Applied Surface Science 450 (2018) 57–65

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Applied Surface Science

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

Full Length Article

Hydrophilic surface coating on hydrophobic PTFE membrane for robust

anti-oil-fouling membrane distillation
Kunpeng Wang a,b, Deyin Hou a,⇑, Jun Wang b, Zhangxin Wang c, Binghui Tian b, Peng Liang d
a
Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, PR China
b
State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, PR China
c
Department of Civil and Environmental Engineering, Vanderbilt University, Nashville, TN 37235-1831, United States
d
School of Environment, Tsinghua University, Beijing 100084, PR China

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

Article history: The hydrophobic membranes used in membrane distillation (MD) are inherently prone to fouling by
Received 30 October 2017 hydrophobic contaminants due to the long-range hydrophobic-hydrophobic interaction, which limits
Revised 29 March 2018 the application of this promising technology. In this study, a novel dual-layer composite membrane
Accepted 20 April 2018
was fabricated through eletrospinning a hydrophilic poly(vinyl alcohol) (PVA) coating on a commercial
Available online 22 April 2018
hydrophobic polytetrafluoroethylene (PTFE) membrane and then cross-linking with glutaraldehyde for
robust anti-oil-fouling MD. The prepared composite membrane showed an asymmetric wettability, the
Keywords:
coating surface was underwater oleophobic with underwater oil contact angle of 148.7° and the PTFE
Membrane fouling
Membrane distillation
substrate surface was hydrophobic with in-air water contact angle of 134.5°. The test results of the adhe-
Surface coating sive force between an oil droplet and membrane surface exhibited that the fabricated membrane had a
Eletrospinning desirable surface to resist oil adhesion. Direct contact MD experiments were conducted using a saline
Hydrophobic emulsion with 1000 mg/L crude oil to compare the performance of the modified membrane and the pris-
Underwater oleophobic tine PTFE membrane. The results demonstrated that the modified membrane can present stable perfor-
mance with robust resistance to oil-fouling compared to the pristine PTFE membrane. It is believed that
the fabricated composite membrane has great potential to be applied in MD process with high concen-
tration of hydrophobic organics.
Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction MD is also insensitive to the salt concentration and can achieve a

With the increasing demand for potable water and the serious
water pollution, water shortage problem has stimulated scientists
to develop efficient technologies to realize wastewater reclamation
and saline water desalination [1]. Among these technologies, based
on membrane technology, membrane distillation (MD) is an
emerging process and has attracted increasing attention in recent
years [2]. Rather than pressure driven membrane process such as
ultrafiltration and reverse osmosis, MD belongs to a thermally-
driven membrane separation technology [3]. The vapor generated
on the hot side results in a higher vapor pressure due to the higher
fluid temperature compared to that on the cold side, which drives
the vapor transporting through membrane and condensing at the
cold side. MD can operate at relatively low temperature and is thus
able to tap into the vast amount of low-grade waste heat or green
thermal energy such as solar energy and geothermal energy [4–6].
⇑ Corresponding author.
E-mail address: dyhou@rcees.ac.cn (D. Hou).
high water recovery (100% in theory) [7].
In MD process, the membrane, acting as a physical barrier to
direct liquid permeation and providing a porous medium for vapor
mass transfer, must be hydrophobic and is typically made of poly-
tetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and
polypropylene (PP) [8,9]. Due to the strong hydrophobic-
hydrophobic interaction between the hydrophobic membrane
and organic contaminants such as hydrocarbons and natural
organic matters [10,11], the hydrophobic membranes are inher-
ently prone to fouling by hydrophobic contaminants, which is
one of the vital obstacles for broad MD application.
In recent years, material scientists have developed high-
performance underwater anti-adhesion surfaces on various
meshes by using the knowledge and theory of bionic design and
material for oil/water separation and anti-biological adhesion
[12–16]. Through hydrogen bonding interaction with water, the
hydrophilic materials can form a hydration layer that may be used
to serve as a robust barrier for the attachment of hydrophobic sub-
stances [17]. However, the hydrophilic biomimetic surfaces cannot

https://doi.org/10.1016/j.apsusc.2018.04.180
0169-4332/Ó 2018 Elsevier B.V. All rights reserved.
58 K. Wang et al. / Applied Surface Science 450 (2018) 57–65
be directly applied in MD process, as the hydrophobicity is imper-
ative to prevent liquid from permeating through the membrane
pores [18]. It is therefore feasible to construct a hydrophilic coating
on the top of hydrophobic membranes for anti-oil-fouling in MD
process. The hydrophilic coating on the hydrophobic substrate
has two main functions in MD process: one is supplying a barrier
to repel oil-fouling, the other is to serve as a channel for saline
solution to reach the surface of the hydrophobic substrate.
Inspired by this principle, Wang et al. modified commercial
hydrophobic PVDF membranes using either in-situ formation of a
hydrophilic skin layer or spraying of a hydrophilic nanoparticle-
polymer composite, and the modified membranes exhibited good
resistance against oil-fouling when contacting with a saline
crude-oil emulsion [19,20]. However, one challenge of fabricating
a hydrophilic skin on a hydrophobic substrate using traditional
surface modification technologies such as dip-coating, spin coating
or spray coating, is the possibility of introducing wetting defects
and destroying the substrate surface hydrophobicity due to the
possible coating of the inner pores [21].
Electrospinning technique has been considered as a versatile
and flexible method for fibrous membrane fabrication in recent
decades [22,23]. Electrospinning involves the use of a high electric
field applied on a polymer or biopolymer solution forming elon-
gated and stretched nanometer- or submicrometer-sized fibers
and collecting on a grounded collector [24,25]. The unusually small
diameter of the electrospun fibers provides a high surface area to
volume ratio, and a high length to diameter ratio. These character-
istics are very useful in variety of applications, such as separation
membranes, biomedical materials, and photovoltaic application
[26–28]. Recently, with the advantages of high porosity and
inter-connected open structure, the electrospun hydrophobic
membranes have been applied in MD desalination and showed
encouraging permeability, low thermal conductivity and anti-
wetting performance [29–31]. Additionally, the properties of the
electrospun fibrous membranes can be easily tailored by adjusting
the electrospinning parameters, materials selection and post pro-
cessing treatment, and the fibrous coating can also be easily spun
on extra substrates to form dual or triple layer membranes
[32,33]. For instance, Tijing et al. electrospun PVDF-co-HFP fibers
on a polyacrylonitrile substrate to fabricate a dual-layer nanofi-
brous membrane that presented a higher permeate flux compared
with the commercial hydrophobic membranes in MD experiment
[34]. Last but not least, the fibrous coating is extremely unlikely
to penetrate through the tortuous pores and to destroy the sub-
strate surface intrinsic wettability due to the ultrahigh aspect
ratios of the electrospun fibers.
In the present study, we developed a novel dual-layer compos-
ite membrane for robust anti-oil-fouling MD via electronspinning a
hydrophilic surface coating on the hydrophobic membrane. The
commercial hydrophobic PTFE membrane was selected as the sub-
strate of the composite membrane due to its low surface tension
(about 20 mN/m) and strong thermal stability (with a melting
point of about 327 °C) [35,36]. Besides, some recent studies also
confirmed the superiority of PTFE membrane over PVDF and PP
hydrophobic membranes [8,37]. As for the hydrophilic coating of
the composite membrane, the inherent hydrophilicity and good
spinnability of poly(vinyl alcohol) (PVA) makes it an attractive
polymer for repelling oil-fouling [38]. Considering the water-
solubility of the PVA polymer, adequate cross-linking treatment
is necessary to prevent the electrospun hydrophilic coating swel-
ling during water treatment application [39–41].
We compared morphology and wettability between the pristine
PTFE hydrophobic membrane and the fabricated composite mem-
branes. The interactions between oil droplet and membrane sur-
face were also measured to compare the propensities of oil
adhesion to different membrane surfaces. Finally, direct contact
MD (DCMD) experiments with saline feed solution containing a
relatively high concentration of crude oil (1000 mg/L) were carried
out to show the drastically different anti-oil-fouling behaviors of
the pristine PTFE and the composite membranes.
2. Materials and methods
2.1. Materials and chemicals
The PTFE flat sheet hydrophobic membrane with mean pore
diameter of 0.45 lm was supplied by Sano Membrane Technology
Engineering Co., Ltd. PVA polymer (99% hydrolyzed, MW = 89,000–
98,000), dimethyl sulfoxide (DMSo), glutaraldehyde (GA), NaCl and
HCl were provided by Sigma-Aldrich. The crude oil, as the fouling
agent, was from Daqing Oil Filed of China National Petroleum Cor-
poration. Deionized water was obtained from a Milli-Q ultrapure
water purification system (Millipore, Billerica, MA).
2.2. Fabrication of composite membrane
The process to fabricate the dual-layer composite membrane
was schematically illustrated in Fig. 1, a. First, a 10 wt% PVA solu-
tion was prepared by adding PVA (10.0 g) to 90 mL DI water under
magnetic slow stirring at 85 °C for 5 h to completely dissolve the
PVA polymer. To lower the tension of PVA solution and enhance
the dope volatility, 2.0 g DMSo were added into 32.0 g PVA solu-
tion, stirring continuously for 3 h at room temperature. Then, sur-
face coating using an electrospining instrument (TL-01, Tongli
Tech., China) was carried out on the top of the commercial
hydrophobic PTFE flat sheet membrane attached onto a rotating
drum. The feed flow rate of PVA solution in syringe with a stainless
steel 18-gauge needle was fixed at 0.2 mL/h using a syringe pump
(CSP-100C, Shenzhen Carewell Electronics Co., Ltd., China). The
voltage applied for electrospinning the PVA fibers was 16 kV (with
positive voltage of 10 kV and negative voltage of 6 kV) over a col-
lection distance of 15 cm. The chamber humidity and temperature
kept at 30% and 30 °C, respectively.
After 60 h electrospinning, the PVA fibers was cross-linked with
GA by placing the nascent composite membrane above a beaker in
which the temperature of GA solution (3 wt%) maintained at 90 °C
for 3 h. The cross-linking reaction of PVA with GA is illuminated in
Fig. 1, b, and the cross-linking treatment is to avoid PVA swelling
and to ensure its long-term stability during MD experiment. Finally,
the cross-linked composite membrane was dried in air for 30 min to
remove redundant GA, then heat-pressed under 130 °C for 3 h. The
resultant composite membrane was denoted as PTFE/PVA-GA. For
comparison, the electrospun membrane without cross-linking and
heat press post-treatment was coded as PTFE/PVA.
2.3. Membrane characterization
The surface morphology of the commercial PTFE membrane and
fabricated composite membranes were characterized by a field
emission scanning electron microscopy (FESEM) (Hitachi SU-70,
Japan). The pore size and pore size distribution were investigated
using a Capillary Flow Porometer (Porolux 1000, IB-FT GmbH, Ger-
many). The membrane porosity was measured by gravimetric
method with a wetting agent (Porefil, IB-GT GmbH, Germany) of
a low surface tension of 16 dyn/cm and density of 1.87 g/mL.
In order to compare membrane surface chemical composition of
the fabricated membranes and the pristine PTFE membrane, atten-
uated total reflection using infrared fourier transform infrared spec-
troscopy (ATR-FTIR) analyses were conducted using a Perkin Elmer
Spectrum One FT-IR spectrometer (Perkin Elmer, USA) equipped
with a Perkin Elmer Universal ATR sampling accessory. Further-
 K. Wang et al. / Applied Surface Science 450 (2018) 57–65
Fig. 1. (a) Schematics of the fabrication procedures for composite membrane with asymmetric wettability. (b) Schematic illustration of the cross-linking reaction of PVA with
GA.
more, the X-ray photoelectron spectroscopy (XPS) (PHI Quantera
SXM, ULVAC-PHI, Japan) analyses for the electrospun nanofibers
were also carried out using a monochromatic Al Ka source, and
high-resolution scans were obtained by averaging 100 scans for C
1s peak from 270 to 295 eV with a resolution of 0.1 eV.
The contact angle of the membrane surface was measured using
the OCA20 Video-Based contact angle meter (DataPhysics Instru-
ments Ltd., Germany) to characterize the surface wettability. Both
the in-air water contact angle (WCA) and underwater oil contact
angle (OCA) of the membrane surfaces were measured, the OCA
was measured using a floating oil droplet that was in contact with
the down-facing membrane surface considering the density of the
crude oil is lower than that of water.
To better understand the interaction between the foulant (i.e.
oil) and the membrane surface, the underwater adhesion force
between oil and membrane surface was tested by using a high-
sensitivity adhesive force measurement system (DCAT11, DataPhy-
sics Instruments Ltd., Germany). A small oil droplet (～10 lL) was
carefully hung on a platinum-iridium ring pre-immerged in a glass
beaker which was filled with DI water, and the membrane sample
was immobilized to the bottom of the glass beaker using double-
sided tape. The beaker, placed on a vertically movable platform,
moved upward at a constant speed of 0.01 mm/s, driving the mem-
brane surface toward the suspended oil droplet until they con-
tacted each other, and then moved downward until the oil
droplet fully detached from the membrane surface. The change of
oil-membrane adhesion force was recorded using a microelectro-
mechanical system pulled by the adhesion force probe.
59
2.4. MD performance test
Before membrane anti-oil-fouling properties test, the oily and
salty feed solution was prepared by adding 4 g of crude oil into
4 L of NaCl aqueous solution (35 g/L) with a laboratory high-
shear dispersible mulser (AE500S-H, Angni Instruments, Shanghai,
China) at 15,000 rpm for 30 min. The concentration of crude oil in
the prepared feed solution was 1000 mg/L.
The DCMD experiments were carried out to evaluate the anti-
oil-fouling performance of fabricated composite membranes (the
schematic of the DCMD set-up can be found in Fig. S1). In the
experiment, the porous membrane with the electronspun PVA
coating facing the oily feed solution and the unmodified surface
contacting with the distillate, and the membrane effective area
was 7.47  10 3 m2. The feed and permeate streams, controlled
by water baths, were kept a constant temperature of 53 °C and
20 °C, respectively. The feed and distillate flowed co-currently
through the membrane module, and their flow rates were adjusted
by two rotameters (LZS-15, YuyaoYinhuanFlowmeter, China) to 70
L/h, which yielded a flow velocity of about 0.28 m/s. The mass and
conductivity of the distillate in the distillate reservoir were auto-
matically monitored throughout the duration of the experiment
using a computer system. The salinity of the distillate was calcu-
lated from the measured conductivity based on a pre-established
calibration curve. The permeate flux and the salt rejection were
calculated based on the change of the rates in the distillate mass
and salinity.
60 K. Wang et al. / Applied Surface Science 450 (2018) 57–65
3. Results and discussion
3.1. Membrane morphology
The SEM images of the pristine PTFE membrane and fabricated
membranes are shown in Fig. 2. In the commercial PTFE mem-
brane, a reticular fiber-nodule structure can be observed (Fig. 2a1
& a2) due to the melt-stretching membrane fabrication technology,
which contributes to the hydrophobicity of membrane. The modi-
fied PTFE membranes with an electrospun fibrous coating have a
drastically different surface morphology as compared to that of
the PTFE membrane. Both of the electrospun coating surfaces pre-
sent a fibrous interconnected open structure.
The PTFE/PVA composite membrane without GA cross-linking
and heat press is fluffy and sponge-like, and the electrospun PVA
fibers are uniform with an average diameter of 189.8 ± 39.9 nm
(Fig. 2b2). In the contrast, the PVA-GA fibers became wider with
the mean diameter of 339.9 ± 122.9 nm due to the cross-linking
reaction and heat press. Compared with the PVA fibers without
cross-linking treatment, the small fluffy branch fibers disappeared
in the PVA-GA fibers, which are similar with the previous studies
[42,43]. After cross-linking and heat press, the PVA-GA fibrous
coating presented an obvious beads-on-string structure as shown
in Fig. 2c1, and the coating surface became rougher due to the
increase of the fibers interconnection (Fig. 2c2).
3.2. Membrane surface chemical analysis
In order to verify the changes in surface chemical composi-
tion of the fabricated composited membranes, ART-FTIR was
conducted and the results can be found in Fig. 3. For the
PTFE membrane, the remarkably peak near 1220 cm 1 and
Fig. 2. SEM images of the pristine PTFE membrane (a1-a3), the PTFE/PVA composite membrane (b1-b3), and the PTFE/PVA-GA composite membrane (c1-c3).
1150 cm 1 represent the asymmetric stretching vibration and
the symmetric stretching vibration of CAFAC bond, respectively.
As for the electrospun fibrous coatings, the characteristic peaks
appearing at 3300 cm 1 are assigned to AOH stretching due to
the strong inter and intra molecular hydrogen bonding, the char-
acteristic absorption bands at 2940 cm 1 could be attributed to
the asymmetric and symmetric stretching vibration of ACH2
groups, and the peaks around 1417 cm 1 is correspond with
CAC bonds. The weak but identifiable peaks at 1087 cm 1 is
due to the stretching vibrations of CAO bonds. As for the PVA-
GA fibrous coating, the PVA fibers was cross-linked with GA
and formed a CAOAC bond. As shown in Fig. 3, a, the peak in
the absorption wave numbers associated with OAH groups near
3300 cm 1 became weak. Besides, it can also be found that the
peak around 1087 cm 1 slightly decreased for the PVA-GA
fibrous coating, which further indicated a cross-linking reaction
between GA and the PVA polymer.
To further confirm the cross-linking reaction between PVA and
GA, XPS had been carried out. It can be seen in Fig. 3b that the C 1s
core-level spectrum of the PVA fibers can be simply curve-fitted
with two main peak components, one at a binding energy (BE) of
284.8 eV for the carbon bonded to hydrogen (CH2) and the other
at a BE of 286.2 eV for a single the carbon bonded to oxygen
(CAO). On the contrast, as presented in Fig. 3c, the C 1s core-
level spectrum of the PVA-GA fibers can be divided into three main
peaks with a new peak at a BE of 288.1 eV, which can be attribute
to the introduction of aldehyde groups (CH@O). In addition, the
increase of the relative content of CH2 groups and the decrease
of the relative content of the CAO groups can also demonstrate
the cross-linking reaction between PVA and GA [44] (the values
and the corresponding positions of the C 1s peaks are listed in
Table S1).
 K. Wang et al. / Applied Surface Science 450 (2018) 57–65 61

a)
PTFE

Transmittance (a.u.) 1220 1150

PVA

PVA-GA

3300 2940 1417 1087

4000 3500 3000 2500 2000 1500 1000

-1
Wavenumber (cm )

b) C 1s
c) C 1s
CH2
C-O
Intensity

Intensity
CH2

C-O
C=O

280 282 284 286 288 290 282 284 286 288 290
Bonding energy (eV) Bonding energy (eV)
Fig. 3. (a) ATR-FTIR spectra of the pristine PTFE membrane, the PVA fibers and the PVA-GA fibers. (b) XPS C 1s core-level spectra of the PVA fibers, and (c) XPS C 1s core-level
spectra of the PVA-GA fibers.

3.3. Membrane structural properties and surface wettability
Undoubtedly, with eletrospinning PVA coating on the
hydrophobic PTFE membrane surface, the overall thickness of the
composite membrane was significantly increased as listed in
Table 1. However, the PVA fibrous coating is hydrophilic with high
porosity and interconnect structure, the feed liquid can permeate
the PVA coating easily and reach the hydrophobic surface of the
PTFE substrate. Compared with the PTFE/PVA composite mem-
brane, the cross-linked PTFE/PVA-GA composite membrane had a
thinner thickness and a lower porosity. This difference was mainly
because of the cross-linking and heat press post-treatment that
made the electrospun fibers closely interweave with each other
and the fibrous coating become thinner and denser. The pore size
distributions of the pristine PTFE membrane and the composite
membranes were presented in Fig. 4a. The pore size distribution
of the pristine PTFE membrane was very narrow with a mean
diameter of about 0.45 lm. The mean pore size and the maximum
pore size of the electrospun composite membranes are smaller
than those of the pristine PTFE membrane, which can be attributed
to the overlapped eletrospun fibers.
The liquid entry pressure of water (LEPw), determined by the
pore size, surface wettability and membrane thickness, is a critical
parameter to evaluate the stability of membrane performance for
long-term MD application in some extent. The membrane with
high LEPw is not easy to be wetted [19,42]. Although the fabricated
composite membranes have thicker membrane thickness and
smaller membrane pores compared with the pristine PTFE mem-
brane, the LEPw vales (2.37 bar for the PTFE/PVA composite mem-
brane and 2.45 bar for the PTFE/PVA-GA composite membrane) are
slightly lower than 2.89 bar of the pristine PTFE membrane. This
result can be explained by the fact that the eletrospun fibrous coat-
ings on top of the PTFE substrate are hydrophilic and can be imme-
diately wetted by water. In essence, the fibrous coatings would not
contribute to the resistance against pressurized water squeezing
into membrane pores.
The PTFE membrane and electrospun composite membranes
showed drastically different surface wettability, and the in-air
WCA and underwater OCA of pristine PTFE membrane and the
composite membranes are shown in Fig. 4b. The pristine PTFE
membrane surface was hydrophobic with in-air WCA 134.5°, but
this surface was underwater oleophilic with underwater OCA

Table 1
Characteristics of the pristine PTFE membrane and the fabricated composite membranes.

Membrane Thickness (lm) Porosity (%) Mean pore size (lm) The maximum pore size (lm) LEPw (bar)
PTFE 185 ± 0.05 54.3 ± 0.02 0.45 ± 0.03 0.82 ± 0.07 2.89 ± 0.27
PTFE/PVA 285 ± 0.03 78.0 ± 0.06 0.26 ± 0.05 0.75 ± 0.05 2.37 ± 0.20
PTFE/PVA-GA 260 ± 0.15 60.4 ± 0.04 0.28 ± 0.04 0.63 ± 0.08 2.45 ± 0.15
62 K. Wang et al. / Applied Surface Science 450 (2018) 57–65

a) 100 of oily foulant. We thus tried to use an adhesion force probe with
PTFE an oil droplet gradually contacting with membrane surface and to
PTFE/PVA record the changes of adhesion force by microelectro-mechanical
80 PTFE/PVA-GA system. Fig. 5, a illustrates the four main events during the force
spectroscopy experiments, which can be classified as contact
Percentage (%)

event, preload event, retract event and detach event. First, the
60
membrane sample was driven toward the oil droplet hung on the
platinum-iridium ring at a constant speed until contact. The mem-
40 brane sample kept moving further after the oil-membrane contact
until it reached the designated position. These two events compose
the advancing stage of the membrane sample, in the receding
20 stage, the membrane sample moved back from the force probe
and the oil droplet was completely split at last. The characteristic
shapes of the force curves were different depending on the interac-
0 tion between the oil droplet and the tested membrane.
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 When the oil droplet contacted with the pristine PTFE mem-
Pore size (μm) brane, because the membrane was underwater oleophilic, the oil
droplet will immediately adhere on the membrane surface and
b) spread out easily. In receding stage, a large amount of the oil dro-
plet will stay on the PTFE membrane due to the strong
hydrophobic-hydrophobic interaction. On the contrary, when the
oil droplet contacted with the fabricated composite membranes,
it still kept spherical due to the presence of the eletrospun hydro-
philic coatings. Under external pressure, the shape of the oil dro-
plet transformed from spherical to elliptical, and the oil would

a)

Fig. 4. (a) Pore size distribution of the pristine PTFE membrane, the PTFE/PVA
composite membrane and the PTFE/PVA-GA composite membrane. (b) In-air water
contact angle and underwater oil contact angle of the pristine PTFE membrane, the
PTFE/PVA composite membrane and the PTFE/PVA-GA composite membrane.

25.5°. In contrast, the in-air WCA was 35.5° for the modified sur-
face of the PTFE/PVA-GA composite membrane, and this mem-
brane showed outstanding underwater oleophobicity with
underwater OCA 148.7°. The drastically different surface wettabil-
ity was attributed to the strong hydration of the electrospun sur- 200
b)
Underwater crude oil adhesive force (μN)

face coating on PTFE substrate. The hydroxyl groups on PVA A

polymer can form hydrogen bonds with surrounding water mole- 150 B
cules and result in a stable interfacial hydration layer. The attach- C
ment of oil and the spreading of an oil droplet on a hydrated 100
surface were significantly mitigated by the presence of the hydra-
tion force [17]. 50
It should be also noted that the electrospun fibrous coating
itself obtains the re-entrant structure that will enhance the wetta- 0
bility of the composite membranes [31]. The Cassie model depend-
ing on a water/air/solid interface can also be applied to the oil/ -50
water/solid system to illuminate the underwater oleophobicity of
membrane surface [45]. When the hydrophilic fibrous coating con- -100
tacts with the oil droplet, water can permeate into the inter-fiber
space, forming an oil/water/solid interface, thus decreases the con- -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
tact area between oil droplet and membrane surface, resulting in Position (mm)
an improvement of the OCA [46].
Fig. 5. (a) Shapes of the oil droplet in different event during adhesive-force
measurement process on different membrane surface. The red line is the position
3.4. Underwater oil-membrane surface interaction where the oil droplet first contacted with membrane surface. (b) Force-distance
curves recorded the changes of the adhesive-force between the oil droplet and
membrane surface at advancing and receding stages (anticlockwise). A, B, C are the
The interaction between oil droplet and membrane surface pristine PTFE membrane, the PTFE/PVA composite membrane and the PTFE/PVA-GA
determines the fouling propensity of a membrane in the presence composite membrane, respectively.
 K. Wang et al. / Applied Surface Science 450 (2018) 57–65 63

not spread out on the underwater oleophobic surface of the com-
posite membranes. In receding stage, only a little oil remained on
the membrane surface.
Fig. 5b recorded the changes of oil-membrane adhesive force at
different position for the different membranes, the value of the
force was set to zero before contact. If the membrane was attrac-
tive to the oil droplet, a positive adhesive force was observed upon
the contact between the oil droplet and the membrane. In contrast,
a negative force would be observed if the membrane-oil interac-
tion was repulsive. There are some strikingly differences in the
force curves for the three membranes, which are in accordance
with Fig. 5a. First, the force curve showed a sharp rise when the
oil droplet contacted with the PTFE membrane due to
hydrophobic-hydrophobic force, while the force became negative
when the oil droplet contacted with the composite membranes
because of the repulsive force between the oil droplet and the
hydrophilic coatings. As the membrane sample moved upwards,
the oil droplet was under compression and the negative force
increased in the curves. The spread out of the oil droplet on the
PTFE membrane surface retarded the increase of the force and also
reduced the final repulsive force. In receding stage, the maximum
adhesive force was recorded just when the oil droplet split away
from the membrane, which can provide semi-quantitation of the
attractive interaction between the oil droplet and membrane.
Because some oil remained on the membrane surface, the buoy-
ancy of the oil droplet declined after leaving from the membrane,
and a positive value would be recorded by the microelectro-
mechanical system. Undoubtedly, the difference in the baseline
forces between the advancing and the receding stages, which pos-
itively correlates with the volume of the oil droplet retained by the
membrane surface, also serves semi-quantitative comparison of
the oil-membrane interaction.
butable to the increased thickness and decreased pore size of the
PTFE/PVA-GA membrane and the hydrophilic coating more or less
enhanced the more or less enhanced the resistance of water vapor
transporting through the membrane. It was obvious that the per-
meate flux of the PTFE/PVA composite membrane was below
10.0 kg/m2 h, this unpromising performance was mainly due to
the PVA polymer swelling in water solution, which induced the
decrease of the pore size and even closed, thus the feed solution
cannot contact the surface of the hydrophobic membrane. Interest-
ingly, the permeate conductivity of all these three membranes was
below 20 lS/m, which indicated that the salt rejection was nearly
100% and the hydrophilic fibrous coatings did not introduce wet-
ting defects to the PTFE substrate.
In order to evaluate the oil-fouling resistance of the mem-
branes, DCMD experiments were conducted with the feed solution
containing 35 g/L NaCl and 1000 mg/L crude oil using the pristine
PTFE membrane and the fabricated PTFE/PVA-GA composite mem-
brane. The size distribution of oil droplets, measured by dynamic
light scattering with a ZetaSizer (Malvern Nano ZS, UK), suggests
a mean diameter of 6.1 ± 0.8 lm (Fig. S2). Because the oil droplets
are significantly larger than the membrane pores, the attachment
of oil droplets onto the membrane surface is expected to block
membrane pores and induce significant fouling. Fig. 6b exhibits
drastically different anti-oil-fouling performance between the
two membranes. The permeate flux of the pristine PTFE membrane
declined from 19.8 kg/m2 h to 13.0 kg/m2 h in the first hour, and
lost about 50% permeate flux within 5 h, these results suggested
that the PTFE membrane had been seriously fouled by crude oil.
a) 90
20
Permeat flux (kg/m2h)

Table 2 summarizes the characteristics of the force curves for

Conductivity (μS/cm)
the three membranes. The PTFE membrane was attractive to the 15 60
oil droplet due to the hydrophobicity of the both membrane sur- PTFE
face and the oil droplet. In comparison, both the PTFE/PVA and PTFE/PVA
PTFE/PVA-GA
PTFE/PVA-GA composite membranes were repulsive to the oil dro- 10
plet, which can be attributed to the hydration force experienced by
30
the oil droplet when it contacted the strongly hydrated PVA and
PVA-GA coatings. The maximum adhesive force and baseline shift 5
indicated that the PVA-GA coating was more effective than the
PVA in resisting oil attachment. The stronger hydrophilicity of
the PVA-GA coating led to a stronger repulsive hydration force that 0 0
significantly mitigated oil attachment onto membrane surface, 0 5 10 15 20
which was consistent with the higher underwater OCA of the Operation time (h)
PTFE/PVA-GA composite membrane.
b)
20
3.5. Membrane distillation performance PTFE Rinsed Membranes
PTFE/PVA-GA
Permeate flux (kg/m2h )

The membranes were tested through a DCMD setup using a 15

solution with 35 g/L NaCl at 53 °C as the feed solution, whereas
the distillate temperature kept at 20 °C. The permeate fluxes of
1.0
the three membranes are shown in Fig. 6a. It can be found that 10
although the permeate flux of the PTFE/PVA-GA composite mem-
J/JO

0.5
brane was slightly lower than that of the commercial PTFE mem-
brane, the modified membrane still maintained well permeability 5 0.0
(with the permeate flux above 15.0 kg/m2 h). This result was attri- 0 10 20 30
Operation time (h)
40

0
Table 2 0 10 20 30 40
Summary of force curves characteristics for the tested membranes.
Operation time (h)
Membrane PTFE PTFE/PVA PTFE/PVA-GA
Fig. 6. (a) Continuous DCMD tests of the pristine PTFE membrane, the PTFE/PVA
Force upon contact Attractive Repulsive Repulsive
membrane, and the PTFE/PVA-GA membrane without crude oil. (b) The DCMD
Max adhesive force (lN) 186.5 128.3 60.9
performance of the pristine PTFE membrane and the PTFE/PVA-GA membrane
Max repulsive force (lN) 50.3 85.7 114.3
under 1000 mg/L crude oil, and the insert showed the variation of normalized
Baseline shift (lN) 110.8 102.6 46.4
permeate flux with time.
64 K. Wang et al. / Applied Surface Science 450 (2018) 57–65
Since the intrinsic hydrophobic and underwater oleophilic prop-
erty, the crude oil is easily adhered to the surface of the PTFE mem-
brane via the strong hydrophobic-hydrophobic interaction,
resulting in the accumulation of the oil droplets on the membrane
surface which would block the membrane pores and thus brought
out the decline of permeate flux that eventually became zero.
By contrast, the PTFE/PVA-GA composite membrane exhibited
stable MD performance while facing the feed with 1000 mg/L
crude oil, which indicated that the composite membrane obtained
robust oil-fouling resistance. The anti-oil-fouling property of the
composite membrane can be ascribed to the electrospun PVA-GA
hydrophilic coating which can form strongly hydrogen bond with
water molecule, resulting in a hydration layer that served as a bar-
rier to resist the crude oil attaching. And the mechanism of anti-
oil-fouling of the composite membrane can also be explained by
the high underwater OCA and the very low adhesion force between
the oil droplet and the PTFE/PVA-GA composite membrane.
After being used in the DCMD experiment, both the fouled PTFE
membrane and the PTFE/PVA-GA composite membrane were
rinsed with DI water for 3 min. The photos of the membranes as
presented in Fig. 7 provided direct evidence that the composite
membrane was more resistant to oil-fouling compared to the PTFE
membrane. The oil foulant can be easily rinsed off from the surface
of the composite membrane, after drying in ambient, there is
almost no difference between the rinsed membrane and the origi-
nal fabricated membrane by appearances. In contrast, the oil-
fouling on the PTFE membrane was largely irreversible, as rinsing
the PTFE membrane surface did not seem to remove the oil foulant.
To further evaluate the performance stability of the composite
membrane, the DCMD experiments with the feed containing 35
g/L NaCl and 1000 mg/L crude oil were conducted again using
the rinsed PTFE and PTFE/PVA-GA membranes. As can be seen in
Fig. 6b, the permeate flux of the rinsed PTFE/PVA-GA membrane,
with little difference compare to the original value, maintained
stable. However, the rinsed PTFE membrane recovered only about
17.5% of its original flux because the most pores of the membrane
were completely blocked by the oil-foulant during the first DCMD
experiment. These results indicate that the fabricated PTFE/PVA-
GA composite membrane has excellent anti-oil-fouling property
and satisfying performance stability, and may potentially enable
MD to desalinate more challenging saline wastewater with a
strong fouling potential.
Fig. 7. The photos of the membranes after DCMD experiments and the photos of the
fouled membranes after rinsing with DI water.
4. Conclusions
The hydrophobic membranes used in MD are inherently prone
to fouling by hydrophobic contaminants due to the long-range
hydrophobic-hydrophobic interaction, which hinders the large-
scale application of MD. In this study, we fabricated a novel dual-
layer composite membrane by eletrospinning hydrophilic PVA
coating on the commercial hydrophobic PTFE for anti-oil-fouling.
The fibrous coating was cross-linked with glutaraldehyde and then
heat-pressed to prevent the PVA polymer swelling in water solu-
tion. We characterized the pristine and the modified membranes
using contact angle measurements and tensiometer-based oil
probe force spectroscopy. The prepared composite membrane
showed an asymmetric wettability, the coating surface was under-
water oleophobic with underwater oil contact angle of 148.7° and
the PTFE substrate surface was hydrophobic with in-air water con-
tact angle of 134.5°. The measure results of the adhesive force
between an oil droplet and membrane surface indicated that the
fabricated membrane had a desirable surface to resist oil adhesion.
DCMD experiments were conducted using a saline emulsion with
1000 mg/L crude oil to compare the performance of the composite
membrane and the pristine PTFE membrane. The results demon-
strated that the modified membrane can present stable perfor-
mance with robust resistance to oil-fouling compared to the
pristine PTFE membrane. This study opens a new path to fabricate
anti-fouling composite membranes via electrospinning hydrophilic
coating on a hydrophobic substrate, and it is also believed that the
fabricated composite membrane has great potential to be applied
in MD process with high concentration of hydrophobic organics,
or to mitigate organic and biological fouling in other pressurized
membrane processes.
Acknowledgements
Financial support provided by the National Key R&D Program of
China (No. 2016YFC0400500), the National Natural Science Foun-
dation of China (No. 51678555 and No. 51478454) and the special
fund of State Key Joint Laboratory of Environment Simulation and
Pollution Control (No. 16L02ESPC) are gratefully acknowledged.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.apsusc.2018.04.180.
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