Fibers and Polymers 2012, Vol.13, No.

6, 698-702
698
A Study of Hydrophobic Electrospun Membrane Applied in Seawater
Desalination by Membrane Distillation
Ching-Iuan Su*, Jyun-Han Shih, Meng-Shun Huang
1
, Chih-Ming Wang,
Wun-Ching Shih, and Yen-sheng Liu
Department of Materials Science and Engineering, National Taiwan University of Science and Technology,
Taipei, 10607 Taiwan, Republic of China
1
Material and Chemical Research Laboratories, Industrial Technology Research Institute, Hsinchu 30011,
Taiwan, Republic of China
(Received October 4, 2011; Revised January 11, 2012; Accepted January 13, 2012)
Abstract: In this study, two composite nanofibrous membranes of Polyvinylidenefluoride (PVDF) and [poly(vinylidenefluoride-
co-hexafluoropropylene)] (PVDF-co-HFP) prepared by the electrospinning process were employed in a direct contact
membrane distillation (DCMD) system. We changed the pump flow rate and temperature difference to examine their effects
on permeate flux and salt rejection. The SEM observations, porosity analyzer technique, and contact angle measurement
indicated the nanobrous membrane with an average fiber diameter of 170 nm and maximum pore diameter distribution of
0.3 m is the best membrane for the DCMD system. However, the ability of the hydrophobic membrane affects the filtration
efficiency of the DCMD system. The contact angle of the PVDF-HFP electrospun membrane (128
o
) shows better
hydrophobic than the PVDF electrospun membrane (125
o
). From the experiment of 12 hours, the salt rejection of PVDF-
HFP (99.9901 %) was better than that of PVDF composite membrane (99.9888 %) and was almost the same as that of the
PTFE commercial membrane (99.9951 %). In addition, the permeate flux of the PVDF-HFP composite membrane is 4.28 kg/
m
2
hr higher than the PTFE commercial membrane.
Keywords: Seawater desalination, Membrane distillation, Electrospinning
Introduction
Many countries and cities around the world suffer from a
scarcity of fresh water. Due to increasing population rates
and enhanced living standards, increasing amounts of fresh
water will be required. The oceans are a major water reservoir
for the earth. The earths water is seawater. The ratio is about
97 % with the remaining 2 % locked in glaciers and icecaps.
Readily available sources of fresh water account for less
than 0.5 % of the earths total water supply [1].
The desalination processes has been classified into two
major categories: (1) thermal (phase change) (2) membrane
separation process. Some of the thermal processes include
MED, TVC, MSF, and MVC technologies. Membrane based
processes include reverses osmosis (RO), and electro
dialysis(ED). However, membrane distillation lies between
the membrane and thermal process [2,3].
Currently, many countries use reverse osmosis (RO)
operations to treat brackish water. However, RO plants typically
recover only 70-75 % of the feed water, and the remaining
25-30 % is saline or brine and RO concentrate. Otherwise,
RO concentrate must find a disposal route. In this situation,
one possible remedy to increase water recovery is by passing
the RO concentrate through an additional process such as
membrane distillation (MD) desalination technology [4,5].
Membrane distillation is a new seawater desalination
technology, and its future is encouraging. The driving force
for desalination is the difference in temperature either side of
a membrane. Membrane distillation uses less energy, is
cheaper, and has many application areas. Membrane distillation
has been applied for water desalination in the nuclear
industry, chemical industry, textile industry, pharmaceutical
and biomedical industries, water reuse, food processing such
as milk and juice concentration, and biomedical applications
such as water removal from blood and treatment of protein
solutions [6,7].
Although membrane distillation has many advantages, the
membrane distillation process is not yet commercialized for
large-scale desalination plants and equipment systems. The
reason is the relatively lower permeation flux compared to
the production of the acknowledged commercialized desalina-
tion technologies such as reverse osmosis. Therefore, many
studies have begun to design a new type of membrane for
membrane distillation [8].
In this study, two composite nanofibrous membranes of
PVDF and PVDF-co-HFP prepared using electrospinning
were employed in a direct contact membrane distillation
(DCMD) system. We changed the pump flow rate and
temperature difference to investigate their effects on permeate
flux and salt rejection. In terms of achieving the best
solution, low cost, high flux and durability are important and
can be achieved by a porous hydrophobic membrane.
Experiment
Preparation of the Electrospun Membrane and the
Optimum Conditions
PVDF (Mw 275,000) and PVDF-co-HFP (Mw 55,000) *Corresponding author: cysu@mail.ntust.edu.tw
DOI 10.1007/s12221-012-0698-3
Electrospun Membrane Applied in Seawater Desalination Fibers and Polymers 2012, Vol.13, No.6 699
was supplied by Taiwan Tong-Hwa Synthetic Fiber Co., Ltd.
in pellets and dissolved in N, N-Dimethyl-Formamide
(DMF) to prepare the spinning solution. The nanofiber
membrane combined the high tenacity spunbond nonwoven.
This membrane is an electrospun nanofiber nonwoven
membrane which is spunbond to form a sandwich structure
of the folder into a SES (Spunbond- Electrospun- Spunbond)
composite nanofiber membrane. The conditions of the
prepared electrospun membrane are: 23 wt% PVDF solution
concentration, 17 wt% PVDF-co-HFP solution concentration,
8/2 DMF/Acetone (ratio): 15 cm spinning distance between
the spinneret and collecting net, 30 kv applied voltage, 1 ml/
hr pump flow rate, 1000 rpm cylinder rate collection, and
3 ml collectable amount in the cylinder (spinning liquid).
Specifications of Commercial PTFE Microfiltration
Membrane
We used the commercial microfiltration membrane to
compare with the electrospun nanofiber membrane. Table 1
shows the commercial PTFE membrane specifications.

DCMD Apparatus
Figure 1 is the schematic diagram of the DCMD apparatus.
The system was horizontally installed. The feed and permeate
were separated by a hydrophobic porous membrane. The
effective area of the membrane was 49 cm
2
. The permeate
vapor is condensed by liquid in direct contact with the
permeation side of the membrane and colder than the feed.
The cold reservoir possesses a double wall. It contained the
cold RO water. The system has four indicators to monitor the
temperature difference of the DCMD module. The purity of
the water was determined through water conductivity using
an electrical conductivity meter. We used the electron balance
to record the weight and calculate the permeation flux.
DCMD Module Parameters Setting
The hot side of the DCMD module feeds 3 % NaCl
solution (50 mS/cm). We fixed the bulk temperature difference
at 45
o
C. We investigated the effect of the flow rate (105,
140, 175, 210, and 245 ml/min) on permeation flux, and
selected the optimum flow rate to learn the effect of bulk
temperature at 25
o
, 35
o
, 45 and 55
o
C on permeation flux.
Results and Discussion
Characteristics of Nanober Membranes
The morphologies of nanober membrane electrospun from
different polymer solutions are shown in Figure 2. The ber
diameters based on the SEM observations are listed in Table
2. As shown in Table 2, the nanofiber diameter, basis weight,
and thickness of the PVDF-co-HFP electrospun membrane
were significantly smaller than the PVDF electrospun
membrane. Although the porosity of PVDF electrospun
membrane was marginally larger than the PVDF-co-HFP
electrospun membrane, the PVDF electrospun membrane
was too thick, which could affect the mass and heat transfer
in the DCMD system. The water contact angle measurements
on both the PVDF and PVDF-co-HFP electrospun membrane
are shown in Figure 3. As shown in Figure 3, the contact
Table 1. Specifications of commercial PTFE microfiltration
membrane
Commercial PTFE microfiltration membrane
Porosity (%) 62 %
Mean pore size (m) 0.2
Pore size distribution (m) 0.1~0.35
Basis weight (g/m
2
) 55.4
Thickness (mm) 0.05
Contact angle (
o
) 115
Figure 1. Schematic diagram of the DCMD apparatus.
Table 2. Characteristics of the nanober membranes
Membranes
Characterization
PVDF PVDF-co-HFP
Average diameter (m) 220 173
Porosity (%) 95 90
Thickness (mm) 0.228 0.055
Basis weight (g/m
2
) 19.2 13.52
Water contact angle (
o
) 125 128
Figure 2. SEM images of the electrospun nanober membranes.
700 Fibers and Polymers 2012, Vol.13, No.6 Ching-Iuan Su et al.
angle of the PVDF-co-HFP electrospun membrane (128
o
)
show better hydrophobic than the PVDF electrospun
membrane (125
o
). However, the ability of the hydrophobic
membrane affects the filtration efficiency in the DCMD
system, so PVDF-co-HFP.
Influence of Pore Size
Using capillary flow porometer (CFP-1200AE, PMI)
measurement (ASTM F316-80 and SAE ARP901) [9], the
mean pore size and the pore size distribution of the
electrospun membrane was measured. Figure 4 shows the
analyses of the electrospun membrane pore size distribution.
The mean pore size of PVDF electrospun membrane was
0.39 m. The range of the PVDF electrospun membrane
pore size was very wide, varying from 0.21 to 0.82 m. The
maximum peak of the pore size distribution was 20 %. The
mean pore size of PVDF electrospun membrane was 0.34 m.
The range of PVDF-co-HFP electrospun membrane pore
size was smaller than the PVDF electrospun membrane,
varying from 0.21 to 0.69 m. The maximum peak of the
pore size distribution was more focused and the distribution
was 37 %. The above two results show the PVDF-co-HFP
electrospun membrane has the better pore characteristic and
structure. It is therefore the most suitable for the membrane
distillation system.
Effect of Flow Rate on Permeation Flux
Figure 5 shows the results of different pump flow rates on
permeate flux. We fixed the bulk temperature difference at
45
o
C and changed the Pump flow rate (105, 140, 175, 210,
and 245 ml/min). As the flow rate increased 210 to 245 (ml/
min), the PVDF-co-HFP electrospun membrane curves
appeared to decline. In addition, the PVDF electrospun
membrane curves appeared to be a linear curve. At the flow
rate of 210 ml/min, the maximum permeation flux achieved
was 10.9 kg/m
2
hr for the PVDF-co-HFP electrospun membrane
and 10.1 kg/m
2
hr for the PVDF electrospun membrane.
With a flow rate of 140 ml/min, the permeation flux of the
PTFE commercial membrane reached the limit, which is
about 4.5 kg/m
2
hr. Since the pump flow rate of 210 ml/min was
the optimal condition, we selected this condition to precede
the next temperature difference on the permeation flux.
Effect of Bulk Temperature Difference on Permeation
Flux
Figure 6 shows the effect of bulk temperature difference
on permeation flux. The permeation flux of the electrospun
membrane and PTFE commercial membrane increases
exponentially with increasing temperature difference. For
Figure 3. Images of water droplets on electrospun membranes.
Figure 4. Analyses of the electrospun membrane pore size
distribution.
Figure 5. Effect of flow rate on permeation flux.
Figure 6. Effect of bulk temperature difference on permeation
flux.
Electrospun Membrane Applied in Seawater Desalination Fibers and Polymers 2012, Vol.13, No.6 701
the bulk temperature difference at 55
o
C, permeation flux of
PVDF-co-HFP and PVDF electrospun membrane 13.28 kg/
m
2
hr and 12.44 kg/m
2
hr were achieved, and the permeation
flux of PTFE commercial membrane was 9 kg/m
2
hr. This
resulted in the maximum permeate flux of PVDF-co-HFP
electrospun membrane being 0.84 kg/m
2
hr higher than the
PVDF electrospun membrane. Note, it was 4.28 kg/m
2
hr
higher than the PTFE commercial membrane. This is because
the porosity of the PVDF-co-HFP electrospun membrane
(99 %) is higher than the PVDF electrospun membrane
(95 %). In addition, the porosity of both electrospun membranes
is much higher than the PTFE commercial membrane
(62 %). Consequently, the electrospun membrane with the
higher porosity has the higher permeation flux.
Water Quality
Figure 7 shows the performance of the DCMD system on
water conductivity over 12 hours. [The brine side feed 3 %
NaCl solution (50 mS/cm). The permeate side feed RO
water (10.5 S/cm).] During the 12-hour experiment, the
conductivity of the PVDF-co-HFP and PVDF electrospun
membrane decreased from 10.5 S/cm to 5.1 S/cm and
5.81 S/cm. In addition, the conductivity of the PTFE
commercial membrane decreased from 10.5 S/cm to
2.6 S/cm. Consequently, the water quality of PTFE was the
best, followed by PVDF-co-HFP, and PVDF was the worst.
This result is due to the PTFE commercial membrane pore
size distribution (0.1-0.35 m) being smaller than the former
two electrospun membranes (0.2-0.65 m for PVDF-HFP
and 0.2-0.8 m for PVDF). The larger pore size distribution
will cause more ions to permeate the membranes, resulting
in worsened water quality. However, the water contact
angles of PVDF-HFP (128
o
) and PVDF (125
o
) are higher
than that of PTFE (115
o
), therefore the water quality of both
former electrospun membranes is kept at a better standard
level.
Salt Rejection
Salt rejection was calculated according to equation (1) as
follows:
Salt rejection (%)
=[Brine concentration (%)Permeate produced
concentration (%)] / Brine concentration (%)
=[Brine conductivity (%)Permeate produced
conductivity (%)] / Brine conductivity (%) (1)
The Table 3 shows the salt rejection of desalination during
the 12-hour experiment. As shown in Table 4, the salt
rejection of PVDF-co-HFP and PVDF electrospun membrane
was 99.9901 % and 99.9888 %. The salt rejection of PTFE
was 99.9951 %. From this 12-hour experiment, the salt
rejection of PVDF-co-HFP was better than that of the PVDF
electrospun membrane, and was almost the same as that of
the PTFE commercial membrane.
Comparison of Water Produced by DCMD with National
Secondary Drinking Water Standards (U.S. Environ-
mental Protection Agency)
National Secondary Drinking Water Standards (U.S.
Environmental Protection Agency) are non-enforceable
guidelines regulating contaminants that may cause cosmetic
effects (such as skin or tooth discoloration) or aesthetic
effects (such as taste, odor, or color) in drinking water. EPA
recommends secondary standards to water systems but does
not require systems to comply. However, states may choose
Figure 7. Water conductivity during 12-hour experiment.
Table 3. Salt rejection of membranes
Membrane categories Salt rejection (%)
PVDF-co-HFP electrospun membrane 99.9901
PVDF electrospun membrane 99.9888
PTFE commercial membrane 99.9951
Table 4. Comparison of water produced by DCMD with national
secondary drinking water standards
Contaminant Secondary standard DCMD
Aluminum 0.05 to 0.2 mg/l 0.05 mg/l
Chloride 250 mg/l 1.77 mg/l
Color 15 (color units) -
Copper 1.0 mg/l -
Corrosivity noncorrosive noncorrosive
Fluoride 2.0 mg/l 0.05 mg/l
Foaming agents 0.5 mg/l -
Iron 0.3 mg/l 0.026 mg/l
Manganese 0.05 mg/l -
Odor 3 threshold odor number -
pH 6.5-8.5 7.7
Silver 0.10 mg/l -
Sulfate 250 mg/l 1.13 mg/l
Total dissolved solids 500 mg/l 120 mg/l
Zinc 5 mg/l -
Note: the symbol of means that the contaminant is not test in
this item.
702 Fibers and Polymers 2012, Vol.13, No.6 Ching-Iuan Su et al.
to adopt them as enforceable standards.
The test results are shown in Table 4, comparing water
produced by DCMD with National Secondary Drinking
Water Standards. Table 4 shows the contaminant of the water
produced by DCMD prepared in this experiment is much
lower than the National Secondary Drinking Water Standards.
Therefore, the PVDF-HFP electrospun membrane prepared
in this experiment is used in DCMD, and will be an ideal
membrane.
Conclusion
We employed PVDF-co-HFP to prepare water using
electrospinning and successfully applied it in a direct contact
membrane distillation (DCMD) system. From this 12-hour
experiment, the salt rejection of PVDF-co-HFP (99.9901 %)
was better than that of the PVDF composite membrane
(99.9888 %) and was almost the same as that of the PTFE
commercial membrane (99.9951 %). Consequently, the PVDF-
co-HFP composite nanofibrous membrane significantly
increased the permeation flux and salt rejection compared to
the PVDF composite nanofibrous membrane in the DCMD
system.
Acknowledgments
The authors thank the Department of Industrial
Technology, Ministry of Econmic Affairs, and National
Science Council (NSC 99-2221-E-011-011), ROC, for
financial support of this research.
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