Journal of Membrane Science 523 (2017) 497504

Contents lists available at ScienceDirect

Journal of Membrane Science

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

Thin-lm composite (TFC) hollow ber membrane with double-polyamide

active layers for internal concentration polarization and fouling mitigation
crossmark
in osmotic processes

Gang Han, Zhen Lei Cheng, Tai-Shung Chung
Department of Chemical and Biomolecular Engineering National University of Singapore, Singapore 117585, Singapore

A R T I C L E I N F O A BS T RAC T

Keywords: Internal concentration polarization (ICP) and severe irreversible fouling occurring within the porous and
Antifouling tortuous substrates of the forward osmosis (FO) and pressure retarded osmosis (PRO) membranes have
Double-skin signicantly hidden their applications for water purication and osmotic power generation. This study
TFC FO and PRO membranes experimentally demonstrates that designing a double-skin structure in FO and PRO membranes can eectively
Water reuse
control ICP and their fouling propensity. Thin-lm composite (TFC) hollow ber membranes consist of an inner
Osmotic power
polyamide selective skin and an outer polyamide sealing layer were successfully fabricated by double interfacial
polymerizations on a tailored polyethersulfone (PES) ber substrate (termed as dTFC-PES). Due to the
outstanding rejection of the outer polyamide sealing layer, the penetration of inorganic salts and foulants into
the substrate is suciently blocked. As a result, not only ICP and fouling inside the membrane are eectively
minimized, but also sustainable FO and PRO performances are achieved. By using real wastewater contains
multiple inorganic salts and organic foulants as the feed, the dTFC-PES membrane shows a quite low ux
decline of 29% in FO operations under the PRO mode at an ultrahigh feed recovery of 80%. Under PRO tests for
power generation, the membrane power density slightly drops to 90.8% of the initial value after a 12-h test at
P=15 bar. In addition, since foulants are primarily accumulated on the surface of the polyamide sealing layer,
physically ushing the fouled membrane surface by either freshwater or commercial cleaner Genesol 704 can
eciently restore the water ux back to its initial level with a recovery rate of 87% or 98%, respectively. This
study may oer useful insights and meaningful strategies for the development of eective antifouling FO and
PRO membranes.

1. Introduction
Forward osmosis (FO) and pressure retarded osmosis (PRO) have
gained renewed attention recently for water reuse, wastewater treat-
ment and renewable osmotic power generation [17]. Both processes
utilize the osmotic pressure gradient () between the solutions with
dierent salinities to induce water permeation across a semipermeable
membrane. When the applied hydraulic pressure on the high salinity
solution is lower than the osmotic pressure gradient (P < ) across
the semipermeable membrane, water spontaneously ows from the low
salinity solution to the high salinity one (which is referred to the draw
solution thereafter). The salinity gradient energy can be therefore
harvested when discharging the inow high pressure water via a
turbine or energy recovery device [810]. Most recent PRO researches
focus on the mixing of brine from reverse osmosis (RO) plants and
retentate from municipal wastewater plants because it can generate
much higher osmotic energy than the feed pair of seawater and river
water [1,4,1115]. In addition, it converts two wastes (i.e., RO brine
and wastewater) into useful energy and mitigates their disposal and
environmental issues.
Signicant progresses have been made in the fabrication of high
performance osmotic membranes with more desirable structure and
transport properties recently [1618]. However, their FO and PRO
performances are severely impeded by internal concentration polariza-
tion (ICP) and membrane fouling particularly when using real waste-
water as the feed [1921]. Under the PRO mode, the porous substrate
of the FO and PRO membranes faces the waste stream. As a result, the
inorganic salts and foulants are easily brought deep inside the substrate
by the convective water ow and get stuck underneath the rejection
layer. This would cause severe ICP and fouling and thus reduce water
ux dramatically and rapidly [2224]. Dierent from the fouling on the
surface of the selective layer, sophisticated washing techniques and

Corresponding author.
E-mail address: chencts@nus.edu.sg (T.-S. Chung).

http://dx.doi.org/10.1016/j.memsci.2016.10.022
Received 12 September 2016; Received in revised form 7 October 2016; Accepted 14 October 2016
Available online 18 October 2016
0376-7388/ 2016 Elsevier B.V. All rights reserved.
G. Han et al.
long cleaning durations are required to remove the foulants under-
neath the selective layer because of the substrate tortuosity. Feed
pretreatment can reduce fouling, however it would increase energy and
chemical consumptions as well as operation costs. Manipulation of
membrane structural properties with enhanced antifouling ability is a
promising strategy to mitigate ICP and fouling [3,17,25].
By leveraging the momentum of developing eective antifouling
membranes for FO and PRO applications, one novel thin-lm compo-
site polyethersulfone (dTFC-PES) hollow ber membrane with an
advanced double-selective-skin structure has been successfully devel-
oped in the current study. In fact, the double-skin concept was
pioneered by Wang et al. in order to take advantages of the high ux
nature of FO membranes under the PRO mode and to mitigate the
internal fouling [26]. The original membranes were fabricated by a
phase inversion method and consisted of a dense skin facing the draw
solution and a loose dense skin facing the feed to reject foulants. Zhang
et al. experimentally demonstrated the reduced colloidal fouling
propensity [27], while Tang et al. mathematically conrmed the ICP
mitigation [28]. Since then, several double-skin FO membranes with
variable barrier layers have been developed [2934]. However, all of
these reported double-skin membranes have a dense skin made from
either phase inversion or thin-lm interfacial polymerization method,
but their loose dense skins were from phase inversion, dip coating or
layer-by-layer (LbL) deposition method. As a result, the loose dense
skins normally possess relatively low rejections, particularly to inor-
ganic salts and small foulants. In addition, these membranes were
never tested using real wastewater as the feed, neither were they tested
for osmotic power generation. In contrast, the newly developed dTFC-
PES membrane was prepared from double thin-lm interfacial poly-
merizations on a PES hollow ber substrate. The hollow ber cong-
uration was utilized in this study because of its high surface area per
module and self-mechanical support characteristics [35,36]. It does not
need spacers in module fabrication so that it eliminates the issue of
spacer induced membrane deformation observed for at-sheet PRO
modules under high pressures [37]. The newly developed dTFC-PES
membrane was characterized and tested using real wastewater brine
containing multiple inorganic and organic foulants as the feed. Their
FO performance for water reuse, PRO for power generation, as well as
fouling propensity, reversibility and cleaning were systematically
investigated. The current work may open up new perspectives and
design strategies for the fabrication of eective antifouling membranes
for FO and PRO applications.
2. Materials and methods
2.1. Materials
Radels A polyethersulfone (PES, Solvay Advanced Polymer, L.
[37], GA), N-methyl-2-pyrrolidone (NMP, 99.5%, Merck), polyethylene
glycol with a molecular weight of 400 Da (PEG400, Sigma-Aldrich) and
deionized water were used as the polymer, solvent, and non-solvent
additive for the preparation of the PES hollow ber substrate.
Polyethylene glycol (PEG) and polyethylene oxide (PEO) with dierent
molecular weights from Merck were utilized to characterize the
molecular weight cut-o (MWCO), mean pore size and pore size
distribution of the as-spun PES ber substrate. Ethylene glycol,
diethylene glycol, triethylene glycol, and glucose from Sigma-Aldrich
were employed to measure the mean pore size and pore size distribu-
tion of the polyamide modied PES hollow ber membrane. A 50/50
(wt%) mixture of glycerol (Industrial grade, Aik Moh Pains &
Chemicals Pte. Ltd, Singapore) and water was applied to post treat
the as-spun PES hollow bers. Trimesoyl chloride (TMC) with 98%
purity and m-phenylenediamine (MPD) with > 99% purity ordered
from SigmaAldrich were acquired as the monomers for the interfacial
polymerization reaction. N-hexane from Merck with > 99% purity was
used as the solvent for TMC. Sodium dodecyl sulfate (SDS, > 97%)
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Journal of Membrane Science 523 (2017) 497504
from Fluka was employed as an additive in the MPD aqueous solution.
The commercial membrane cleaner Genesol 704 was provided by
Genesys International Ltd., UK for membrane cleaning. Sodium
chloride (NaCl) from Merck was employed for the preparation of
synthetic draw solutions. Deionized (DI) water with a resistivity of
15 M cm was produced by a Milli-Q unit (Millipore).
2.2. Fabrication of dTFC-PES hollow ber membrane
The PES hollow ber substrate was rstly fabricated via an
optimized dry-jet wet spinning process [38,39]. After that, a polyamide
skin was deposited onto the outer and inner surfaces of the PES ber
via interfacial polymerization between m-phenylenediamine (MPD)
and trimesoyl chloride (TMC), separately. The detailed procedures and
conditions for PES ber spinning, interfacial polymerization and
module fabrication are described in Supporting Information (SI) and
documented in our previous works [36,38,39].
2.3. Membrane characterizations
Membrane morphology was characterized by a eld-emission
scanning electron microscope (FESEM), and the surface chemistry
was obtained by X-ray photoelectron spectroscopy (XPS). Membrane
porosity of the PES ber substrate was measured using a well-
established method descried elsewhere [36,38]. The mean pore size,
pore size distribution and molecular weight cut-o (MWCO) of the
ber substrates were determined by solute rejection experiments as
described in SI [40,41]. Pure water permeability coecient (A) and salt
rejection (R) of the dTFC-PES membrane were measured by testing the
membranes under the reverse osmosis (RO) mode (solutions ow
through the ber lumen side) via a lab-scale ltration apparatus; while
the membrane salt permeability coecient (B) and structural para-
meter (S) were subsequently obtained following the methods described
in SI and elsewhere [39,42]. In order to ensure the experimental
reproducibility, three tests were carried out for each condition and the
averaged value was reported. During each test, one new membrane
coupon was used.
2.4. FO and PRO tests
The FO and PRO performance tests were carried out via a lab-scale
crossow PRO setup reported in our previous work [38,39]. For all the
tests, the draw solution was owed against the inner polyamide
selective layer of the dTFC-PES membrane. The owrate of the draw
solution through the ber lumen side was kept at 2.2 m/s Re=2434
with an adjustable hydraulic pressure of 025 bar. The feed solution
was counter-currently circulated through the shell side of the module at
a owrate of 0.13 m/s. There was no hydraulic pressure dierence
(P=0 bar) across the ber during FO tests; while a hydraulic pressure
of 15 bar (P=15 bar) was applied on the draw solution side in PRO
operations by a high pressure pump.
2.5. Fouling experiments and membrane cleaning
To characterize membrane fouling, wastewater brine (termed as
WWBr) containing multiple inorganic and organic foulants from a local
water recycling plant was employed as the feed [20,21]. An 1 M NaCl
solution was used as the draw solution. The fouling tests were started
with 1 L WWBr feed and stopped when the cumulative permeate
volume or the testing duration reached the predetermined values.
Baseline experiments were also performed under the same operating
conditions but using deionized water as the feed. After the fouling
experiments, the fouled membrane was immediately cleaned by
physical rinse of deionized water along the fouled surface for 6 h to
determine the fouling reversibility. Membrane cleaning was conducted
by ushing the fouled surface with a commercial membrane cleaner
G. Han et al.
Fig. 1. FESEM images of the PES hollow ber substrate: (a) inner surface, (b) outer surface, (c) overall cross-section, and (d) enlarged partial cross-section.
Genesol 704 (1 wt%, pH=11) for 0.5 h. Fouling reversibility and
cleaning eciency were assessed in terms of membrane initial water
ux recovery (i.e., the averaged ux during the rst 10 min) using
deionized water as the feed. The detailed descriptions of the FO/PRO
setup, the WWBr feed, and procedures for the determination of water
ux and power density, and membrane cleaning are disclosed in SI.
Each fouling and cleaning test was carried out three times and the
averaged data were reported. In order to make the gures clearly
visible, the error bar was not included in the reported gures.
3. Results and discussion
3.1. Characterizations of the PES hollow ber substrate
In order to obtain the dTFC-PES membrane with a desirable
morphology and properties, the PES hollow ber substrate was
molecularly tailored via optimizing the dope composition and spinning
conditions. As depicted in Fig. 1, the PES ber substrate shows a highly
centric structure with an outer diameter of 1125 m and a cross-
section thickness of 300 m (Table 1). By employing water as the bore
uid and external coagulant to induce a fast phase inversion, both the
inner and outer surfaces of the PES ber are relatively smooth and
dense without any large surface holes. Table 1 also shows that the PES
ber possesses a small mean pore size of 11.6 nm in diameter with a
relatively narrow pore size distribution as indicated by the small
geometric standard deviation (p=1.9). These surface morphology
Table 1
Membrane mean pore diameter, porosity, molecular weight cut-off (MWCO), PWP and dimension of the PES hollow fiber substrate.
Membrane code Mean pore diameter, dp Geometric standard
(nm) variation, p
PES hollow ber 11.6 1.9
substrate
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Journal of Membrane Science 523 (2017) 497504
and pore feature are critical for the subsequent formation of a thin
and less defective polyamide selective layer on top and bottom of the
PES substrate via interfacial polymerization [38,43,44]. The highly
porous cross-section morphology consists of two layers of nger-like
macrovoids because of instantaneous demixing and non-solvent intru-
sion during phase inversion from both sides. This cross-section
morphology together with the great membrane porosity of about
74.4% (Table 1), not only facilitate the water transports across the
substrate but also help reduce ICP. As a result, the PES ber substrate
has a MWCO of 183.2 kDa and a large PWP of 130 L m2 h1 bar1 as
tabulated in Table 1. However, a relatively thick sublayer with fully
sponge-like macrovoid-free structure is observed underneath the ber
inner surface, which is favorable for the formation of a robust TFC layer
[36,4345].
3.2. Characterizations of the dTFC-PES hollow ber membrane
Fig. 2 shows the surface and cross-section morphologies of the
double-skin dTFC-PES hollow ber membrane. A typical ridge-and-
valley polyamide morphology was observed on both inner and outer
surfaces of the PES ber substrate with an estimated thickness of
around 375 nm and 470 nm, respectively. The inner polyamide layer is
the selective layer while the outer one is utilized as the sealing layer to
mitigate ICP and internal fouling. To understand the pore size and its
distribution of the outer sealing layer, a polyamide layer was purposely
interfacial-polymerized on the outer surface of the PES ber substrate.
Porosity (%) MWCO (kDa) PWP (L m2 OD/ID (m/
h1 bar1) m)
74.4 183.2 130 1125/525
G. Han et al. Journal of Membrane Science 523 (2017) 497504

Fig. 2. FESEM images of the double-skin thin-lm composite polyethersulfone (dTFC-PES) hollow ber membrane: (a) overall cross-section of the membrane, (b) surface of the inner
polyamide selective skin, (c) cross-section of the inner polyamide skin, (d) surface of the outer polyamide antifouling layer, and (d) cross-section of the outer polyamide antifouling layer.

membrane selectivity. The relatively high A and ultralow B values are

crucial to achieve a high water ux in FO and PRO operations. Owing to
the porous nger-like macrovoid structure in the ber cross-section,
the dTFC-PES membrane has a reasonably small structural parameter
S of 996 m even though it possesses a thick cross-section of 300 m.
Most importantly, the membrane shows remarkable mechanical
strength which can withstand a hydraulic pressure of larger than
20 bar. The superior membrane structure, transport characteristics and
mechanical strength make the dTFC-PES as a desirable membrane for
FO and PRO applications.

3.3. Fouling of dTFC-PES membrane in FO and PRO operations

By using the wastewater brine (WWBr) as the feed and 1 M NaCl as

the draw solution, fouling phenomena and propensity of the double-
skin dTFC-PES membrane were investigated under the PRO mode for
Fig. 3. Pore size distribution of the modied PES hollow ber substrate by interfacially
FO processes and osmotic power generation. Deionized water was also
polymerizing a polyamide layer on the outer surface.
used as a feed for benchmarking purpose. Fig. 4(a) shows a comparison
of the normalized water ux, Jw/Jw0, as a function of feed permeate
Fig. 3 displays its pore size distribution. Compared to the original PES
volume (or feed recovery) in FO operations. When using deionized
substrate of 11.6 nm in diameter (Table 1), the modied PES substrate
water as the feed, the water ux slightly drops to 7% of the initial value
has a very small mean pore diameter of around 0.7 nm with a narrow
at a relatively low permeate volume (i.e., less than 150 ml) followed by
pore size distribution. Thus, inorganic salts and foulants in the feed
a mild decay till to the end of the test with a total ux reduction of 18%
may be suciently prevented from entering the substrate with the aid
at the feed recovery of 80% (i.e., permeate volume of 800 ml). This ux
of this outer polyamide layer [2628,33].
decline is mainly attributed to the combined eects of reverse salt ux,
Table 2 summarizes the intrinsic transport properties of the dTFC-
concentration of the feed, and ICP. When WWBr is used as the feed, the
PES membrane in terms of pure water permeability (A), NaCl rejection
newly developed dTFC-PES membrane also displays a slow and mild
(R), and salt permeability coecient (B). Due to the hydrophilic and
ux decline to 8% of the initial value at a relatively low permeate
ultrathin nature of the polyamide layers, a high A of
volume of 150 ml followed by a mild decrease till to the end of the test
1.5 L m2 h1 bar1 was acquired. In addition, the dTFC-PES mem-
with a total ux reduction of 29% at the feed recovery of 80% (i.e.,
brane possesses a great R of 94.2% at a low pressure of 1 bar and an
permeate volume of 800 ml). Even though the normalized ux at 80%
impressively low B of 0.02 L m2 h1, suggesting the outstanding
feed recovery declines from 18 to 29% when replacing deionized water

Table 2
Specifications of the dTFC-PES hollow ber membrane.

Membrane code Water permeability, A Salt permeability, B Rejection to NaCl, Structural parameter, S Burst pressure
(L m2 h1 bar1) (L m2 h1) R (%) (106 m) (bar)

dTFC-PES 1.5 0.2 0.02 94.2 2.5 996 > 20

Deionized water and 1000 ppm NaCl solution were used as the feed to measure water permeability A and salt rejection R of the dTFC-PES membrane at 1 bar, respectively.

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G. Han et al. Journal of Membrane Science 523 (2017) 497504

Fig. 4. (a) Normalized water ux, Jw/Jw0, of the dTFC-PES hollow ber membrane as a function of permeate volume in FO under the PRO mode. (The initial water ux Jw0 was the
averaged ux within the rst 10 min. The initial volume of the feed solution was 1 L); (b) variations of membrane power density, W, as a function of operation time at P=15 bar.

Fig. 5. Outer surface and cross-section morphology of (ad) fouled and (eh) cleaned dTFC-PES hollow ber membranes. Membrane cleaning was performed by ushing the fouled
outer surface with freshwater for 6 h.

Fig. 4(b) shows the power density (W) of the dTFC-PES membrane
as a function of operation time within a 12-h PRO test at P=15 bar
using 1 M NaCl as the draw solution. Both deionized water and WWBr
are used as the feeds. The initial power density (W) is 10.7 W/m2 when
deionized water is employed as the feed. W shows negligible decrease
with time because of the great membrane selectivity and reduced ICP
by the double-skin structure. When changing the feed to WWBr, the
initial W slightly drops to 9.8 W/m2 because of the increased feed
salinity (i.e., WWBr has a small salinity, thus the osmotic driving force
across the membrane is reduced). Interestingly, the decline of power
density with time is very mild where W slightly drops to 8.9 W/m2
during a 12-h test. This corresponds to a small power density reduction
of 9.2%. Clearly, ICP and fouling caused by the WWBr feed in FO and
PRO can be eectively mitigated by the newly designed double-skin
dTFC-PES hollow ber membrane. Thus, sustainable FO and PRO
operations could be achievable.

3.4. Antifouling mechanisms of the dTFC-PES membrane

Fig. 6. Outer surface XPS spectra of the pristine and fouled dTFC-PES membranes.
After the fouling tests, the outer surface of the fouled dTFC-PES
membrane was characterized. As displayed in Fig. S1, a dark brown
by WWBr as the feed, this antifouling performance against WWBr
fouling layer is clearly observed on the membrane outer surface,
surpasses almost all TFC FO membranes reported in the open
suggesting that fouling induced by the WWBr feed is quite signicant.
literatures [35,17,30,32].
The FESEM images illustrated in Fig. 5(a) further show that the outer

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Fig. 7. Schematic of fouling phenomena: (a) the conventional TFC membrane and (b) the newly developed double-skin TFC membrane in FO (under the PRO mode) and PRO processes.

Fig. 8. (a) Normalized initial water uxes of the fouled and cleaned dTFC-PES membranes and (b) outer surface XPS spectra of the fouled and cleaned membranes. The membranes
were cleaned by ushing with freshwater for 6 h or commercial membrane cleaner Genesol 704 (pH=11.0) for 0.5 h on the fouled surface. Jw,DI and Jw0,DI were obtained under the
PRO mode at P=0 bar using deionized water as the feed.

surface is fully covered by a dense fouling lm with a large thickness.
Since the pristine outer polyamide layer has a thickness of 470 nm
(Fig. 2), the estimated thickness of the attached fouling layer is around
3530 nm. Fig. 6 compares the XPS data between the pristine and
fouled membrane surfaces. The signals of Na, Cl, Ca, P and Si elements
on the fouled membrane surface are quite signicant, which suggest the
existence of both inorganic fouling and silica scaling. However, Fig. S2
shows that the membrane inner surface morphology has negligible
changes before and after fouling tests. These indicate that the outer
polyamide sealing layer can eectively reject the salts and foulants and
prevent them from entering the substrate layer, making the fouling
mainly occur on the membrane surface.
Fig. 7 elucidates the fouling mechanisms of conventional TFC FO
membranes and the newly developed double-skin dTFC-PES mem-
brane. Due to the outstanding rejection of the polyamide skin facing
the draw solution and the transmembrane water permeation from the
feed side, insignicant fouling is observed on the draw solution side
[46,47]. However, the inorganic salts and foulants of WWBr feed can
easily penetrate into the porous and tortuous substrate and accumulate
there because of the water permeation across the membrane
[20,21,46]. It not only results in severe pore blockage, ICP, irreversible
fouling, and thus dramatic ux and power density drops [20,21,48
50], but also brings about diculties to clean up the membrane. By
introducing a sealing layer with outstanding selectivity on the back side
of the TFC membrane, one can easily block the entry of inorganic salts
and foulants, as illustrated in Fig. 7(b). As a result, fouling primarily
takes place on the polyamide surface. Although external concentration
polarization (ECP) might be enhanced, its eects on FO and PRO
performance are much lower than those induced by ICP and fouling
within the substrate. In addition, as the fouling occurs on membrane
surface, the shear force of physical rinsing can eectively ush o the
deposited foulants and satisfactorily recover the membrane ux.
3.5. Fouling reversibility and membrane cleaning
After the fouling tests, fouling reversibility of the dTFC-PES

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G. Han et al.
Fig. 9. Normalized water ux, Jw/Jw0, of the dTFC-PES hollow ber membrane as a
function of permeate volume in FO under the PRO mode using WWBr as the feed. After
the rst test cycle, the membrane was cleaned by ushing with commercial membrane
cleaner Genesol 704 (pH=11.0) on the fouled surface for 0.5 h. (The initial water ux
Jw0 was the averaged ux within the rst 10 min. The initial volume of the feed solution
was 1 L).
membrane was evaluated by immediately rinsing the fouled membrane
surface with deionized water for 6 h. The initial water uxes, Jw, DI, of
the fouled and rinsed dTFC-PES membranes were measured using
deionized water as the feed and then normalized by the initial ux,
Jw0, DI, of a fresh membrane. As shown in Fig. 8(a), Jw, DI of the
fouled membrane drops to 60% of Jw0, DI after the fouling test in FO
at a high feed recovery of 80%. Compared to the conventional TFC
membranes reported in the literatures [37], the dTFC-PES membrane
exhibits a much lower ux decline under the same conditions, indicting
its good antifouling properties. Physically rinsing the fouled surface by
deionized water can considerately clean the membrane and restore the
water ux back to 87% of the original ux, suggesting the great fouling
reversibility of the double-skin membrane. Fig. S1 shows that the color
of the dTFC-PES bers is restored back to its original gray color after
water rinse. Similarly, Fig. 5 indicates that the thickness of the fouling
layer is signicantly reduced from 3530 nm to 230 nm after water
rinsing. The XPS spectra displayed in Fig. 8(b) further conrm that the
inorganic salts are removed from the outer surface by water rinse.
Clearly, the shear force of physical water rinsing can readily remove the
foulants.
However, compared to the pristine dTFC-PES membrane (Fig. 2), a
certain amount of foulants is still found on the polyamide sealing layer
(Fig. 5). This might be due to the relatively rough surface of the
polyamide skin and the negatively charged carboxylate groups which
may enhance the foulant-surface interactions. In order to further
improve the cleaning eciency and recover the membrane ux,
chemical cleaning was also applied to regenerate the fouled membrane
[46,47]. As shown in Fig. 8, ushing the fouled surface with a
commercial membrane cleaner, Genesol 704 (1 wt%, pH=11), exhibits
outstanding eectiveness in removing foulants. The water ux is
restored back to its initial level (i.e., the ux recovery reaches 98%).
The intermittent cycle tests presented in Fig. 9 also conrm the
outstanding fouling reversibility and great eectiveness of chemical
cleaning. These demonstrate that the double-skin structure of the
newly developed dTFC-PES membrane not only can eectively mitigate
fouling in FO and PRO but also make the fouling reversible and easy to
be cleaned.
4. Conclusions
By creating a polyamide sealing layer on the back side of the
substrate, one eective approach has been demonstrated to mitigate
ICP and fouling within the porous substrate layer of asymmetric FO
and PRO membranes. The newly developed double-skin TFC poly-
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Journal of Membrane Science 523 (2017) 497504
ethersulfone hollow ber membrane (dTFC-PES) possesses an inner
polyamide selective skin and an outer polyamide sealing layer with a
mean pore size of 0.7 nm in diameter. Due to the outstanding rejection
of the polyamide sealing layer, the entry of inorganic salts and foulants
into the substrate could be eectively blocked, making the fouling
primarily happens on the membrane surface. By using real wastewater
brine (WWBr) as the feed, superior antifouling performance has been
demonstrated by the dTFC-PES membrane. The membrane water ux
slightly drops to 71% of the initial value at a high feed recovery of 80%
in FO under the PRO mode. In PRO, the membrane also shows a quite
stable performance where the power density only decreases to 90.8% of
the initial value after a 12-h test at P=15 bar. Since the fouling
primarily happens upon the surface of the outer polyamide layer
instead of within the porous and tortuous substrate, the fouling layer
shows great reversibility. Flushing the fouled surface by deionized
water and commercial cleaner Genesol 704 can eectively restore the
membrane ux to its initial level with a high ux recovery of 87% and
98%, respectively. To the best of our knowledge, the achieved antifoul-
ing performances of the dTFC-PES are superior to other membranes
reported in the literature. In summary, the current study demonstrates
the advantages of a double-skin membrane structure made from
double interfacial polymerizations to inhibit ICP and fouling in FO
and PRO applications.
Acknowledgments
This research grant is supported by the Singapore National
Research Foundation under its Environment & Water Research
Programme and administered by PUB, Singapore's national water
agency, under the project titled Membrane development for osmotic
power generation, part 1. Materials development and membrane
fabrication (1102-IRIS-11-01) and the NUS Grant no. of R-279-
000-381-279; and Membrane Development for Osmotic Power
Generation, Part 2. Module fabrication and system integration
(1102-IRIS-11-02) and NUS grant no. of R-279-000-382-279.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.memsci.2016.10.022.
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