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Tailoring PES Nanofiltration Membranes through Systematic Investigations on

the Effect of Prominent Design, Fabrication and Operational Parameters

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DOI: 10.1039/C5RA05985B

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RSC Advances
PAPER

Tailoring PES nanofiltration membranes through

systematic investigations of prominent design,
Cite this: RSC Adv., 2015, 5, 49080
fabrication and operational parameters
Mohammad Amin Alaei Shahmirzadi,a Seyed Saeid Hosseini,*a Guoling Ruanb
and N. R. Tanc

Received 3rd April 2015
Accepted 13th May 2015
DOI: 10.1039/c5ra05985b
www.rsc.org/advances
Design and fabrication of nanofiltration (NF) membranes with the desired characteristics and separation
performance is of paramount importance. In this study various asymmetric nanofiltration membranes
were designed and fabricated using poly(ethersulfone) (PES) via phase inversion technique. The effects of
variation in polymer concentration, solvent type, additives in the dope solution and composition of
coagulating agent were studied as the selected design parameters. The effects of variation in solvent
evaporation time, coagulation bath temperature, casting speed (shear rate) and membrane thickness
were also investigated as the selected fabrication parameters. The results obtained reveal that increasing
the polymer concentration, promoting a delay in demixing through a change of solvent and composition
of coagulating agent as well as decreasing the coagulation bath temperature, increasing the solvent
evaporation time and membrane thickness all result in NF membranes with less overall porosity and
mean pore size, lower water flux and higher salt rejections. Furthermore, addition of hydrophilic organic
acids, (e.g., ascorbic and citric acids) in the dope solution and incrementally increasing the casting shear
rate promote overall porosity of the membrane, water flux and salt rejection. Membranes derived from
PES/N-methyl-2-pyrrolidone (30/70 wt%) could offer maximum salt rejections of 47.35% and 99.84% for
sodium chloride and magnesium sulfate, respectively. The pure water flux in the membranes could be
enhanced up to 54.88 l m
2 h
1 by addition of 1 wt% citric acid into the dope solution. In terms of
operational parameters, increase in both feed pressure and pH could enhance the membrane flux and
salt rejections. The findings in this study provide useful guidelines and methods for the design and
fabrication of high performance asymmetric NF membranes with the desired microstructure, productivity
and separation performance.

size range of about 1–10 nm. The governing mechanisms in NF

1. Introduction
Membrane technology has gained widespread acceptance for a
variety of separation applications ranging from microltration
to gas separation, pervaporation and fuel cells.1–6 Many activi-
ties are in progress in various parts of the world on material
synthesis, membrane fabrication, membrane modication,
process design and development, process modeling and opti-
mization, all aiming to overcome the remaining obstacles and
to improve the competitiveness of the membrane technolo-
gies.7–13 Nanoltration (NF) is a relatively new type of pressure
driven membrane technology that lies between ultraltration
and reverse osmosis.14 NF membranes are employed effectively
for the separation of charged and/or uncharged species in the
a
Department of Chemical Engineering, Tarbiat Modares University, Tehran,
14115-114, Iran. E-mail: saeid.hosseini@modares.ac.ir
b
Institute of Seawater Desalination and Multipurpose Utilization, Tianjin, 300192,
China
c
Research & Development Dept., HOSSTECH Group, Singapore 528844, Singapore
membranes are solution diffusion, Donnan effect, dielectric
exclusion, electromigration or a combination of them.15
Numerous advantages such as energy efficiency, high ux as
well as a higher rejection of multivalent than monovalent
ions15,16 have led to the widespread application of NF
membranes in various industries, including, but not limited to,
water soening,17,18 seawater desalination,19,20 brackish water
treatment,21–23 dye removal,24–26 industrial wastewater treatment
and reuse,27–29 food and beverage processing30 and the phar-
maceutical industry.31
Development of high performance NF membranes requires a
thorough understanding of proper material selection, formu-
lation, design and fabrication procedures in addition to the
adoption of appropriate knowledge and skills. Phase inversion
can be described as a process of making membranes in which
an initially homogeneous polymer solution is transformed into
a solid structure through a complicated, yet controlled proce-
dure. Non-solvent induced phase separation (NIPS), thermal
induced phase separation, evaporation induced phase

49080 | RSC Adv., 2015, 5, 49080–49097 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

separation and vapor induced phase separation are among the Apart from the design parameters, fabrication parameters
well-established phase inversion processes. NIPS is commonly also play an important role in the properties of the resultant
used for fabrication of asymmetric NF membranes. According membranes. For example, the inuence of solvent evaporation
to this procedure, a polymer solution is cast on a proper time was investigated in some previous research.51,52 It was also
substrate, then immersed in a coagulation bath containing a shown that increasing the coagulation bath temperature (CBT)
non-solvent or a blend of non-solvents.32 The non-solvent resulted in an accelerated phase inversion rate and conse-
diffuses into the polymer solution and the solvent escapes quently an improved water ux.53–55 However, in some cases, a
from the polymeric solution to the non-solvent bath, known as decrease of the water ux has been reported.46 The casting
the demixing process, through which a system comprised of a speed also affects the membrane morphology, porosity and pore
polymer rich and polymer lean phases is formed. The former size which is attributed to the alternation of the molecular
results in the formation of a solid membrane matrix, while the orientation caused by the induced shear rate.35,56–58 It was also
latter creates membrane pores.33 shown that the overall thicknesses of the membrane as well as
Essentially, various kinetic and thermodynamic parameters the top layer increased by increasing the casting knife gap.59–61
including selection of polymer, solvent, non-solvent and addi- The main objective of the present research was to perform a
tive to the polymer solution and its composition play important systematic investigation on the effect of key parameters
roles in the properties and characteristics of the ultimate involved in the development of asymmetric NF membranes
membranes.34 from the viewpoint of formation, structural characteristics,
These parameters may generally be classied into two main productivity and separation performance. For this purpose, the
groups of design and fabrication as shown in Fig. 1. Design effect of various design parameters such as polymer concen-
parameters may include material selection, polymer concen- tration in the dope solution, solvent type, additives in the dope
tration in the dope, solvent type, additives in dope solution, and solution, composition of the coagulating agent as well as
composition of the coagulating agent. Various materials various fabrication parameters such as solvent evaporation
including but not limited to polysulfone,35 cellulose acetate36 time, coagulation bath temperature, casting speed (shear rate)
and poly(vinylidene uoride)37 have been used for the prepara- and membrane thickness on the characteristics and perfor-
tion of asymmetric NF membranes. Among them, poly- mance of the membranes were investigated and determined.
(ethersulfone) (PES) has been widely used for the preparation of The effect of feed pressure and pH as operational parameters
a variety of membranes mainly because of its particular char- were also studied in detail. To the best of our knowledge, and
acteristics such as prominent oxidative stability, thermal based on the detailed review and analysis of the previous
hydrolysis stability (Tg  220  C), chemical stability and research, this is the rst comprehensive report on the system-
mechanical stability.38,39 It is also shown that the polymer atic investigation of NF membranes. Furthermore, the effect of
concentration can play a major role in the structure of the the addition of selected hydrophilic additives (i.e., ascorbic and
membrane. A study by Balta et al.40 revealed that the increase in
the polymer concentration led to the formation of NF
membranes with less porosity and less nger-like pores and
consequently decreased water ux and increased salt rejection.
Membranes with different morphologies and performance can
be achieved but it depends on the type and nature of the
solvents and non-solvents used. Various approaches such as
bulk modication, blending, additive embedding, surface
coating, interfacial polymerization, graing (e.g., photon-
induced, gamma ray, electron/ion beam induced, plasma
induced, thermal induced), plasma treatment, immobilization
and surface initiated atom transfer radical polymerisation have
been applied for altering the hydrophobic nature of the PES
derived membranes.41 The use of additives consisting of func-
tional groups has also been considered as a possible technique
for altering the hydrophilicity, surface roughness, surface
charge and the pore size of the membranes.42–44 For example,
pore forming agents, such as poly(vinylpyrrolidone) and poly-
(ethylene glycol) have been added to the polymer solution for
improving the permeability of the membranes.45 Another
effective parameter is composition of coagulating agent. While
water has been the dominant coagulating agent, several types of
additive such as ethanol,46,47 isopropanol,46–48 2-butanol49 and N-
methyl-2-pyrrolidone (NMP)50 have been examined separately or
as additives to water in order to tailor the characteristics of the Fig. 1 Classification of prominent design and fabrication parameters
membranes. involved in the preparation of asymmetric membranes.

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 49080–49097 | 49081
RSC Advances Paper

solution, the dope solutions were held at the ambient temper-

Fig. 2 Chemical structures of (a) PES (b) NMP (c) DMAc (d) ascorbic
acid (e) citric acid.
citric acids) into the dope solution was assessed for the rst
time for PES NF membranes.
ature for about 24 h and then degassed. Then the solutions were
cast onto a glass plate using a semi-automatic lm applicator
with an adjustable gap at controlled temperature and relative
air humidity. The nascent lms on the glass plate were
immersed immediately in the coagulation bath (except in one
case which was used to investigate the effects of the solvent
evaporation time) and remained there for 24 h to allow the
residual solvents to leach out. Finally, the membranes were
stored between two lter papers at room temperature and dried.
The controlled conditions for the membrane formation are
given in Table 1. The effect of various design parameters
including polymer concentration in the dope solution, solvent
type, additive type and amount in dope solution, composition of
coagulating agent as well as fabrication parameters such as
solvent evaporation time, coagulation bath temperature,
casting speed (shear rate) and membrane thickness on the
characteristics and performance of the membranes were
studied systematically.

2. Experimental 2.3. Membrane characterizations

2.1. Materials
Polyethersulfone [PES, Ultrason E 6020 P, molecular weight
(MW) ¼ 58 000 g mol
1] was supplied by BASF (Germany).
N- Methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide
(DMAc) both from Merck (Germany) were used as the solvent for
the preparation of dope solutions mainly because of their good
miscibility with PES. Ascorbic acid (C6H8O6, pKa ¼ 4.10) and
citric acid (C6H8O7, pKa ¼ 3.15) both from Merck (Germany)
were employed as additives for the dope solutions. Sodium
chloride (NaCl) and magnesium sulfate (MgSO4) salts were
obtained from Merck. Ethanol and distilled water were used as
coagulating agents. The chemical structure of the materials
used in this study are illustrated in Fig. 2.
2.2. Membrane preparation
Dope solutions were prepared by dissolving the specied
amounts of PES akes in the respective solvents. Ascorbic and
citric acids were used in the specied amounts to the selected
dope solutions as additives. The solutions were stirred for at
least 24 h at 300 rpm and at room temperature to ensure
complete dissolution. Aer formation of a homogeneous
2.3.1. Morphology analysis. A VEGA (TESCAN, Czech
Republic) scanning electron microscope (SEM) was used for
characterization of the cross-sectional morphology of the
fabricated membranes. The membrane samples were fractured
in liquid nitrogen and then sputtered with gold. ImageJ so-
ware (version 1.48) was used for further analysis of the types and
population of macrovoids in the cross-section of membranes.
2.3.2. Porosity and pore size measurements. Overall
porosity (3) was calculated as a function of the membrane
weight using the following equation:62
w1
w2
3¼ (1)
Alr
where w1 and w2 are the weights (kg) of the wet and dry
membranes, A is the membrane effective area (m2), r is the
density of water (998 kg m
3) and l is the membrane thickness
(m). The Guerout–Elford–Ferry equation (eqn (2)) was used to
determine the mean pore radius (rm) of the membrane using
pure water ux and porosity data:63
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð2:9
1:753Þ  8mlQ
rm ¼ (2)
3ADP

Table 1 The effect of solvent type and polymer concentration in dope solution on the characteristics of the PES NF membranesa

Polymer concentration Membrane thickness Mean pore size Porosity Area fraction Contact angle
Solvent (wt%) (mm) (nm) (%) of macrovoids (%) ( )

NMP 24 125 4.93 55.5 54.96 63.4

27 130 3.19 52.3 — 72.6
30 133 1.20 46.2 40.58 75.5
DMAc 24 100 4.96 58.9 65.78 60.5
27 107 4.09 55.7 — 67.3
30 111 1.64 47.6 48.54 72.9
a
Conditions: casting temperature: 25  3  C; relative air humidity: 30  5%; casting knife gap: 200 mm; casting shear rate: 23.54 s
1; solvent
evaporation time: 0 min; coagulating agent: pure water; coagulation bath temperature: 20  2  C.

49082 | RSC Adv., 2015, 5, 49080–49097 This journal is © The Royal Society of Chemistry 2015
Paper
where m is the viscosity of water (8.9  10
4 Pa s), Q is the
volumetric ow rate of the permeated water (m3 s
1) and DP is
the operating pressure (Pa). The average pore size, rm, was
determined by ltration velocity method, in which the pure
water ux of the wet membrane was measured by applying
pressure (1 MPa) for a limited period.
2.3.3. Contact angle measurements. To evaluate
membrane surface properties, contact angles were measured
using the sessile drop method with a G10 goniometer (KRÜSS,
Germany). Deionized water was used as the probe liquid in all
the measurements. To minimize the experimental error,
contact angle was measured at ve random locations for each
sample at room temperature, and the average value was
reported.
2.4. Performance evaluation
The performance of the membranes was evaluated using a
bench scale set-up as shown in Fig. 3. Rectangular shaped
membrane sheets with an effective surface area of 15 cm2 were
cut and sandwiched between the test cells. The feed was pum-
ped into the cell by using a high pressure pump, owing
tangentially to the membrane surface. The permeate stream was
directed to the permeate tank while the retentate stream
returned to the feed tank. In this way, the concentration of the
feed remains almost unchanged because of the limited amount
of permeate stream. The feed ow rate and stream pressures
were adjusted using a back pressure regulator and by-pass
valves. The following procedure was used in all experiments:
(1) Before starting the experiments, each membrane was
soaked in deionized water for 2 h to provide the required
saturation and wetting in the membrane structure.
(2) Each membrane sheet was rstly subjected to pre-
compaction at 1.5 MPa for 2 h using pure water. However,
pure water permeate ux (J) was measured at 1 MPa and feed
ow rate of 5 l min
1 using eqn (3):
Fig. 3 Cross-flow filtration system: (1) feed tank (2) pump (3) valve (4) by-pass stream (5) pressure gauge (6) membrane module (7) back-pressure
regulator (8) flowmeter (9) retentate stream (10) permeate stream (11) permeate tank (12) temperature control system.
This journal is © The Royal Society of Chemistry 2015
RSC Advances
V
J¼ (3)
A Dt
where V is the volume of permeated water (l), A is the membrane
area (m2) and Dt is the permeation time (h).
(3) The single salt rejection of the membranes was measured
using a synthetically designed salt solution (formula based on
typical seawater properties) containing 10 500 ppm of NaCl and
1300 ppm of MgSO4.
(4) The feed solution was circulated for about 1 h until the
system reached steady state, and then the permeate ux was
measured at 1 MPa and feed ow rate of 5 l min
1. Samples
from the feed and permeate were collected and analyzed sepa-
rately using a standard MIC 99702 conductivity meter (Mic
Meter, Taiwan).
(5) The single salt rejection (R) was determined using eqn (4):
 
CP
Rð%Þ ¼ 1
 100% (4)
Cf
where Cp and Cf are the concentrations of ion in the permeate
and feed, respectively.
3. Results and discussion
3.1. Effect of the polymer concentration in dope solution on
the structure and performance of NF membranes
The effect of polymer concentration in the dope solution on the
water ux and salt rejection of the NF membranes prepared
using NMP and DMAc as solvents is shown in Fig. 4. It can be
seen that polymer concentration has a considerable effect on
the membrane permeation and separation performance.
According to Fig. 4(a), the pure water ux decreased from 38.35 l
m
2 h
1 to 2.78 l m
2 h
1 for the membranes prepared using 24
wt% and 30 wt% PES in DMAc, respectively. Similarly, the pure
water ux decreased from 27.65 l m
2 h
1 to 1.24 l m
2 h
1 for
the membranes prepared using 24 wt% and 30 wt% PES in
NMP, respectively. This can be attributed to the fact that an
RSC Adv., 2015, 5, 49080–49097 | 49083
RSC Advances
increase in the PES concentration results in an increment in
the dope viscosity. This increase in viscosity consequently
brings about a reduction of the solvent and non-solvent
exchange rate, and thus the polymer concentration increases
at the interphase of the dope solution and the coagulating
agent. Thus, smaller amounts of coagulating agent can pene-
trate to the dope solution and the precipitation rate decreases
through delayed demixing. It is well demonstrated that the
instantaneous demixing leads to a nger-like structures, while
delayed demixing leads to a sponge-like structures.64 Fig. 5
presents SEM cross sectional images of membranes prepared
using dopes having different polymer concentrations. It can
clearly be seen that regardless of the solvent type, membranes
formed from a low polymer concentration (i.e., 24 wt%) were
comprised of nger-like macrovoids with interconnections
extended to the bottom of the membranes. However,
increasing the polymer concentration suppressed the forma-
tion of the nger-like macrovoids and created more spongy-
like porous structures. Thus, it can be seen that an increase
in polymer concentrations and delayed demixing resulted in
membranes with lesser porosity, less nger-like pores, lower
mean pore size, while there was a denser and thicker layer on
the top. Data in Table 1 provide a good overview on the trend of
changes in the morphological and structural characteristics of
the membranes as a result of changes in polymer concentra-
tion. The data reveal that an increase in the polymer concen-
tration led to the formation of up to about 11% thicker NF
membranes. Similar results have been reported elsewhere.46
This may arise from the fact that a higher polymer concen-
tration provides less opportunity for the penetration of the
coagulating agent and accordingly less contraction ratio is
achieved because of the slowed demixing rate.
Fig. 4 The effect of PES concentration in the dope solution on (a) pure water flux (b) NaCl rejection (c) MgSO4 rejection of NF membranes
prepared using NMP and DMAc as solvents.
49084 | RSC Adv., 2015, 5, 49080–49097
Paper
On the other hand, by increasing the polymer concentration,
the mean pore size decreased from 4.93 nm to 1.20 nm and
from 4.96 to 1.64 in NF membranes prepared using NMP and
DMAc, respectively. Similarly, the porosity decreased by about
17% and 19% in NF membranes prepared using NMP and
DMAc, respectively. The higher porosity can be attributed to a
higher diffusional exchange between the solvent and coagu-
lating agent at a lower polymer concentration.46 According to
the data in Table 1 and also shown in Fig. 5, an increase in the
polymer concentration produced a reduction in the area frac-
tion of macrovoids in the cross-section of membranes, a
reduced number of macrovoids and turned the overall
membrane morphology into a more spongy-like structure. In
addition, the contact angle of the prepared membrane
increased from 63.4 to 75.5 and from 60.5 to 72.9 in NF
membranes prepared using dope solutions containing 24 wt%
and 30 wt% of polymer in NMP and DMAc, respectively. Sotto
et al.62 determined that increasing the polymer concentration
decreases the solvent and coagulating agent diffusional
exchange rate and thus, the surface porosity and the pore size
decreases. It should be noted that the wettability of the
membrane is inuenced by the membrane material as well as
the surface porosity and roughness. Thus, because the mate-
rials are the same, the greater contact angle of the membrane
prepared using the dope with a higher concentration can be
mainly attributed to the decreased surface porosity.65 In other
words, a higher polymer concentration leads to a lower surface
porosity causing a decrease in the hydrophilicity of the
membrane and the water ux.
The effect of the polymer concentration in the dope solutions
on the performance of NF membranes was investigated in terms
of monovalent and divalent salt rejections. Generally, an
increase in polymer concentration led to improvements in the
This journal is © The Royal Society of Chemistry 2015
Paper
Fig. 5 Cross section SEM images of PES NF membranes: (a) polymer concentration: 24 wt%; solvent: NMP, (b) polymer concentration: 30 wt%;
solvent: NMP, (c) polymer concentration: 24 wt%; solvent: DMAc, (d) polymer concentration: 30 wt%.; solvent: DMAc.
rejection of both NaCl and MgSO4 by the membranes. Accord-
ing to Fig. 4(b), NaCl rejection increased from 23.36% to 47.35%
and from 18.62% to 40.80% in NF membranes prepared using
dope solutions containing 24 wt% and 30 wt% of polymer in
NMP and DMAc, respectively. Membranes gave even higher
rejections for MgSO4. According to Fig. 4(c), MgSO4 rejection
increased from 86.35% to 99.84% and 82.78% to 99.10% in NF
membranes prepared using dope solutions containing 24 wt%
and 30 wt% polymer in NMP and DMAc, respectively. Because of
the negative surface charge of the PES membranes, the sepa-
ration mechanism of these membranes is not only affected by
steric hindrance, but also by charge effect interaction. Accord-
ing to the Donnan effect, if a negatively charged ion is rejected
because of electrostatic surface charge of the PES membrane,
then the counter ion will also have to be rejected to neutralize
the electric charge across the membrane. For salts, an increase
in co-ion charge and a decrease in counter ion charge improve
the rejection of salts.66 Because of the higher charge of sulfate
ions, the rejection of Mg2+ ions also increased because of the
Donnan effect. On the other hand, as reported by Ali et al.,58 the
surface charge density of the membrane increases as the
membrane pore size decreases. As shown in Table 1,
membranes prepared using solutions with high polymer
concentrations possessed smaller pores and high surface
This journal is © The Royal Society of Chemistry 2015
RSC Advances
charge density. Consequently, a smaller pore size increases the
rejection of salts through both physical size sieving and elec-
trostatic repulsion mechanisms.
3.2. The effect of solvent type on the structure and
performance of NF membranes
Several studies have demonstrated the important role of solvent
selection on the membrane properties and performance. This
was also investigated in the present study and the effects of
solvent type on pure water ux and rejection of salts are shown in
Fig. 4. According to Fig. 4(a), membranes prepared using DMAc
as the solvent exhibited higher water ux than those prepared
using NMP. This trend was regardless of the polymer concen-
tration in the dope solution. It should be noted that the differ-
ence between the pure water ux of the membranes prepared by
the two solvents was minimal when the polymer concentration
in the dope solution was 30 wt%. The pure water ux in the NF
membranes prepared using dope solutions containing 24 wt%
and 30 wt% of PES in DMAc was 38.35 l m
2 h
1 and 2.78 l m
2
h
1, respectively. However, the pure water ux in NF membranes
prepared using dope solutions containing 24 wt% and 30 wt%
PES in NMP was 27.65 l m
2 h
1 and 1.24 l m
2 h
1,
respectively. Therefore, the membrane prepared using DMAc
RSC Adv., 2015, 5, 49080–49097 | 49085
RSC Advances Paper

exhibited a higher pure water ux compared to those prepared Table 2 Solubility parameters of the materials and compounds used in
using NMP. As shown by the data in Table 1, this result can be this study
attributed to the higher porosity, lower thickness and hydro-
Solubility parameter (MPa0.5)
philic nature of the membrane prepared using DMAc. As
porosity and hydrophilicity increases and membrane thickness Material/compound dd dp dh dt
decreases, the water permeation through the membrane
PES 19.6 10.8 9.2 24.19
increases.
NMP 18.0 12.3 7.2 22.9
Analysis of the morphology of the membranes can provide DMAc 16.8 11.5 10.2 22.7
useful insights about the effect of solvent type on the properties Water 15.5 16 42.3 47.8
of the membranes. As shown by the cross-sectional SEM images Methanol 15.1 12.3 22.3 29.6
in Fig. 5, switching the solvent from DMAc to NMP enabled Water–methanol (75/25 vol%) 15.4 15.08 37.3 43.07
Water–methanol (50/50 vol%) 15.3 14.14 32.26 38.4
suppression of the number and progress of macrovoids to a
certain extent. Instead, relatively large macrovoids were formed.
The following points provide insights about the effect of
solvent type on the morphology and performance of NF
layer is usually observed with the delayed demixing process.67
membranes:
According to the three phase diagram for water–DMAc–PES and
(1) The solubility parameter and mutual diffusivity between
water–NMP–PES systems (Fig. 6(b)), the theoretical and experi-
the solvent and non-solvent in the coagulation bath are
mental binodal curve of the water–DMAc–PES system is closer
important factors in membrane preparation.67 A smaller
to the polymer–solvent axis than that of the water–NMP–PES
difference between the solubility parameters results in faster/
system. Therefore less water is needed for the precipitation of
instantaneous demixing causing formation of a porous top
PES (instability of polymer lm) in the water–DMAc–PES
layer and nger-like pores in the support layer. However, a delay
system.70 The time to rst precipitation may be almost instan-
in demixing is oen related to the formation of a dense layer.
taneous for the water–DMAc–PES system. The nal structure of
The solubility parameter data for various components are
the membrane depends on whether the delayed or instanta-
shown in Table 2. They indicate that the difference in solubility
neous demixing is dominant. As shown by Fig. 6(b), instanta-
parameters between DMAc and water is the highest and this is
neous demixing occurred for the water–DMAc–PES system
attributed to the fact that the porosity, number of nger-like
when compared to that of the water–NMP–PES system; resulting
pores and mean pore size of membranes prepared using this
in the formation of a thin skin layer and nger-like pores in the
solvent is increased. In addition, the diffusivity coefficient of the
support layer.65
intended solvent and coagulating agent systems was calculated
(3) As reported by Hasbullah et al.,71 the boiling point of the
using the Wilke–Chang equation and is shown in Table 3.
solvent contribute positively to the dope solution viscosity.
According to eqn (5), the diffusivity of solute a into solvent b
Accordingly, the higher boiling point of NMP (202  C) compared
(Da–b(cm2 s
1)) can be described by:
to that of DMAc (166  C) results in dope solutions with
ð4b Mb Þ0:5 T increased viscosity. As mentioned previously, this increase in
Da
b ¼ 7:4  10
11 (5) viscosity resulted in a reduction of the solvent and non-solvent
hb Va 0:6
exchange rate and delayed demixing occurred. Consequently, a
where 4, m, Va, Mb and T are the association factor, viscosity membrane with lower porosity, less nger-like pores and lower
(g cm
1 s
1), molar volume at boiling point (cm3 kmol
1), mean pore size was formed.
molecular weight of the solvent (g kmol
1), and temperature The data in Table 1 provide a good overview on the trend of
(K), respectively. The average mutual diffusivities of the DMAc– changes in the morphological and structural characteristics of
water system is higher than that of the NMP–water system. By membranes as a result of solvent selection. For example, the
increasing the diffusion rate between the solvent and the non- data revealed that membranes prepared using DMAc as the
solvent, instantaneous demixing occurred which led to an solvent experienced more contraction and possessed a lower
increase in porosity in the top and the support layers.67 A strong thickness than their counterparts prepared using NMP. In
interaction between solvent and non-solvent is related to a addition, the mean pore size of the membranes prepared using
small difference between solubility parameters of the solvent
and non-solvent. A lower mutual diffusivity and lower porosity
are the results of a strong interaction between the solvent and
non-solvent.68 Table 3 Mutual diffusivity of various coagulating agent (c) and solvent
(s) systems and the average values (Dm)
(2) Another aspect is a consideration of the delay time (time
between immersion of a polymer lm into the coagulation bath Diffusivity coefficient (cm2 s
1)
to the inception of liquid–liquid demixing) and gelation time
(time between demixing and solidication) and their role in the System Dc–s  106 Ds–c  106 Dm  106
phase diagram (Fig. 6(a)).69 A nger-like structure with very thin
Water–NMP 11.56 7.92 9.74
skin layer is generally expected with the instantaneous demix- Water–DMAc 20.89 8.10 14.49
ing process, whereas a sponge-like structure with a thick skin Methanol–DMAc 12.01 6.12 9.06

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Paper RSC Advances

Fig. 6 (a) Schematic representation of a ternary phase diagram;69 (b) theoretical binodal (—) and spinodal (– –) curves for water–DMAc–PES and
water–NMP–PES systems. Experimental cloud point data () are used for verification of the theoretical calculations.70

DMAc was relatively high especially when higher dope concen- through both physical size sieving and electrostatic repulsion
trations were used. This is in good agreement with the pure mechanisms.
water ux data. The exchange rate between solvent and coagu-
lating agent affects the pore size. It should be noted that the 3.3. The effect of additive type and concentration in dope
diffusional exchange rate between the solvent and coagulating solution on the properties and performance of NF membranes
agent in the DMAc–water system is faster than that in the NMP–
The effect of the addition of ascorbic acid as a polyhydroxy acid
water system and because of delayed demixing, the solvent
and citric acid as a polyacid and the effect of their concentration
outow is faster than the coagulating agent inow. In this case,
on the characteristics and performance of NF membranes were
the pores tend to collapse and shrink.72 However, the porosity of
investigated. This was based on the idea that the incorporation
the prepared membrane decreased from 55.5% to 46.2% and
of these acids may enhance the performance of the membranes
from 58.9% to 47.6% in NF membranes prepared using dope
by altering their surface and structural characteristics. The
solutions containing 24 wt% and 30 wt% polymer in NMP and
investigation was carried out on the NF membranes prepared
DMAc, respectively. In fact, when DMAc was used as solvent,
using a dope solution containing 24 wt% PES dissolved in
instantaneous demixing occurred which led to the formation of
DMAc. As shown in Fig. 7(a), it can be seen that addition of both
a more porous structure as also reported previously by others.67
acids resulted in enhanced pure water ux in the membranes.
As shown in Table 1, when NMP was used as a solvent, the
The pure water ux of PES membranes increased from 38.35 l
solvent and coagulating agent diffusional exchange rate
m
2 h
1 (bare) to 52.99 l m
2 h
1 and 54.88 l m
2 h
1 by
decreased and thus, the surface porosity and pore size
addition of 1 wt% of ascorbic and citric acids, respectively.
decreased. The greater contact angle of NMP-based membranes
However, further addition of the acids beyond 1 wt% had
in comparison with DMAc-based membranes could be attrib-
negative effects. The pure water ux of the modied membrane
uted to the decreased surface porosity.62 Thus, DMAc-based
was expected to be higher than that for the unmodied
membranes exhibited a higher pure water ux. This improve-
membrane. As shown in Table 4, improvement of water ux can
ment in pure water ux could be attributed to an increase of
be attributed to membrane thickness, porosity and hydrophi-
membrane hydrophilicity.
licity. Structural analysis and characterization of membranes
Considering the effect of solvent type on the membrane
can provide useful information about the performance of the
performance, as shown in Fig. 4(b), it can be seen that NaCl
membranes. The porosity of the membranes increased to
rejection increased from 23.36% to 47.35% and from 18.62% to
75.87% and 77.68% upon addition of ascorbic and citric acids
40.80% in NF membranes prepared using dope solutions con-
up to 1.0 wt%, respectively. This could be attributed to the
taining 24 wt% and 30 wt% polymer in NMP and DMAc,
interactions between the additive with a component of the
respectively. According to Fig. 4(c), MgSO4 rejection increased
casting solution (polymer and solvent). By addition of both
from 86.35% to 99.84% and 82.78% to 99.10% in NF
organic acids into the dope solution, hydrogen bonds were
membranes prepared using dope solutions containing 24 wt%
formed between the hydrogen atoms of the organic acids and
and 30 wt% polymer in NMP and DMAc, respectively. The
the oxygen atoms of the PES, thus, weaker interactions occurred
rejection of both monovalent and divalent salts was higher in
between polymer chains. In addition, the hydrophilic nature of
NMP-based membranes in comparison to DMAc-based
the organic acids and the formation of hydrogen bonds between
membranes which is related to the smaller pore size in the
additive molecules and DMAc, decreases the ratio of the solvent
NMP-based membrane which increases the rejection of salts
outow to the coagulating agent (water) inow which causes
instantaneous demixing.73,74 Instantaneous demixing results in

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 49080–49097 | 49087
RSC Advances
the formation of macrovoids, a porous top and support layers
and a lower concentration of the polymer at the surface which
leads to a thinner skin layer.67 However, further addition of
organic acids beyond 1 wt% resulted in an increase in binding
force between the polymer chains and additive molecules and
thus, the remaining free volume was reduced because of the
tighter and stronger entanglements. Furthermore, according to
the data in Table 4, and by comparing to the thickness of the
reference membrane (100 mm), thinner membranes were
obtained by using dope solutions containing either ascorbic or
citric acids. The addition of additives decreased the ratio of the
solvent outow to the coagulating agent (water) inow
providing more opportunity for the penetration of coagulating
agent and accordingly a bigger contraction ratio was obtained
because of the faster demixing.73 It was also found that the
addition of both acids improved the hydrophilic properties of
the membranes and this was largely attributed to the hydro-
philic functional groups of the organic acids.73 The effect of
ascorbic acid on the contact angle of the membranes was
greater than that of citric acid. The contact angle reduced from
60.5 to 38.6 and 45.3 upon addition of 1.5 wt% of ascorbic
and citric acids, respectively.
Also, as shown in Fig. 7(b) and (c), it can be seen that the
rejection of both monovalent and divalent salts increased by
increasing the concentration of both organic acids in the dope
solutions. Size exclusion (steric hindrance) and electrostatic
charge repulsion are two important mechanisms that may affect
the rejection of ionic solutes. It was shown that PES membranes
possess a negative surface charge because of the breakdown of
Fig. 7 The effect of type and concentration of organic acids as additives to the dope solutions on (a) pure water flux (b) NaCl rejection (c) MgSO4
rejection in NF membranes.
49088 | RSC Adv., 2015, 5, 49080–49097
Paper
surface functional groups or adsorption of ions from the
aqueous solution.75 As shown in Table 4, mean pore size of the
modied membrane was smaller than that of the unmodied
membrane. An increase in salt rejection by addition of organic
acids might be attributed to two factors: (i) reduction of pore
size of the membrane which promoted the salt rejection by a
size exclusion mechanism, and (ii) increase in surface negative
charge and reduction of pore size (higher surface charge
density) which promoted the salt rejection through the elec-
trostatic charge repulsion.73
3.4. The effect of type and concentration of coagulating
agent on the properties and performance of NF membranes
The effects of adding methanol to the coagulating agent
(distilled water) were investigated for the NF membranes
prepared using a dope solution containing 24 wt% PES dis-
solved in DMAc. In order to study the effects of the composition
of the coagulating agent on the structure and performance of
the PES membrane, three different compositions were used
(Table 5). The characteristics and performance of the
membranes prepared at different compositions of coagulation
agents are shown in Table 5. The pure water ux for different
membranes are given in Table 5. The pure water ux of the
membranes reduced from 38.35 l m
2 h
1 to 29.15 l m
2 h
1
when methanol was added to the coagulation bath from 0 to 50
vol%. This is because of the formation of membranes with
lower porosity, smaller pore size and lesser hydrophilicity and
increased thickness. Data are in good agreement with those for
the membrane structural properties. By using a mixture of
This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

Table 4 The effect of additives in dope solutions on the structural characteristics of PES NF membranesa

Additive concentration Solvent concentration Membrane thickness Mean pore size Porosity Contact angle
Additive type (wt%) (wt%) (mm) (nm) (%) ( )

None 0 76.0 100 4.96 58.9 60.5

Ascorbic acid 0.5 75.5 93 4.63 67.8 53.1
1.0 75.0 86 4.51 75.8 43.4
1.5 74.5 91 4.46 73.8 38.6
Citric acid 0.5 75.5 96 4.73 66.9 55.7
1.0 75.0 86 4.44 77.6 48.6
1.5 74.5 89 4.21 74.7 45.3
a
Conditions: dope solution: 24 wt% PES in DMAc, casting temperature: 25  3  C; relative air humidity: 30  5%; casting knife gap: 200 mm; casting
shear rate: 23.54 s
1; solvent evaporation time: 0 min; coagulating agent: pure water; coagulation bath temperature: 20  2  C.

methanol and water as coagulation agent, the porosity of
prepared membrane decreased from 58.9% to 52.74% and the
mean pore size decreased from 4.96 nm to 4.68 nm in NF
membranes prepared using a coagulating agent containing
water and mixtures of water–methanol (50/50 vol%). Further-
more, according to the data in Table 5, a thicker membrane (107
mm) was obtained from using the coagulation bath containing a
mixture of water–methanol (50/50 vol%) when compared to the
reference membrane (100 mm).
The following points provide more insights about the effect
of the composition of the coagulating agent on the structure
and performance of NF membranes:
(1) If alcohols are used as the coagulating agent, the binodal
curve in the ternary phase diagram shrinks signicantly and
shis toward the coagulating agent–polymer axis.76 This
signies that more amounts of coagulating agent are needed for
the casting solution to become thermodynamically unstable
and to reach a binodal curve. As found in previous work,77 the
delay time increases gradually when the coagulating agent was
changed from water to alcohol. This results in delayed demixing
which leads to the formation of a thicker membrane with a
smaller pore size in the top layer and lower porosity in the
support layer.46
(2) As explained in Section 3.2, polymer–solvent and solvent–
coagulating agent interactions as well as the mutual diffusivity
between the solvent and the non-solvent have great effects on
membrane performance and structure. If the difference
between the solubility parameter of solvent and coagulating
agent is low, the coagulating agent penetrates slowly into the
cast lm and delayed demixing occurs.67 According to the
solubility parameters shown in Table 2, by addition of methanol
into the coagulation bath, the difference between the solubility
parameters of the solvent–coagulating agent decreased and led
to delayed demixing.78 From the kinetic viewpoint, it is possible
to correlate the diffusional exchange of solvent–coagulating
agent to the demixing process. Generally, a higher diffusion of
coagulating agent in the solvent results in a faster precipitation.
The average mutual diffusivity for the intended solvent–coagu-
lating agent systems are given in Table 3. The diffusivity coef-
cient between the solvent and coagulating agent was
calculated using the Wilke–Chang equation (eqn (5)). The
average mutual diffusivity of the DMAc–water system is higher
than that of DMAc–alcohol system. Therefore, the lower
exchange rate between solvent and methanol as coagulating
agents leads to delayed demixing which is associated with a
thicker membrane, smaller pore size in the top layer and lower
porosity.
(3) The difference in solubility parameters between PES and
the coagulating agent is in the order: (PES–water) > [PES–(25%
methanol–75%water)] > [PES–(50%methanol–50%water)]. The
decrease in the difference between the solubility parameter of
the polymer and the coagulating agent usually implies a slower
precipitation rate which results in delayed demixing and as a
consequence, a thicker membrane with a lower porosity and
smaller pore size is formed.79
The contact angle of the prepared membrane increased as
methanol was added to the coagulation bath. Because the
materials and dope solution composition were the same, the
greater contact angle of the membrane prepared in the coagu-
lation bath containing methanol can be mainly attributed to the

Table 5 The effect of coagulating agent on the structural characteristics of PES NF membranesa

Membrane thickness Mean pore size Porosity Contact angle Pure water ux NaCl rejection MgSO4 rejection
Coagulating agent (mm) (nm) (%) ( ) (l m
2 h
1) (%) (%)

Water 100 4.96 58.9 60.5 38.35 18.62 82.78

Water–methanol (75/25 vol%) 103 4.93 57.2 62.1 35.13 19.17 89.35
Water–methanol (50/50 vol%) 107 4.68 52.7 65.9 29.15 25.20 91.22
a
Conditions: dope solution: 24 wt% PES in DMAc, casting temperature: 25  3  C; relative air humidity: 30  5%; casting knife gap: 200 mm; casting
shear rate: 23.54 s
1; solvent evaporation time: 0 min; coagulation bath temperature: 20  2  C.

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 49080–49097 | 49089
RSC Advances
decreased surface porosity.65 The addition of methanol into the
coagulation bath decreased the solvent and coagulating agent
diffusional exchange rate and thus, the average membrane
surface porosity decreased and as a consequence, the wettability
of the membrane decreased.62
The effect of composition of the coagulating agent on the
performance of the NF membranes was investigated in terms of
rejection of monovalent and divalent salts. Generally, an
increase in the methanol fraction in the coagulating agent led to
improvements in rejection of both NaCl and MgSO4. As shown
in Table 5, the salt rejection increased from 18.62% to 25.2% for
the NaCl solution and from 82.78% to 91.22% for the MgSO4
solution when the mixture of water and methanol were used as
the coagulating agent. The improvement in salt rejection can be
explained by a reduction in the mean pore size of the membrane
and enhanced size sieving effect.
3.5. The effect of solvent evaporation time on the properties
and performance of NF membranes
The time interval between the polymeric solution casting and
immersion of the cast lm into the coagulation bath is called
the solvent evaporation time. This period signicantly alters the
structure and performance of the fabricated membrane. Struc-
tural analysis and characterization of the membranes can
provide useful information about the performance of the
membranes. According to the data shown in Table 6, and in
comparison with the data for the reference membranes, the
porosity of the membranes decreased from 58.90% to 53.76%
and mean pore size decreased from 4.96 nm to 4.53 nm at 0 and
3 min solvent evaporation times, respectively. The changes in
porosity and mean pore size could be attributed to the increase
of polymer concentration in the top layer of the nascent lm as
well as the entanglement of macromolecules caused by the
relaxation of the polymer chains at longer solvent evaporation
times.80 As the polymer concentration increases in the top layer,
it acts as a more impenetrable barrier against the solvent
outow and coagulating agent inow, which decreases the
diffusional exchange rate. As a consequence, a membrane with
a lower porosity and smaller pore size is formed.81 Furthermore,
the thickness of the membrane increased from 100 mm to 107
mm over longer solvent evaporation times. This may arise from
the fact that the increase in the polymer concentration at the
top layer of the cast lm provides less opportunity for the
Table 6 The effect of solvent evaporation time and coagulation bath temperature on the structural characteristics of PES NF membranesa
Solvent evaporation Coagulation bath Membrane Mean pore size
time (min) temperature ( C) thickness (mm) (nm)
0 20 2 100 4.96
3 20 2 107 4.53
0 0 2 111 4.58
0 20 2 100 4.96
0 50 2 93 5.13
a
Conditions: dope solution: 24 wt% PES in DMAc, casting temperature: 25  3  C; relative air humidity: 30  5%; casting knife gap: 200 mm; casting
shear rate: 23.54 s
1; coagulating agent: pure water.
49090 | RSC Adv., 2015, 5, 49080–49097
Paper
penetration of coagulating agent and therefore, less contraction
ratio is provided because of the slowed demixing rate.46
Membranes prepared over a longer solvent evaporation time
exhibited a lower water ux. The pure water ux decreased from
38.35 l m
2 h
1 to 26.73 l m
2 h
1 as the solvent evaporation
time increased from 0 min to 3 min. The pure water ux was
directly proportional to the porosity and pore size and inversely
proportional to the membrane thickness. At longer solvent
evaporation times, the membrane porosity and pore size
decreased and the membrane thickness increased causing a
lower water ux. Increase in solvent evaporation time consid-
erably affected the rejection of salts. As shown in Table 6, the
rejection of salts increased from 18.62% to 30.65% for NaCl
solution and from 82.78% to 91.58% for MgSO4 solution at
0 and 3 min solvent evaporation time, respectively. This is
associated with the diminution of pores that improve the
rejection of salts through both size sieving and electrostatic
charge repulsion (because of the increase in surface charge
density).58 About the contact angle, no clear changes can be
inferred. A minor increase in contact angle by increasing the
solvent evaporation time may be attributed to the lower surface
porosity.65
3.6. The effect of coagulation bath temperature (CBT) on the
properties and performance of NF membranes
The effects of three different levels of CBT (0  C, 20  C, 50  C) on
membrane structure and performance are shown in Table 6.
The pure water ux of the PES NF membrane prepared at a CBT
of 0  C was 25.35 l m
2 h
1. When the CBT increased to 50  C,
the pure water ux increased greatly to 52.12 l m
2 h
1. The
increase of pure water ux may be attributed to three reasons.
The rst is the lower resistance caused by the thinner top layer;
the second is the enlarged pores on the top layer; and the third
is the higher porosity. In general, the porous structure with
macrovoids occurred with an instantaneous demixing condi-
tion and demixing is faster at a higher CBT. On the other hand,
at a lower CBT, delayed demixing occurs causing inhibition of
the free growth of limited nuclei on the top layer, and instead
many small nuclei are formed and distributed throughout the
cast lm. Accordingly, despite the instantaneous demixing,
formation of macrovoids is suppressed and denser membranes
are formed.64
Porosity Contact Pure water ux NaCl rejection MgSO4
(%) angle ( ) (l m
2 h
1) (%) rejection (%)
58.9 60.5 38.35 18.62 82.78
53.7 63.4 26.73 30.65 91.58
52.8 63.3 25.35 31.33 92.25
58.9 60.5 38.35 18.62 82.78
65.2 54.8 52.12 9.25 72.95
This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

The porosity of the prepared membranes increased from
52.89% to 65.29% and the membrane thickness decreased from
111 mm to 90 mm in NF membranes prepared in coagulation
bath temperatures of 0  C and 50  C, respectively. The diffusivity
coefficient between the solvent and the coagulating agent is
temperature dependent. According to eqn (5), an increase in
temperature enhances the diffusional exchange rate between
the solvent and the coagulating agent in the casting solution
during the solidication process which leads to instantaneous
demixing and thus, induces the formation of a membrane with
a more porous structure. Decrease in the diffusivity coefficient
by temperature slows down the penetration of the coagulation
agent and thus, the contraction ratio is less because of the
slowed demixing rate. Accordingly a thicker membrane was
obtained.
The CBT values have a great inuence on membrane perfor-
mance in rejection of salts. By decreasing the CBT, the NaCl
rejection increased from 9.25% to 31.33% and the MgSO4 rejec-
tion increased from 72.95% to 92.25% in NF membranes prepared
in coagulation bath at temperatures of 0  C and 50  C, respec-
tively. Decrease of the CBT can also increase the dope viscosity, the
chain rigidity, and the surface tension of the solution which will
cause slow precipitation and a membrane with a smaller pore size
is formed.82 As a result, the rejection of salts is increased.
The contact angle can be improved by increasing the CBT.
Similar results have been reported previously.82 It should be
noted that the wettability of the membrane as well as the
surface porosity and roughness are inuenced by the
membrane material. Thus, because the materials and dope
solution composition were the same, the greater contact angle
of the membrane prepared at the higher CBT can mainly be
attributed to the decreased surface porosity.65
3.7. The effect of membrane casting speed on the properties
and performance of NF membranes
Casting speed signicantly affects the membrane performance
and structure. The shear rate experienced during casting was
calculated using the following relationship:
  Casting knife speed ðm s
1 Þ
Shear rate s
1 ¼ (6)
Membrane thickness ðmÞ
As shown in Table 7, the membrane thickness decreased by
increase in the applied shear rate. Consequently, the pure water
ux was affected by the membrane thickness and increased
from 25.13 l m
2 h
1 to 41.32 l m
2 h
1 in membranes prepared
at shear rates of 9.23 s
1 and 42.76 s
1, respectively. Based on
the structural data, a thinner membrane with more porosity was
formed at a higher shear rate resulting in higher pure water
ux.56 These ndings are in agreement with other results
reported in the literature.56,58 Kusworo et al.57 reported that at
higher shear rates, a decrease in dope viscosity occurred
because of the reduction of chain entanglement. Boussu et al.46
claimed that at a lower dope viscosity, the diffusional exchange
rate between the solvent and the coagulating agent increased
causing the formation of a porous structure. Furthermore, by
increasing the shear rate, the pore size of the membranes was
decreased. The decrease in pore size resulted in better solute
rejection. The NaCl rejection increased from 17.12% to 23.32%
and the MgSO4 rejection increased from 80.32% to 89.12% in
NF membranes prepared at shear rates of 9.23 s
1 and 42.76
s
1, respectively. These results agree well with those reported
by Ali et al.58 The signicant improvement in rejection of salts
can be attributed to the molecular orientation induced by the
shear rate during the casting of the polymer lm.83 As shown in
Fig. 8, macromolecules exposed to a higher shear rate tend to
have a more ordered alignment than those under a lower shear
rate. Enhancement of the molecular orientation causes the
polymer chains to pack closer leading to a decrease in free
volume or pore size.58,83,84 The formation of a smaller pore size
and an increase in surface charge density of the membrane
(because of the lower pore size) enhance the separation
performance of PES NF membranes.58 No change in contact
angle of the membranes prepared at different shear rates was
identied.
3.8. The effect of membrane thickness on the properties and
performance of NF membranes
Membrane thickness plays an important role in determining
ux and rejection properties of NF membranes. The effect of
membrane thickness on pure water ux is shown in Table 7.
The pure water ux decreased from 56.41 l m
2 h
1 to 17.87
l m
2 h
1 in membranes prepared with a thickness of 100 mm

Table 7 The effect of casting shear rate and casting knife gap on the structural characteristics of PES NF membranesa

Casting shear Casting knife Membrane thickness Mean pore size Porosity Contact angle Pure water ux NaCl rejection MgSO4 rejection
rate (s
1) gap (mm) (mm) (nm) (%) ( ) (l m
2 h
1) (%) (%)

9.23 200 110 5.06 48.3 59.1 25.13 17.12 80.32

23.54 200 100 4.96 58.9 60.5 38.35 18.62 82.78
42.76 200 92 4.54 64.4 60.1 41.32 23.32 89.12
23.54 100 73 5.09 63.6 57.6 56.41 13.54 80.98
23.54 200 100 4.96 58.9 60.5 38.35 18.62 82.78
23.54 300 162 4.59 52.9 65.8 17.87 28.32 90.83
a
Conditions: dope solution: 24 wt% PES in DMAc, casting temperature: 25  3  C; relative air humidity: 30  5%; solvent evaporation time: 0 min;
coagulating agent: pure water; coagulation bath temperature: 20  2  C.

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 49080–49097 | 49091
RSC Advances Paper

Fig. 8 A hypothetical mechanism for the conformation of polymer chains induced by shear rate.84

and 300 mm, respectively. The results demonstrate that the
membrane with the lower thickness was more permeable
because of the lower membrane resistance, higher porosity and
larger pore size. At the beginning of the phase inversion
process, because of the increase in the ratio of the solvent out-
diffusion on the coagulating agent (water) inow, the polymer
concentration at the top layer increases. When the delay time is
long, a higher polymer concentration is achieved at the inter-
phase between the polymer lm and the coagulating agent,
which leads to the fast growth of the dense layer. As a result, a
thicker and denser top layer with a smaller pore size was formed
and as consequence, the pure water ux decreased.85 The
membrane porosity decreased signicantly from 63.60% to
52.91% in the membrane prepared with a casting knife gap of
100 mm and 300 mm, respectively. Using a higher casting knife
gap decreased the diffusional exchange rate between the solvent
and the coagulating agent and thus, the membrane structure
became thicker and less porous.59 The mean pore sizes of the
membranes are given in Table 7. As the initial casting thickness
increases, the diffusion rate of the coagulating agents in the cast
lms decreases and thus, delayed demixing occurs. Therefore,
the mean pore size was shied to a lower value as the
membrane thickness increased.59
The effect of casting solution thickness on rejection of salts
is shown in Table 7. By increasing the membrane thickness,
the NaCl rejection increased from 13.54% to 28.32% and the
MgSO4 rejection increased from 80.98% to 90.83% in NF
membranes prepared with thicknesses of 100 mm and 300 mm,
respectively. The decrease of pore size enhanced the rejection
of salts through both size sieving and electrostatic repulsion
mechanisms. As the membrane thickness increased, the
contact angle decreased. Because the materials and the dope
solution are the same, the greater contact angle of the thicker
membrane can mainly be attributed to the decreased surface
porosity.65
3.9. Effect of operating parameters on the properties and
performance of NF membranes
3.9.1. Feed pressure. The effect of feed pressure on water
ux and rejection of salts of the reference membrane (PES–
DMAc 76%/24%) is shown in Fig. 9. Because of the porous
nature of the membrane, the Hagen–Poiseuille equation can be
considered under the hypothesis of constant pressure gradient
along the membrane pore.86 According to the Hagen–Poiseuille
ow as expressed in eqn (7), increase in water ux is propor-
tional to the increase in pressure difference across the
membrane:
rp 2
JV ¼ DP ¼ Lp DP (7)
8hd
where JV (m s
1), rp (m), h (Pa s
1), d (m), DP (Pa) and Lp
(m s
1 Pa
1) are volume ux, average pore radius, water
dynamic viscosity inside the pore, effective membrane thick-
ness, pressure difference across the membrane and hydraulic
membrane permeability, respectively. According to Fig. 9(a),
water ux data versus feed pressure is approximately linear and

Fig. 9 Effect of feed pressure on (a) pure water flux (b) NaCl and MgSO4 rejection of PES NF membranes. (Conditions: dope solution: 24 wt% PES
in DMAc, casting temperature: 25  3  C; relative air humidity: 30  5%; casting knife gap: 200 mm; casting shear rate: 23.54 s
1; solvent
evaporation time: 0 min; coagulating agent: pure water; coagulation bath temperature: 20  2  C; feed composition: 10 500 ppm NaCl, 1300
ppm MgSO4, pH ¼ 7).

49092 | RSC Adv., 2015, 5, 49080–49097 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

The effect of feed pH on water flux and salt rejection of PES

Table 8 3.9.2. Feed pH. The rejection of salts and the water ux as a
NF membranesa function of feed pH were investigated for the reference
Water ux NaCl rejection MgSO4 rejection
membrane (PES–DMAc 76%/24%) and the results are shown in
Feed pH (l m
2 h
1) (%) (%) Table 8. The zeta potential of the bare membrane was also
measured to determine the membrane surface charge as a
5 33.12 12.43 75.47 function of pH, as shown in Fig. 10. The higher zeta potential of
7 35.21 17.96 81.97 the PES membrane at a higher solution pH value indicates the
9 37.19 19.65 86.09
membrane surface is more negative. It is believed that the
a
Conditions: dope solution: 24 wt% PES in DMAc, casting temperature: negative charge of the PES membrane originates from the
25  3  C; relative air humidity: 30  5%; casting knife gap: 200 mm;
casting shear rate: 23.54 s
1; solvent evaporation time: 0 min; functional groups of PES (O]S]O).75 Because of the electro-
coagulating agent: pure water; coagulation bath temperature: 20  2 static charge repulsion between SO42
and Cl
molecules and
C; feed composition: 10 500 ppm NaCl, 1300 ppm MgSO4; testing the negative charges on the membrane surface, SO42
and Cl

pressure ¼ 10 bar.
molecules are rejected. An increase in solution pH results in an
increase in the negative surface charge of membrane, which
leads to a stronger electrostatic charge repulsion between the
anions and the membrane surface and increases the rejection of
anions. Subsequently, the rejection of cations (Mg2+, Na+)
increases because of the Donnan effect. In other words, if
anions (SO42
and Cl
) are rejected because of electrostatic
charge repulsion with the negative surface charge of the PES
membrane, then the cations will also have to be rejected to
retain the electric charge neutrality of the solution. An increase
in co-ion charge and a decrease in counter ion charge improves
the rejection of salts.66 Because of the higher charge of the
sulfate ions, the rejection of Mg2+ ions also increases caused by
the Donnan effect. The electrostatic charge repulsion between
the anion molecules and the membrane surface increases by
increasing the solution pH, which hinders adsorption of anion
Fig. 10 The zeta potential of the bare PES membrane as a function of molecules on the membrane surface. Hence, the barriers for the
pH.75
passage of solutions across the membrane decreases and
therefore the water ux increases.73

calculated water permeability is 16.47 l m2 h
1 bar
1. Also, the
salts rejection increased with the increase in feed pressure
(Fig. 9(b)). This is because the water permeate ux through the
membrane is linearly related to the trans-membrane pressure,
whereas the salt ux is relevant to both the concentration
gradient across the membrane and the water ux. When the
feed pressure increases, the water permeate ux increases
relatively more compared to the salt permeate. This causes a
decreasing salt concentration in the permeate stream and an
increasing rejection of salts.87
3.10. Comparison with literature
Table 9 provides the salt rejection and water ux performance of
several commercial and non-commercial NF membranes
reported in literature. It can be seen that the water ux for the
membranes developed in this study were almost higher than all
the others in the table, except that of NF90. This can be
attributed to high porosity, low thickness and formation of
more free volume in the structure of the developed membranes.
On the other hand, the salt rejection performance of the fabri-
cated membranes seems to be satisfactory considering the salt

Table 9 Performance comparison for several commercial and non-commercial NF membranes

Water ux NaCl rejection MgSO4 rejection

Membrane type (l m
2 h
1) (%) (%) Operating conditions Ref.

Polyethersulfone with citric acid as 54.88 26.83 89.36 P ¼ 10 bar, CNaCl ¼ 10 500 ppm, Present
additive CMgSO4 ¼ 1300 ppm study
Oxidized multiwalled carbon nanotube/ 8 20 58 P ¼ 4 bar, C ¼ 200 ppm 90
polyethersulfone nanocomposite
Amine-functionalized multiwalled 5.23 20 50 P ¼ 4 bar, C ¼ 200 ppm 75
carbon nanotubes
NF90 (commercial) 80 22 99 P ¼ 10 bar, C ¼ 800 ppm 88
DS-5 DL (commercial) 18 1.3 93 P ¼ 14 bar 89
NE2540-70 (commercial) NA 7.2 3.56 P ¼ 14 bar 89

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 49080–49097 | 49093
RSC Advances
concentration used for testing in comparison with other
research. The membrane separation performance for divalent
ions was better than that for monovalent ions. The authors are
working for further improvements in this respect.
4. Conclusions
The properties and performance of asymmetric PES NF
membranes were investigated through a systematic analysis on
the effects of design, fabrication and operational parameters,
with the main aim of obtaining membranes with high rejection
of monovalent and divalent salts while possessing a reasonable
water ux. The results obtained revealed that among the
studied parameters, polymer concentration greatly affected the
membrane morphology and performance. It was also found
that the membrane structure and performance were consider-
ably dependent on the solvent–coagulating agent and solvent–
polymer interactions. Overall, membranes prepared using
DMAc exhibited a higher water ux than those prepared using
NMP as solvent. Modied membranes containing organic acids
exhibited structures with a lower thickness, higher porosity and
smaller pore size compared to the unmodied membrane. This
was attributed to the hydrophilic functional groups of additives
as proven by the water contact angle data indicating that the
wettability of membranes was increased by both citric and
ascorbic acids. The water ux of the modied membrane was
improved by the addition of 1 wt% of organic acids, although
the rejection of salts improved for all concentrations of organic
acids. Structural analysis of the membranes indicated that the
membranes prepared with coagulating agent containing
methanol had a lower porosity, smaller pore size, less hydro-
philic surface and higher thickness because of slower diffu-
sional exchange between the solvent and the coagulating agent.
Despite the decline in pure water ux, rejection of both NaCl
and MgSO4 was improved in membranes prepared using a
water–methanol mixture as a coagulating agent. Furthermore,
membranes cast at a lower temperature, with a higher thickness
and higher solvent evaporation time were found to be less
porous with a lower mean pore size and were less permeable to
water and more capable of rejecting salts. In all the membranes,
the rejection of divalent ions was greater than monovalent ones,
owing to the negative surface charge of the PES membranes. As
a consequence, addition of organic acids and increase in
casting shear rate simultaneously improved both water ux and
salt rejection. However, there was a trade-off between rejection
and permeability for other parameters. These ndings provide
valuable information and guidelines for the development of
high performance nanoltration membranes for specialized
separation applications.
Acknowledgements
The authors would like to thank the Iran Nanotechnology
Initiative Council (INIC) for partial nancial support to this
project.
49094 | RSC Adv., 2015, 5, 49080–49097
Paper
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RSC Adv., 2015, 5, 49080–49097 | 49097