Desalination 347 (2014) 175183

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

Superhydrophobic PVDFPTFE electrospun nanobrous membranes for

desalination by vacuum membrane distillation
Zhe-Qin Dong, Xiao-hua Ma, Zhen-Liang Xu , Wen-Ting You, Fang-bing Li
State Key Laboratory of Chemical Engineering, Membrane Science and Engineering R&D Lab, Chemical Engineering Research Center, East China University of Science and Technology (ECUST),
130 Meilong Road, Shanghai 200237, China

H I G H L I G H T S

PVDFPTFE electrospun nanobrous membranes (ENMs) were fabricated by electrospining.

The ENMs with different PTFE micro-powder contents were prepared and characterized.
The PVDFPTFE electrospun nanobrous membranes were superhydrophobic.
The ENMs were used for desalination via vacuum membrane distillation.
The ENMs presented a high permeate ux with stable performance.

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

Article history: In this study, a superhydrophobic nanobrous membrane was prepared on the basis of an electrospun
Received 16 November 2013 polyvinylidene uoride (PVDF)polytetrauoroethylene (PTFE) nanobrous scaffold coupled with a micropo-
Received in revised form 7 May 2014 rous PTFE substrate. The PVDFPTFE nanobrous scaffold was fabricated by electrospining of PVDFPTFE blend
Accepted 8 May 2014
solutions, it was observed that by changing the PTFE micro-powder content in the dope solutions from 0 wt.%
Available online 17 June 2014
to 12 wt.%, the water contact angle (WCA) and the liquid entry pressure (LEPw) of the membrane vary from
Keywords:
130.4 and 84 kPa to 152.2 and 137 kPa, respectively. The superhydrophobic PVDFPTFE nanobrous membrane
Electrospining was then tested for desalination by vacuum membrane distillation (VMD), a stable ux of 18.5 kg/m2 h and salt
PVDFPTFE rejection higher than 99.9% was presented throughout the entire testing period of 15 h, indicating the great po-
Superhydrophobic tential of the PVDFPTFE nanobrous membranes in VMD. For further application of the PVDFPTFE nanobrous
Nanobrous membrane membranes in VMD, a mathematical model was presented to predict the vapor ux of the novel membrane
Membrane distillation under various operation conditions. A good agreement between the experimental and theoretical values for
vapor uxes was obtained; the results indicated that the VMD ux increased with the increase of feed tempera-
ture and ow rate and decreased with the increase of permeate pressure.
2014 Elsevier B.V. All rights reserved.

1. Introduction surface morphology and pore structure. An ideal membrane for MD

Membrane distillation (MD) is a non-isothermal separation process
which is driven by a vapor pressure difference through a porous hydro-
phobic membrane. There are generally four different MD congurations
including direct contact membrane distillation (DCMD), sweeping gas
membrane distillation (SGMD), vacuum membrane distillation (VMD)
and air gap membrane distillation (AGMD). Compared with other sepa-
ration process, MD has a great potential in desalination for possessing
the advantages of lower operating temperature, less energy consump-
tion as well as 100% theoretical rejection of non-volatile solute [14].
Although the membrane only acts as a physical barrier in membrane
distillation, the performance of MD is strongly affected by the membrane
Corresponding author. Tel.: +86 21 64253061; fax: +86 21 64252989.
E-mail address: chemxuzl@ecust.edu.cn (Z.-L. Xu).
should exhibit a superhydrophobic surface to avoid pore wetting and a
well-designed pore structure to enhance water ux [511]. These proper-
ties mainly depend on the polymer or additives that are used for prepar-
ing the membrane and also on the method of synthesis of membrane.
Most of the materials employed in the preparation of membranes
for MD applications are hydrophobic, such as polypropylene (PP),
polytetrauoroethylene (PTFE), and polyvinylidene uoride (PVDF).
However, the commercial membranes fabricated out of these polymers
are commonly made through a melting process or phase inversion pro-
cess, the surface of these membranes is not highly hydrophobic and the
porosity is low, which is the major barrier impeding MD industry appli-
cations [12,13].
Electrospinning is an attractive approach for the fabrication of nano-
meter or submicrometer-sized bers which received an increasing atten-
tion in recent years [1417]. Compared with commercial membranes

http://dx.doi.org/10.1016/j.desal.2014.05.015
0011-9164/ 2014 Elsevier B.V. All rights reserved.
176 Z.-Q. Dong et al. / Desalination 347 (2014) 175183
made through conventional process, the electropsun nanober mem-
branes (ENMs) have showed great potential in membrane distillation
due to their high void volume fraction and interconnected open
structure [1821]. Feng et al. rstly attempted to use ENM in MD [18],
up to 22% of saline water was treated with the membrane. The salt re-
jection was about 99%, and the uxes were as high as or higher than
those of commercial PVDF membrane, which shows the great potential
of PVDF ENM in MD. Essalhi and Khayet [19] investigated the effect of
eletrospinning time on ENMs; a considerable increase of both the thick-
ness and the liquid entry pressure of water with the electrospinning
time was observed, while only a slight enhancement was detected for
the void volume fraction. Yuan Liao et al. [20] optimized the pore sizes
of PVDF ENMs by varying polymer dope compositions, electrospinning
process parameters and heat-press treatment. The DCMD test for the
post-treated PVDF ENMs was much better than the commercial PVDF
membranes, suggesting the competency of PVDF ENMs for MD applica-
tions. However, the uniform electropsun nanober membranes fabri-
cated by pure polymer dopes without hydrophobic additives are
usually not superhydrophobic [1820]. Preparation and characteriza-
tion of superhydrophobic ENMs for MD were reported by Prince et al.
[21]. The superhydrophobic membrane with a water contact angle of
154.2 was obtained by electrospining of PVDF blended with clay nano-
composites, but the PVDFclay membrane presented quite a low ux
(b 5.5 kg/m2 h) in direct contact membrane distillation, which limits
its application.
The goal of this study was to fabricate a superhydrophobic
nanobrous membrane with high water ux for membrane distilla-
tion. The PTFE micro-powders were added in the electrospining of
PVDF dope solutions to improve the surface hydrophobicity of the
nanobrous membrane, as previous studies showed that the PVDF
PTFE composite membranes fabricated by phase inversion method
or coxial-electrospining method exhibited enhanced hydrophobicity
[2225]. In this work, PVDFPTFE nanobrous membranes with dif-
ferent properties were prepared by electrospining of PVDFPTFE
blend solutions on a PTFE microporous substrate, which acts as a
support layer to improve the mechanical properties. The schematic
diagrams for the assembly of the PVDFPTFE nanobrous mem-
branes were shown in Fig. 1. The prepared membranes were charac-
terized by scanning electron microscopy (SEM), atomic force microscopy
(AFM), water contact angle (WCA) and liquid entry pressure of water
(LEPw) to investigate their surface and structure. Subsequently, these
nanobrous membranes were tested in vacuum membrane distillation
to compare with a commercial MD membrane.
Fig. 1. Fabrication schematics of PVDFPTFE nanobrous composite membrane.
2. Experimental
2.1. Materials
Polyvinylidene uoride (PVDF, Solef 6010) was purchased
from Solvay Advanced Polymers, L.L.C. (Alpharetta GA, USA) and
polytetrauoroethylene (PTFE) micro-powders (Dyneon TF9207)
were purchased from Shanghai Xianglan chemicals CO. LTD (China). For
PTFE micro-powders, the primary particles are 120 nm in diameter, and
the average aggregate length is 4 m. All other solvents and reagents
were analytical grade and purchased from Shanghai Sinopharm Chemical
Reagent CO. LTD (China). The PTFE microporous substrate was purchased
from Shanghai Nuozhen New Chemical Materials CO. LTD (China), the
thickness of the substrate was 65 m, with a mean pore size of 1 m
and porosity of 75%. Commercial PTFE membrane manufactured
by Sumitomo Electric Industries, Ltd was used to compare with the
nanobrous membranes in vacuum membrane distillation.
2.2. Preparation of PVDFPTFE nanobrous membranes
The dope solutions were rst prepared by dissolving 15 wt.% PVDF in
the solvent mixture of N, N-dimethylacetamide (DMAC) and acetone
(50/50 wt.%), different amounts of PTFE micro-powders at 0, 3, 6 and
12 wt.% were added into the dope solutions to enhance the hydropho-
bicity of the membrane. The compositions of the dope solutions for
electrospinning corresponding to the membrane samples S1S4 are
presented in Table 1. The PVDFPTFE solutions were allowed to stir at
50 C for about 24 h before electrospinning.
The electrospinning setup used in the present work was the same in
our previous study [2528]. It consisted of a 20 mL plastic syringe to
hold the polymer solution connected to a syringe pump (WC50C6,
Zhejiang) to control the injection rate of the polymer solution, two
electrodes (a metallic needle and a grounded metallic collector kept in
horizontal position), and a high-voltage power supply (DWP3031ACD8,
Tianjin) which could generate positive direct current voltage up to
30 kV. The polymer drop from the tip of the needle (0.4 mm inner
diameter) connected to the syringe by a Teon tube is drawn into a
ber due to the high voltage. The whole setup was placed in a temper-
ature controlled room.
The PVDFPTFE nanobrous membranes were fabricated by
electrospinning the dope solutions on a PTFE microporous substrate,
as shown in Fig. 1. A positive voltage of 18 kV was applied across a dis-
tance of 15 cm; the polymer was electrospun at a rate of 0.5 mL/h to get
 Z.-Q. Dong et al. / Desalination 347 (2014) 175183
Table 1
Compositions of electrospining dope solutions.
Sample PVDF (wt %) PTFE (wt.%) DMAC (wt.%) Acetone (wt.%)
S1 15 0 42.5 42.5
S2 15 3 41.0 41.0
S3 15 6 39.5 39.5
S4 15 12 36.5 36.5
a uniform mat of thickness about 30 m, while the humidity and tem-
perature were controlled at 50 5% and 25 1 C, respectively. After
electrospinning, the nanobrous membranes were dried for a day at
room temperature for the solvents to evaporate. The dried membranes
were stored in a desiccator before use.
2.3. Membrane characterization
The morphologies of the membranes were observed by scanning
electron microscope (SEM; JSM-6360LV, Japan). The average ber
diameter and average pore size of the nanobrous membranes were
measured from the SEM images using J MicroVision image analyzer.
Quantitative surface roughness analysis of the nanobrous
membrane was measured using AFM (Veeco, Nanoscope IIIa Multi-
mode AFM). Air-dried membrane sample was xed on a specimen
holder and 5 m 5 m areas were scanned by tapping mode in air.
In the AFM analysis, the average roughness (Ra) was used to evaluate
the morphology of the membrane.
A JC2000D1 (produced by Shanghai Zhongcheng Digital Technology
Apparatus Co. Ltd., China) system was used for the determination of the
dynamic contact angles () of the nanobrous membranes at ambient
temperature. A water droplet of 0.2 mL was dispersed from a needle
tip onto the membrane surface. The machine was coupled with a
camera, enabling image capture at 10 frames/s. The contact angles
were determined from these images using the specic calculation soft-
ware. To ensure that the results were sufciently credible, the measure-
ment for each set of samples was performed in triplicate, and the
average data of contact angles was taken.
The membrane porosity is dened as the volume of the pores divided
by the total volume of the membrane. It can be determined by using iso-
propyl alcohol (IPA), which penetrates inside the inter-ber space of the
membranes and distilled water, which does not enter in the inter-ber
space. Detailed information was reported elsewhere [29].
The evaluation of the membrane wetting resistance was conducted
by liquid entry pressure of water (LEPw) measurements. The LEPw
value is the minimum applied pressure to water before it penetrates
into the membrane pores, which mainly depends on the pore size and
membrane hydrophobicity according to the Laplace equation [30]:
2B L cos
LEPw NP interface P liquid P vapor
r max
where B is a geometric factor determined by pore structure, L is the
liquid surface tension and is the liquid/solid contact angle.
LEPw values were measured using a dead-end ltration set-up
which was designed according to the method described extensively by
Smolder and Franken [31]. The dry hydrophobic membrane was placed
in a dead end cell and the cell was topped up with DI water. Compressed
nitrogen was used to apply pressure in the cell. The pressure was noted
when the rst drop of water came from the cell. The experiment was
carried out thrice using three different membranes made from the
same condition. The results were averaged to obtain the nal LEPw.
2.4. VMD performance test
The nanobrous membranes and commercial PTFE membrane were
tested in a VMD setup with an effective membrane area of 0.00785 m2
177
under identical operating conditions. The inuence of operation condi-
tions of VMD on the performance of nanobrous membranes was also
investigated, the feed temperature, the pressure at the permeate side
and the ow rate were varied in the range of 313343 K, 315 kPa
and 1890 L/h, respectively.
The VMD experimental installation of this work is shown in Fig. 2.
The feed water was driven by a circulation pump (Nanjing Lvhuan
Pumps Co. Ltd.) and the feed ow was measured by a owmeter con-
nected between the pump and the module. A thermostatic bath was
used to provide the feed with heat energy to perform VMD. The tem-
perature of the feed water at the inlet of the membrane module was
continuously measured by a Pt100 probe connected to an automatic
temperature regulator.
In order to maintain the feed concentration, water was added in the
feed tank every 1520 min during experiments. The quantity of the
replenishing water was determined by the decrement weight of the
feed tank measured by an electronic balance.
At the permeate side of the membrane module, a vacuum pump
(Shanghai Vacdo Vacuum Equipment CO. LTD.) was connected and a
glass condenser with refrigerating machine was used to recover the
water permeating vapor. The permeate pressure was measured by a
mercurial pressure gauge. The permeate ux was calculated, in every
case, by measuring the volume of the condensed water.
3. Theoretical approach
The system to be investigated consists of a composite membrane
maintained between hot feed solution and vacuum permeate side. In
VMD processes, evaporation takes place at the hot feed side while con-
densation takes place at the vacuum side after water vapor transferred
through the pores of the nanobrous top-layer and porous sub-layer.
Both mass and heat transfer occur simultaneously across the membrane
under vapor pressure difference. Consequently, the temperatures and
concentrations at the membrane surfaces differ from those at the bulk
liquid phases, leading to a decrease of the driving force and reduction
of the VMD ux, as shown in Fig. 3.
3.1. Heat transfer
The following heat transfer ux is involved in the VMD system as
described previously [12]:
Through the feed solution boundary layer:
Q f h f T b T m : 2
Through the nanobrous top-layer:
Q t ht T m T s J w Hv : 3
1
Through the porous sub-layer:
Q s hs T s T v : 4
At steady state, the overall heat transfer ux through the whole VMD
system, Q, is given by
Q Q f Q t Q s: 5
In the above equations, h is the heat transfer coefcient, Jw is the per-
meate ux, Hv is the latent heat of vaporization and T is the absolute
temperature. The subscripts specifying the location of the temperature,
b, m and s refer to the bulk solution, top-layer of the membrane and its
sub-layer, respectively.
178 Z.-Q. Dong et al. / Desalination 347 (2014) 175183

Fig. 2. Schematic diagram of vacuum membrane distillation.

The heat transfer coefcients hf can be estimated with the help of the 3.2. Mass transfer
known empirical correlations:
The permeate ux of water vapor, Jw, is related to the vapor pressure
Nu difference as follows:
hf 6
dh
J w K t P m P s K s P s P v 10
where Nu can be obtained by empirical equations described in Ref. [5].
where Pm is the partial vapor pressure at membrane surface as the
0:74 0:33 function of membrane surface temperature Tm as described in Eq. (11)
Nu 0:0142Re Pr 7 and Ps and Pv are the vapor pressure at the sub-layer and vacuum side,
respectively.
where Re and Pr are the Reynolds and Prandtl numbers, respectively.
The heat transfer coefcient of the top-layer (ht) and sub-layer (hs), P m P sat T m T m xm 11
can be calculated from the thermal conductivities of the hydrophobic
membrane polymer and the gas present inside the pores: where Psat(Tm) is the saturated vapor pressure of pure water at mem-
brane surface temperature Tm, (Tm) is the activity coefcient of water
kg t kt 1t and xm is the molar fraction of water at membrane surface.
ht 8 Kt and Ks are the permeability of the nanobrous top-layer and
t
porous sub-layer, respectively. According to the kinetic theory of
the dusty-gas model, the Knudsen diffusion and molecular diffusion
are taken place in the process of the vapor transporting through the
kg s ks 1s
hs : 9 membrane pores. As reported previously [5], the Knudsen diffusion of
s
water molecules is dominant in VMD process, Kt and Ks can be calculated
by Eqs. (12)(13)
In the above equations, k is the thermal conductivity, is the porosity
s
of the layer and is the thickness of the layer. The subscripts g, t, s refer 8 t rt 1
to gas present inside the pores, nanobrous top-layer and porous sub- Kt 12
3 t t 2RT m
layer, respectively.

s
8 s rs 1
Ks 13
3 s s 2RT s

where is the pore tortuosity, is the membrane thickness, R is the gas

constant and M is the water molecular mass. The subscripts t and s
refer to nanobrous top-layer and porous sub-layer, respectively.
According to Eqs. (2)(13), the prediction ux can be obtained by
the iteration method.

4. Results and discussions

4.1. Membrane morphology analysis

The SEM images of the surface of the PVDFPTFE nanobrous mem-

Fig. 3. Heat and mass transfer through nanobrous composite membrane in vacuum
membrane distillation.
branes prepared with various PTFE micro-powders contents are shown
in Fig. 3. The nanobers fabricated by pure PVDF solution (S1) were
smooth and uniform, due to the good solubility and volatility of the
mixed solvents. Rough particles emerged in the nanobers when PTFE
micro-powders were added into the dope solution, it is noted that the
 Z.-Q. Dong et al. / Desalination 347 (2014) 175183
amount of rough particles increased with the increase of PTFE concentra-
tions in dope solutions. Previous studies show that superhydrophobic
surfaces can be produced mainly in two ways. One is to create a rough
structure on a hydrophobic surface (CA N 90), and the other is to
modify a rough surface by compounds with low surface free energy,
such as uorinated or silicon compounds [32]. The addition of PTFE
micro-powders not only reduces the surface energy of the membranes
but also improves the surface roughness, which is benecial to surface
hydrophobicity.
The ber diameters and pore sizes of the fabricated membranes
were determined from the SEM image using the J Micro Vision image
analyzer and Image software. The ber diameters and pore sizes for
various membranes are summarized in Table 2. Both the ber diameter
and pore size of the membranes increase slightly as the concentration of
PTFE micro-powder increases in the dope solution, since a high viscosity
favors the formation of thicker bers and bigger pore size. Similar inves-
tigations of dope solution viscosity on membrane properties have been
conducted previously [19].
4.2. Membrane surface analysis
The water contact angles (WCA) for all the electrospun membranes
(S1S4) are shown in Table. 2, the WCA of the PTFE commercial mem-
brane is also characterized and denoted as S0. The result shows that
all the electrospun membranes (S1S4) have impressive water contact
angles (130.4 to 151.2) compared with the PTFE commercial mem-
brane (121.5). It can also be seen that the WCA of the electrospun
membranes increased as the concentration of PTFE micro-powders in-
creased in the dope solution, the superhydrophobic membrane (S4)
with a WCA of 151.2 was obtained when the concentration of PTFE
micro-powders was 12 wt.%, while the membrane (S1) prepared with
pure PVDF solution only had a WCA of 130.4. The phenomenon that
the WCA increased signicantly with the addition of PTFE micro-
powders can be explained as follows.
Generally, the water contact angle for a at surface can be obtained
by the well known Young equation as the following:
SA SL
cos 0 : 14
LA
The characteristic angle 0 is called the static contact angle. SA and
SL are the surface energies of solid against air and liquid, respectively,
and LA is the surface energy of liquid against air [33]. If a water droplet
is placed on a rough surface with a homogeneous interface, the area of
interface increases with respect to that for a smooth surface. The
Wenzel equation [34] could be used to predict the contact angle:
cos w R f cos 0 15
where w is the contact angle of a water droplet upon a rough solid sur-
face calculated by Wenzel equation. Rf is the non-dimensional surface
factor, equal to the ratio of the surface area to its at projected
area. This Wenzel model also illustrates that a hydrophobic surface
(0 N 90) becomes more hydrophobic with an increase of surface
roughness (Rf).
Table 2
Properties of nanobrous membranes and commercial MD membrane.
Sample Fiber diameter (nm) Membrane thickness (m) Mean pore size (m)
S0 81 0.1
S1 460 160 94 0.35
S2 490 135 97 0.38
S3 510 175 92 0.42
S4 580 190 98 0.49
179
Thus, the addition of the PTFE micro-powders increased the static
contact angle 0 since PTFE has a lower surface energy (19 dyn/cm)
than PVDF (25 dyn/cm) according to Eq. (2). Furthermore, the AFM im-
ages shown in Fig. 4 indicated that the average surface roughness (Ra)
increased from 276 nm to 472 nm by changing the PTFE content from
0 wt.% to 12 wt.%, which further increased the water contact angle w.
The dynamic contact angle of these membranes is shown in Fig. 5.
The result shows that the water contact angle of all the membranes de-
creases slightly over the entire time period, with the smallest decrease
coming from the membrane dope solution containing 12 wt.% PTFE
micro-powders (S4). This indicates that the membranes with the
highest PTFE content are able to retain their hydrophobicity over a lon-
ger period of time.
4.3. Premilinary evaluation of PVDFPTFE nanobrous membranes in
vacuum membrane distillation
A 15 hour continuous separation test was carried out for the PVDF
PTFE nanobrous membrane samples (S1S4) and the commercial PTFE
membrane (S0), the results are summarized in Fig. 6. As shown in
Fig. 6(a), the conductivity of the permeate water maintains at a quite
low level for all the membranes (b 5 S/cm), since the feed solution
can hardly penetrate to the condensed water in VMD. It can be seen
from Fig. 6(b) that the initial permeate ux of the S4 was 18.5 kg/m2 h
for a feed solution containing 3.5 wt.% NaCl, while the feed temperature
and the permeate pressure side were 333 K and 9 kPa, respectively. This
permeation ux is as competitive as under the same MD conditions, the
permeate ux of the commercial PTFE membrane S0 was around 15 kg/
m2 h. The high ux performance for the nanobrous membrane (S4) is
mainly due to the high void volume fraction and interconnected open
structure of the nanober layer compared with the commercial PTFE
membrane.
The uxes of the nanobrous membranes increased slightly from S1
to S4, since the pore size of the nanobrous membranes increased
slightly with PTFE addition. Besides, the uxes of all the nanobrous
membranes decreased over a period operation of around 15 h which
is an indication of pore wetting as reported previously [29]. As time
progressed, more and more pores become wetted, thus resulted in the
decrease of membrane permeability and water ux. The smallest de-
crease was coming from the membrane S4 (b5%), suggesting that the
superhydrophobic surface of nanobrous membranes can alleviate the
pore wetting problem in vacuum membrane distillation. This phenome-
non can be explained by the LEPw values listed in Table 2. The LEPw
values of the nanobrous membranes increased with the increase of the
PTFE content, which was mainly due to the change of WCA (Eq. (1)). Be-
sides, the LEPw value of the superhyphobic membrane S4 is competitive
as the LEPw values of the electrospun nanobrous membrane reported
in the previous literature was around 100 kPa [1820], indicating the su-
perior anti-wetting properties of this membrane in vacuum membrane
distillation.
Due to the superhydrophobic surface and inter-connected structure,
the PVDFPTFE nanobrous membrane S4 exhibited a stable perfor-
mance and satised water quality over the 15 h testing, which shows
the great potential of the PVDFPTFE nanobrous membranes in vacuum
membrane distillation.
Porosity (%) CA () CA reduction (%) LEPw (kPa)
55% 121.5 1.0 6.0 151 2
0.10 72 1.5 130.4 1.5 5.6 84 2
0.13 72 2.0 137.0 1.8 5.1 101 3
0.08 71 2.0 142.3 1.0 4.1 118 3
0.15 69 1.5 152.2 2.0 3.0 137 4
180 Z.-Q. Dong et al. / Desalination 347 (2014) 175183

Fig. 4. Surface morphology and water contact angle of PVDFPTFE nanobrous membrane prepared with different PTFE contents.

Fig. 5. AFM images of surface for PVDFPTFE nanobrous membranes S1 and S4.
 Z.-Q. Dong et al. / Desalination 347 (2014) 175183 181

Fig. 6. Dynamic water contact angle of PVDFPTFE nanobrous membranes and PTFE
commercial membrane.

4.4. Effect of the operating conditions on VMD performance of PVDFPTFE

nanobrous membranes

To further investigate the operating conditions on VMD perfor-

mance of PVDFPTFE nanobrous membrane, the inuence of feed
temperature, permeate pressure and feed ow rate on the water ux
of the superhydrophobic PVDFPTFE nanobrous membrane (S4) was
studied.
As a highly important operating parameter, the effect of feed tem-
perature on the permeate ux of the PVDFPTFE nanobrous mem-
brane was investigated in this study. The variation of the permeate
ux with feed temperatures at different ow rates was summarized in
Fig. 7, the temperatures ranged from 313 K to 343 K at various ow
rates (90 L/h, 54 L/h, 18 L/h), while the pressure at the permeate side
was maintained invariable. A good agreement between the experimen-
tal and theoretical values for vapor uxes was obtained; the exponential Fig. 7. Long time performance of the PVDFPTFE nanobrous membranes and PTFE com-
mercial membrane for VMD application: (a) permeate conductivity; (b) ux.
increase of the MD ux with the increase of the feed temperature is due
to the exponential increase of the vapor pressure (Pm) with membrane
surface temperature (Tm), which increases the transmembrane vapor and the membrane surface is formed due to the large amount of heat
pressure as all the other involved MD parameters are maintained invari- requirement for vaporizing water at the membrane surface, which is
ables. [35] However, considering the limit of membrane material heat called the temperature polarization. Higher ow rate promotes more
resistance and energy consumption for heating, the feed temperature turbulence and eddies in the boundary layer, which would increase the
should be controlled in suitable range.
In VMD, The permeate pressure is an indispensable factor which is
directly related to the transmembrane pressure difference, the inuence
of permeate pressure on water ux was studied and the results are
shown in Fig. 8. The permeate pressure was varied from 3 kPa to
15 kPa at different temperatures (50 C, 60 C and 70 C), while feed
ow rate was maintained constant. It is found that the MD ux de-
creases linearly with the increase of the permeate pressure (Pv), similar
investigations have been reported previously [36]. About 1015 kg/m2 h
water ux decline was observed when the permeate pressure increased
from 3 kPa to 15 kPa, which indicates the obvious effect of permeate
pressure on MD ux. In VMD, both the permeate ux and the trans-
membrane hydrostatic pressure increase with the decrease of the vacu-
um pressure applied in the permeate side (downstream), which results
in the high risk of membrane pore wetting, so the choice of pressure
should be cautious.
Fig. 9 presents the effect of the feed ow rate on the permeate ux of
the PVDFPTFE nanobrous membrane. A practically linear increase of
the MD ux with the feed ow velocity was observed when the feed
ow rate increased from 18 L/h to 90 L/h, the permeate ux improved
about 2 times at 333 K feed temperature and 9 kPa permeate pressure. Fig. 8. Effect of feed temperature on the permeate ux of the PVDFPTFE nanobrous
In VMD process, the difference of temperature between the feed solution membrane.
182 Z.-Q. Dong et al. / Desalination 347 (2014) 175183

membranes in VMD. The inuence of operation parameters, feed temper-

ature, permeate pressure and feed ow rate, on the VMD performance of
the PVDFPTFE nanobrous membrane was also investigated. A good
agreement between the experimental and theoretical values for vapor
uxes was obtained; the results indicated that the VMD ux increased
with the increase of feed temperature and ow rate and decreased with
the increase of permeate pressure.

Nomenclature
h heat transfer coefcient
dh hydraulic diameter of channel (m)
Hv latent heat of vaporization (J/mol)
Jw permeate ux (Lh1m2)
K membrane permeability
M molecular mass (mol/kg)
Nu Nusselt number
P pressure (kPa)
Psat saturated vapor pressure (kPa)
Fig. 9. Effect of permeate pressure on the permeate ux of the PVDFPTFE nanobrous Pr Prendtl number
membrane. r size of membrane pore (m)
R gas constant (Jmol1K1)
transfer coefcients hf, thus results in the increase of temperature (Tm) Re Reynolds number
and vapor pressure (Pm) at membrane surface according to Eqs. (5) T temperature (K)
and (11). Therefore, higher ow rate increases permeate ux (Fig. 10). v solution velocity (m/s)
x molar fraction

5. Conclusions
Greek letters
Superhydrophobic PVDFPTFE nanobrous membranes with stable activity coefcient
MD performance were fabricated by electrospining of PVDFPTFE membrane thickness (m)
blend solution on a PTFE microporous substrate. The effect of PTFE porosity of the membrane
micro-powder contents in the dope solution on the properties of the viscosity of feed solution (Pas)
PVDFPTFE nanobrous membranes was investigated, the water con- density of solution (kg/m3)
tact angle (WCA) and the liquid entry pressure (LEPw) of the mem- pore tortuosity
branes increased signicantly as the PTFE concentration increased. The
highest water contact angle 151.2 was obtained at PTFE concentration
12% due to the hierarchical micro/nanostructure membrane surface.
Subscripts
Both the ber diameter and pore size of the nanobrous membranes
b bulk
increased slightly as the PTFE micro-powder concentration increased
f feed
in the dope solution, due to the increase of dope solution viscosity.
g gas
The long time performance of the PVDFPTFE nanobrous mem-
m membrane surface
branes for VMD application was studied. The superhydrophobic
s porous sub-layer
PVDFPTFE nanobrous membrane maintained a stable ux of
t nanobrous top-layer
18.5 kg/m2 h and salt rejection higher than 99.9% after a 15 h continuous
v vacuum side
separation test, suggesting the great potential of PVDFPTFE nanobrous

Acknowledgments

The authors thank for the nancial support by the Key Technology
R&D Program of Shanghai Committee of Science and Technology in
China (11DZ1205201), Special Project of the Development and Industri-
alization of New Materials of National Development and Reform Com-
mission in China (20132548), the Fundamental Research Funds for the
Central Universities (WA1214062) and the First-class General Financial
Grant from the China Postdoctoral Science Foundation (2013M540336).

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