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Procedia Materials Science 11 (2015) 370 375

5th International Biennial Conference on Ultrafine Grained and Nanostructured Materials,

UFGNSM15

Effect of Salt Additives on the Fabrication of Poly (vinylidene

fluoride-co-hexafluropropylene) (PVDF-HFP) Nanofiber
Membranes for Air Gap Membrane Distillation
A. Hemmata,*, S. M. Ghoreishia, J. Karimi Sabetb
a
Department of Chemical Engineering, Isfahan University of Technology, Isfahan, Iran
b
NFCRS, Nuclear Science and Technology Research Institute, Tehran, Iran

Abstract

In the past few years, application of electrospun nanofiber has gained intensive attention for membrane distillation (MD) that
exhibit promising results. In this study the effects of three salt additives including calcium carbonate (CaCO3), lithium chloride
(LiCl) and calcium chloride (CaCl2) on the morphology, hydrophobicity, porosity and permeation performance of poly
(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) nanofiber membranes were investigated. Scanning electron
microscopy (SEM), geniometer, gravimetric method and air gap MD (AGMD) setup were used to characterize the resultant
PVDF-HFP membranes. It was observed that addition of LiCl and CaCl 2 improved the electrospinability of polymer dope
solution and changes the morphology of fibers from beaded fiber to a uniform fiber structure. Also the membrane made from the
dope with LiCl as the additive salt possessed the highest porosity of % 89. The membrane hydrophobicity was affected less by
CaCO3 as compared with LiCl and CaCl2. The synthesized membrane was applied in desalination via air gap membrane
distillation, in which a water permeation flux of 13.6, 12.2 and 9.8 Lh -1m-2 were obtained when LiCl, CaCl 2 and CaCO3 was used
as the additive, respectively.
2015Published
2015 The Authors. Published
by Elsevier Ltd. by
ThisElsevier Ltd.
is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of UFGNSM15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of UFGNSM15
Keywords: Electrospun nanofiber membrane; Membrane distillation; Polyvinylidenefluoride co - hexafluoropropylene (PVDF-HFP); Calcium
Carbonate (CaCO3); Lithium Chloride (LiCl); Calcium Chloride (CaCl2).

* Corresponding author. Tel.: +98-938895-2260.

E-mail address: a.hemmat@ce.iut.ac.ir

2211-8128 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of UFGNSM15
doi:10.1016/j.mspro.2015.11.132
 A. Hemmat et al. / Procedia Materials Science 11 (2015) 370 375 371

1. Introduction

Fabrication of polymer nanofibers with large specific surface area has been attracted increasing attention in the
last decade. Compared to the conventional fiber drawing, electrospinning is an effective and versatile method to
produce the nanofibers with controllable composition characteristic. More than 100 polymers, both synthetic and
natural, have been successfully electro-spun into nanofibers. This type of nano-scale materials are employed in
various applications such as textile industry, air cleaning, drug delivery, energy storage, affinity membranes and
enzyme immobilization, Burger et al. (2006).
Recently, electrospun nanofiber membrane (ENMS) exhibit high potential for application in desalination of
seawater by membrane distillation (MD). In the electrospinning process, under the electrical field ceaselessly jet is
ejected from the dangling droplet of polymer solution or melts at the needle tip and then stretching, elongated and
shrivel to form polymer nanofiber on the grounded collector. In particular, hydrophobicity of polymeric material
significantly enhanced at the electrospun nanofiber surface, which is one of the necessary properties for membrane
distillation. Furthermore, the higher porosity of these membranes provides large spaces for evaporation and
diminishes the heat loss conduction. Tijing et al. (2014) wrote a review on the trends in electrospun nanofiber
membranes and their suitability for MD and reported the use of nanofibrous membranes is still in its infancy for MD
application. Recently, electrospinning has been developed to fabricate polyvinylidenefluoride-co-
hexafluoropropylene (PVDF- HFP) nanofibers and fibrous films for applications in membrane distillation, Lalia et
al. (2013).
It must be mentioned morphology and measure of ENMS are more controllable than the phase inversion hollow
fiber membranes, which is obtain by varying the solution properties such as concentration, surface tension and
conductivity and processing condition such as applied voltage, flow rate, tip-to-collector distance, Essalhi and
Khayet (2013). Essalhi and Khayet (2014) investigated effects of the polymer concentration on the characteristics
and DCMD performance of PVDF ENMs and reported bead-free ENMs prepared with higher concentration exhibits
higher void volume fractions and DCMD performance than the ENMs with beads. Lalia et al. (2013) show the effect
of different fiber size obtain using different concentrations of polymer solution on the pore size distribution (PSD),
porosity and hydrophobicity of the membrane when investigated on the DCMD performance of PVDF-HFP ENMs.
In addition, it was found that a small amount of salt additives in the polymer solution improved the
electrospinability and changes the morphology of ENMs from beaded fiber to a uniform fiber structure. Liao et al.
(2012) fabricated a PVDF membrane by electrospinning and reported that the addition of 0.004wt% LiCl inorganic
salt additive resulted in formation of bead-free nanofibers with relatively thinner and more uniform diameters. But,
the systematic effects of the salt additives on the MD performance are not studied yet although the influence of this
parameter on the nano-fibers characteristics has been previously reported in various studies.
The current work aims to fabricate electrospun PVDF-HFP nanofiber membranes and investigate the impact of
three salt additives including calcium carbonate (CaCO3), lithium chloride (LiCl) and calcium chloride (CaCl2) on
the morphology, hydrophobicity, porosity and permeation performance of membranes. The prepared membranes
were characterized by different techniques and applied for desalination by air gap membrane distillation (DCMD)
using salt (NaCl) aqueous concentrations. It is expected that this study can help have a better understanding of
optimal electro-spinning conditions to fabricate new nanofiber membranes suitable for membrane distillation with
enhanced performance.

2. Experimental

2.1. Materials

PVDF-HFP (Mw = 455 kg/mol, Mn = 110 kg/mol) and the mixed solvents of N,N-dimethyl acetamide (DMAC)
and acetone purchased from SigmaAldrich Chemical Co. Calcium carbonate (CaCO3), lithium chloride (LiCl) and
calcium chloride (CaCl2) were adopted as additives into the dope solution. Isopropyl alcohol (IPA) was used to
determine the porosity () of the ENMs and sodium chloride (NaCl) used in AGMD experiments were also
purchased from Sigma-Aldrich Chemical Co.
372 A. Hemmat et al. / Procedia Materials Science 11 (2015) 370 375

2.2. Polymer solutions Preparation and characterization

The polymer solution was prepared by dissolving 20 wt% PVDF-HFP with/without additive in a mixture of
DMAC and Acetone at a weight ratio of 6 to 4. The PVDF HFP membranes were prepared by electrospinning a
solution containing of each additive. A 20 wt% PVDF solution without any additive was also electrospun and used
as the control membrane. The composition of the dope solution for electrospinning corresponding to the membrane
samples M1M4 is presented in Table 1. All solutions were stirred for at least 1 day at 650C and degassed at room
temperature for overnight.

Table 1. Composition of electrospinning dope solution.

Sample PVDF (wt %) solvent Additive

M1 20 DMAC/ Acetone NA
M2 20 DMAC/ Acetone LiCl, 0.02 wt%
M3 20 DMAC/ Acetone CaCl2, 0.02 wt%
M4 20 DMAC/ Acetone CaCO3, 0.02wt%

The PVDF-HFP solution was holed in a 10 ml glass syringe that shoved by a syringe pump (New Era Pump
System, NE1000, USA) in the controlled flow rate of 1.2 mLh-1. The glass syringe was connected to stainless steel
needle (22gauge, O.D= 0.7 mm, and I.D= 0.4 mm) by a PTFE pipe. A potential difference from of 13 kV was
applied across a distance of 18 cm between the tip of the needle and the grounded collector through high-voltage
power supply (Gamma High Voltage Research, RR60, USA). The relative humidity of electrospining was 16% and
the temperature was 28oC. The electrospun membranes of PVDF-HFP to ensure that all solvents have been
evaporated completely were placed in an oven under vacuum at 60 oC for overnight.

3. Result

3.1. Characterization of the PVDFHFP ENMs

The SEM images of the electrospun nanofibers after preparation with different salt additive are shown in Fig. 1.
The fiber diameters and average pore size of the membranes were determined from the SEM image using the
UTHSCSA Image Tool 3.0 (University of Texas Health Science Center in San Antonia). The fiber diameters and
average pore size for the various membranes are shown in Table 2. (All data are mentioned as mean standard
deviation (SD). The Levels of significance was determined from the Students t-test (n = 20). Differences were
considered statistically significant when the P-value is less than 0.05 at 95% level of confidence). The membrane
M1 spun without any additive exhibit beaded nanofiber with various diameters in a wide distribution (Fig. 1(a)). In
contrast, the membranes M2 and M3 made of dope solution with LiCl and CaCl2 as an additive has bead-free
nanofibers with relatively thinner and more uniform diameters as shown in Fig. 1(b,c). For M4, addition of CaCo3
in the dope solution has lower effect on the morphology of electrospun nanofiber in comparison with LiCl and
CaCl2 and combination of fibers and beads is observed.
The formation of desired fiber morphology is critically influenced by the viscoelasticity of the solution, charge
density of electrospinning jet and surface tension of the solution that this factors can be influenced by additives into
the polymer solution. The PVDF-HFP solution without any additive has low conductivity as 3.07 scm-1. After the
addition of small amount of salt molecules, since the ionic charge of molecules have a direct relation with the
electrical conductivity of the solution, the conductivity of PVDF-HFP solution were increased significantly into
44.71 scm-1, 45.31scm-1 and 31.25scm-1 for LiCl, CaCl2 and CaCo3 , respectively. A higher conductive
polymer solution can generate a higher charge density on the surface of the electrospinning jet. Since the charge
density of electrospinning jet determines the over tension in fibers and higher charges result in a larger stretching
and elongation, therefore, the diameters of nanofibers become thinner and causing a reduction in the bead formation.
 A. Hemmat et al. / Procedia Materials Science 11 (2015) 370 375 373

Moreover, the salt ions with a smaller atomic radius such as chloride ions have a higher charge density and mobility
under applied external electric field, thus generating a larger elongation force, Zong et al. (2002).

Table 2. Fiber diameter, pore size, porosity and contact angle of the electrospun nanofiber membranes.

sample Diameter (nm) Pore size ( m) Porosity (%) Contact angle

M1 343129 1.680.28 611.1 136.02.1
M2 25159 1.630.19 891.4 129.21.3
M3 29392 1.570.24 871.8 127.91.5
M4 312151 1.641.1 761.5 133.32.6

The void volume fraction () for all the prepared PVDFHFP ENMS are shown in Table 2. The calculated
porosity of electrospun membranes are in the range of 61-89%. MD membrane porosity is reported to be from 35%
to as high as 93%, Essalhi and Khayet (2013). Lalia et al. (2014) reported a porosity of 90 5% range for PVDF-
HFP electrospun membrane. It was observed that the prepared ENMs with the salt additive, M2, M3 and M4, have
higher porosity in comparison with M1 membrane. This result is attributed to the presence of beads. The observed
increase of by addition of salts may be attributed to the decrease of the bead density and the increase of the fibrous
network. The highest value is obtained for the M2 membrane.
Also the average water contact angle of the membrane samples is shown in Table 2. It was observed a slightly
higher contact angle of the PVDF- HFP ENMs with structures containing beads (M1, M4) than the bead-free ENMs
(M2, M3). In general, the water contact angle seems to decrease with the addition of the salts due to the decrease of
the total beads density. It can be seen the prepared membranes showed water contact angle higher than 120
(CA>120), which good agreement by the range reported for PVDF-HFP membranes.

Fig. 1. SEM images of PVDF-HFP membranes prepared with (a) 12 wt% PVDF; (b) 12 wt% PVDF + 0.2 wt% CaCO3;
(c) 12 wt% PVDF + 0.2 wt% LiCl; and (d) 12 wt% PVDF + 0.2 wt% CaCl2, respectively.
374 A. Hemmat et al. / Procedia Materials Science 11 (2015) 370 375

Fig. 2. AGMD flux of samples M1M4 as function of feed temperature (T f).

3.2. Membrane performance by AGMD

The electrospun membranes M1-M4 were tested in the AGMD setup to examine their potential for membrane
distillation application. Fig.2 shows the AGMD permeate flux as a function of inlet feed temperature (T f) for a feed
solution containing 3.5 wt% NaCl. As expected, the membranes flux increases when the feed temperature increases.
Similar results are observed in previous publications, Qtaishat et al. (2009), Bonyadi et al. (2007). At all the inlet
feed temperature tested, it was noted that the water flux was highest for M2 and lowest for M1. The difference could
be due to the larger porosity of M2. High porosity membrane exhibit more evaporation surface area or more pore
channels for diffusion that lead to higher permeate flux. Maximum flow rates achived 13.6 L/m 2h for M2 at a
maximum Tf of 80oC and feed concentrations of 3.5 wt%.

4. Conclusion

In the present work, the effects of three salt additives including calcium carbonate (CaCO3), lithium chloride
(LiCl) and calcium chloride (CaCl2) on the morphology and permeation performance of PVDF-HFP membranes
were studied. It was found addition of small amount of salt additive changes the morphology of fibers from beaded
fiber to a uniform fiber structure. Based on the SEM images, the contact angle of PVDF-HFP membrane decrease
with the addition of salt and thus membrane M1 without any salt additive has the highest contact angle, 136.0,
compared to other membranes. Also, it was observed that the prepared ENMs with the salt additive, M2, M3 and
M4, have higher porosity in comparison with M1 membrane. The highest porosity of 89% is obtained for the M2
membrane with LiCl as the additive salt. The PVDFHFP electrospun nanofiber membrane can be used in AGMD
to produce potable water from 3.5 wt% NaCl feed aqueous solution, where the water flux was found to be 13.6
L/m2h for M2 membranes with LiCl as the additive salt.

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