethanol at 50 °C. linker-concentrations (1–10%) and UV irradiation duration
(2.5–15 min). It is speculated that the lower swelling observed in
as described in Section 2.5. As presented in Fig. 10, the separation longer durations of irradiation is due to the one-dimensional swelling of
factor and the permeation flux decreased during the first few days and the tethered hydrogel. It was also found that the composite membrane
stabilized afterward (at a separation factor of approximately 90), has a thin-film hydrogel active layer of approximately 100–300 nm.
indicating that the long-term operation stability should be improved. The separation factor of the composite membrane significantly
The performance reduction was observed within 24–48 h from the increased with increasing IEC values, probably due to the increase in
beginning of the long-term experiments. The reason for the decrease in water sorption. However, high swelling resulted in a lower separation
membrane performance is not completely understood. The ATR-FTIR factor. The extensive swelling was successfully limited by means of
spectra before and after the long-term operation were very similar (data cross-linking. The optimal pervaporation performance for ethanol
not shown), and degradation of the hydrogel would have resulted in an dehydration (separation factor =303; flux =7.6 kg/m2h) was obtained
increase, rather than a decrease, in the permeate flux. Thus, it can be at conditions that combined a high IEC value (2.99 meq/gr) and a
assumed that the hydrogel remains intact. It can be speculated that the limited degree of swelling (5% MBAA, 7.5 min). The very high flux was

89
J. Liu, R. Bernstein
10000
1000
Separation factor
100
10
1
0.01 0.1 1 10
Flux (kg.m-2.h)
Fig. 11. Graphic representation of the performance of polyelectrolyte and composite membranes from the data presented in Table SI2 (Supporting information).
also due to the thin active layer. As expected, the performance of the
membrane further improved by increasing the temperature of the feed
solution (separation factor =410; flux =9.89 kg/m2h), and the change
in the flux with the temperature correlated with an Arrhenius-type
equation.
The membrane presented in this report displays a high separation
factor, as compared with other composite polyelectrolyte-based mem-
branes that were studied for pervaporation, and a very high perme-
ability and PSI factor, as compared with other polymeric membranes
used for pervaporation -mediated ethanol dehydration. The membrane
stability still needs to be improved, as its performance decreased within
24–48 h, after which it reached a plateau. The decrease in performance
with duration might be the result of an ageing effect and an increase in
the ethanol permeation, which reduces the separation factor and
swelling (and, thus, the flux). This caveat can be improved by using
various methods, including the fabrication of a hybrid inorganic-
organic membrane, which often improves the mechanical stability of
polyelectrolytes.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.memsci.2017.04.018.
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