Microporous and Mesoporous Materials 228 (2016) 1e13

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Microporous and Mesoporous Materials

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

Preparation and characterization of novel microporous ultrafiltration

PES membranes using synthesized hydrophilic polysulfide-amide
copolymer as an additive in the casting solution
Aazam Jalali, Abbas Shockravi*, Vahid Vatanpour, Mohsen Hajibeygi
Faculty of Chemistry, Kharazmi University, 15719-14911 Tehran, Iran

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

Article history: Novel asymmetric microporous polyethersulfone (PES)/polysulfide-amide (PSA) blended ultrafiltration
Received 13 February 2016 membranes with superior properties were prepared using the phase inversion induced by immersion
Received in revised form precipitation method. The hydrophilic PSA copolymer with nitro groups, thiazole rings, and thioether
12 March 2016
linkages was synthesized via phosphorylation polycondensation. Different concentrations of the copol-
Accepted 20 March 2016
ymer were used in the PES casting solutions for improving membrane properties and the results were
Available online 22 March 2016
compared with polyvinyl pyrrolidone (PVP)/PES membrane. The presence of amide band, correlated with
the stretching vibration of the carbonyl group and bending vibration of NH group on the ATR-FTIR
Keywords:
Ultrafiltration
spectra of the modified membranes confirmed the existence of PSA in the PES membrane structure.
Microporous The cross-section SEM images showed that the membranes with lower skin layer thickness were formed
Polymeric additive by addition of PSA in the casting solution. Not only the pure water and BSA solution flux of the blended
Thiazole-based copolymer membranes were increased by enlarging PSA concentrations in the casting solutions up to 2% PSA, but
PES blend membrane also antifouling properties were improved. Comparing PSA with PVP additive showed that the PSA could
Hydrophilicity improve membrane hydrophilicity, porosity, permeability and antifouling properties. However, the PVP
has better performance in case of the porosity and the permeability improvement. Therefore, for
coupling of the effect of these two additives, the membrane with 1 wt% PVP and 1 wt% PSA was prepared.
The results showed that the prepared membrane had good solution flux with good antifouling
properties.
© 2016 Elsevier Inc. All rights reserved.

1. Introduction [12e14]. Polyethersulfone (PES) can be considered as a standard

material in membrane manufacturing. It has been widely used in
Membrane technology due to high efficiency, low cost and its preparation of ultrafiltration membranes due to its extra features
role in reducing energy consumption during the separation process such as high glass transition temperature, high chemical stability
is known as a full application separation process [1,2]. In recent against aggressive materials, high values of tensile strength, and
years, high performance synthetic polymeric membranes have high amount of elongation at break [15,16]. Nevertheless, the PES
been widely used in medicine [3], water and wastewater treatment membranes are restricted with theirs relative high hydrophobicity.
[4], removal of heavy metals [5], blood purification [6], DNA/RNA When solutions containing proteins or other hydrophobic sub-
separation [7], recycling of rare metals [8] and a wide variety of stances are filtered, fouling phenomenon occurs and the flux
liquid separation applications such as ultrafiltration, reverse permeation of membrane highly decreases [1,9]. A useful technique
osmosis and nanofiltration [9e11]. to overcome this limitation of the PES membranes is enhancement
Ultrafiltration (UF) as a separation technique has widely been of membrane hydrophilicity by blending hydrophilic polymers. The
applied in water and wastewater treatment and various industries blending of a hydrophilic polymer as an additive in the PES matrix
as a membrane forming polymer offers combination of their
properties [16,17]. Many hydrophilic polymers have not good
properties for formation of uniform film with acceptable strength
* Corresponding author.
and stability. Therefore, they could not be used in preparation of
E-mail addresses: [email protected], [email protected]
(A. Shockravi). membranes as a main matrix. However, they might be used as

http://dx.doi.org/10.1016/j.micromeso.2016.03.024
1387-1811/© 2016 Elsevier Inc. All rights reserved.
2 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13

blending hydrophilic additives with membrane forming polymers

such as PES, polysulfone, polyvinylidene fluoride, etc. [17e19] for
improvement of the properties of the resulted membranes.
Sidiney and Srinivasa are the pioneers of the membrane prep-
aration by the phase inversion method and employed the reverse
osmosis membranes to produce fresh water from brackish water
such as seawater [20,21]. After that, many researches have been
performed numerous studies to understand the mechanism of
membrane formation. Lee and Kim have added polyethylene glycol
200 as an additive to the casting solution of polyetherimide (PEI)
membranes and investigated its effect on the structure and
permeation properties of the prepared membranes [22]. Sinha and
Purkait prepared amphiphilic polyurethane macromolecules with
functional groups of carboxylic acid and used it in preparation of
fouling resistant polysulfone (PSf) flat sheet UF membrane. The
blended membranes presented enhanced pure water flux, pore
density and hydrophilicity compared to non-blended membrane
[23]. Boam et al. investigated the effect of polyvinyl pyrrolidone
(PVP) on the morphology and performance of PES membranes and
found that addition of PVP increased the formation of macrovoids
in the sublayer [24]. Improving the antifouling property of PES
membrane by blending phosphorylcholine copolymer was done
and it was found that the rejection ratio of bovine serum albumin
Fig. 1. Schematic of synthesis of polysulfide-amide copolymer.
(BSA) was decreased and the flux recovery ratio was remarkably
increased [25]. Eren et al. prepared PSf composite UF membranes
by blending of poly [2,20 -(m-phenylene)-5,50 -dibenzimidazole] 18 h at 150  C under vacuum. Aromatic diacid from Aldrich and
(PBI). The resulted membrane properties such as hydrophilicity, polyvinyl pyrrolidone (PVP) with 25,000 g/mol molecular weight
porosity and thermal stability can be considerably enhanced with from Merck were used. Bovine serum albumin powder (BSA) was
the incorporation of PBI [26]. Totally, it could be concluded that obtained from Sigma Aldrich and distilled water was used as pure
addition of the polymers with multifunctional groups such as car- water in this study.
boxylic acid, amine, hydroxyl, sulfide, sulfonate, nitro, carbonyl and
etc. could improve properties of UF membranes.
In this study, in order to increase efficiency of PES membrane, a 2.2. Synthesis of polysulfide-amide copolymer
hydrophilic polymer i.e. aromatic polyamide with nitro groups,
thiazole rings, and thioether linkages was synthesized and added to The used polysulfide-amide was synthesized according to our
the casting solution of PES membrane in various concentrations. previous work [29]. The PSA copolymer was synthesized by
Our previous work is shown that polysulfoxide-amide as an addi- condensation reaction of 5, 5'-thiobis (4-(3-nitrophenyl) thiazol-2-
tive in the casting solution resulted in membranes with higher amine) as diamine monomer with terephthalic acid as an aromatic
water flux and protein rejection [27]. Also, another work presented dicarboxylic acid as presented in Fig. 1. Briefly, a mixture of 1.416 g
that synthesis of sulfonated polyethersulfone (SPES) and blending (3 mmol) of diamine, 0.498 g (3 mmol) of terephthalic acid, 0.9 g of
it in PES matrix resulted in improved hydrophilicity and perme- LiCl, 1.5 mL of TPP, 1.5 mL of pyridine and 9 mL of NMP was heated
ability respect to the bare PES [28]. The PES membrane blended and stirred at 120  C for 6 h, under nitrogen atmosphere. As the
with sulfonated polyarylene ether sulfide sulfoxide sulfon polycondensation proceeded, the reaction mixture became gradu-
(SPAESSS) exhibited less finger-like pores in sublayer and lower ally viscous. At the end of the reaction, the polymer solution was
thickness of dense skin layer. That led to improving protein rejec- poured slowly into 600 ml of methanol under rapid stirring. The
tion of the modified membranes [1]. stringy, fiber-like precipitate was collected by filtration, washed
In this work, polysulfide-amide (PSA) was synthesized and thoroughly with hot methanol (200 mL), and dried in a vacuum
characterized as a hydrophilic copolymer (Fig. 1). Then novel oven at 100  C overnight.
asymmetric microporous PES membranes blended with the PSA
were prepared. Surface morphology, cross-sectional structure, hy- 2.3. Membrane preparation
drophilicity, permeability and BSA rejection of the prepared PES
membranes were investigated in different concentrations of PSA Asymmetric PES flat membranes were fabricated by the phase
copolymer. inversion method via immersion precipitation technique. Appro-
priate amounts of two polymers (PES and synthesized PSA) at
2. Experimental different compositions dissolved in DMAc at around 25  C and stir-
red for 24 h with a magnetic stirring at speed of 300 rpm. The ob-
2.1. Materials tained homogeneous polymer solutions were kept constant to
remove the bubbles. The solutions were cast using a casting knife
Polyethersulfone (PES Ultrason E6020P with Mw ¼ 58,000 g/ with 175 mm thickness on glasses and then produced films were
mole and glass transition temperature Tg ¼ 225  C) and dimethy- rapidly immersed in water bath as a non-solvent. Next, they pulled
lacetamide (DMAc) as a solvent were supplied by BASF company. N- out the water and moved in to another vessel containing distillated
methyl-2-pyrrolidone (NMP) and pyridine (Py) were supplied by water for completing the phase separation and leaching out the
Merck Company, distillated under reduced pressure over calcium remaining solvent for 24 h. Finally, the prepared membranes were
hydride, and stored over 4 Å molecular sieve. Triphenyl phosphite dried by sandwiching among filter papers for 24 h. The compositions
(TPP) and LiCl were supplied by Merck Company. LiCl was dried for of the casting solutions are listed in Table 1 and the photographs of
 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13 3

Table 1 2.4.2. FTIR analysis

Composition of casting solutions. FTIR spectra of PSA polymer, bare PES membrane and PES/PSA
Membrane PES (wt%) PA (wt%) PVP (wt%) DMAc (wt%) blended membranes were obtained for spectroscopic investiga-
Bare PES 18 0 0 82
tion. All of the FTIR spectra were recorded by attenuated total
PSA 1% 18 1 0 81 reflection (ATR) technique using Bruker-IFS 48 FTIR spectrometer
PSA 2% 18 2 0 80 (Ettlingen, Germany) with horizontal ATR device (Ge, 45 ). Thirty
PSA 5% 18 5 0 77 two scans were taken with 4 cm1 resolution between 500 and
PSA 10% 18 10 0 72
4000 cm1.
PSA 1% þ PVP 1% 18 1 1 80
PVP 2% 18 0 2 80
2.4.3. 1H NMR assay
Proton nuclear resonance spectroscopy (1H NMR) analysis was
the membranes are shown in Fig. 2. The color of the synthesized PSA carried out on a Bruker 300 MHz spectrometer for the synthesized
is yellow. Therefore, by increasing of PSA concentration in the PES PSA copolymer. The PSA was dissolved in DMSO as a solvent. Tet-
matrix, the resulted membranes become yellowish. ramethylsilane (TMS) was used as an internal reference.
For comparing the efficiency of the prepared PSA with another
pore former or hydrophilic additive, PVP blended membrane was 2.4.4. Scanning electron microscopy (SEM)
also fabricated. For providing the visual information of the top surface and cross
sectional morphology of the membranes, a Cambridge scanning
2.4. Characterization electron microscope (SEM, Cam Scan MV2300) was used. The
membranes were cut into small pieces, cleaned with filter paper,
2.4.1. Contact angle measurements of membranes immersed in liquid nitrogen for 15e20 s, frozen, broken and kept in
To study the surface wetting characteristics of blended PES air for drying. Then, the samples were gold sputtered for producing
membranes as a function of PSA concentration in the casting so- electric conductivity. Next, they were viewed with the microscope
lutions, water contact angle was measured on membrane surface at 20 kV.
using a contact angle measuring instrument (G10, KRUSS, Ger-
many). De-ionized water was used as a probe liquid in all mea- 2.4.5. Porosity
surements. To minimize the experimental error, the contact angles To estimate the overall porosity of the membranes (ε), the
were measured at five random locations for each sample and the gravimetric method was applied. The used equation is presented in
average number was reported. the Eq. (1) [10]:

Fig. 2. The photographs of the prepared PES membranes with different PSA concentrations.
4 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13

!
u1  u2 Jw;2
ε¼ (1) FRR ð%Þ ¼  100 (4)
A  l  dw Jw;1
In this equation, u1 and u2 are the weights of the wet and dry
membranes, respectively; A, l and dw are the membrane area (m2), where, Jw,1 and Jw,2 are pure water flux and second water flux after
thickness (m) and water density (0.998 g/cm3), respectively. BSA filtration, respectively.

2.4.6. Flux and retention 3. Results and discussion

The pure water flux, BSA solution permeation and protein
rejection properties of the membranes were investigated with a 3.1. Characterization of the synthesized PSA copolymer
dead-end filtration setup at room temperature. This dead-end cell
can test flat sheet membrane pieces with an effective area of The polysulfide-amide as a hydrophilic copolymer was synthe-
19.6 cm2. Distilled water and a solution with 500 ppm concentra- sized to modify the surface properties of PES membrane. This
tion of BSA were employed as the feed for evaluation of membrane copolymer containing thiazole rings, thioether linkages, bulky
performance. The membranes were pre-compressed with pure pendant phenyl rings and nitro groups was prepared by Yamaza-
water at 6 bar for 10 min and at 5 bar for 20 min. Then, the first pure kieHigashi phosphorylation polycondensation [30] from 5,50 -thi-
water flux, BSA permeation, and second pure were flux evaluated at obis(2-amino-4-phenyl-thiazole) as a diamine monomer and
4 bar for 90 min. The following equation was used to calculate the terephthalic acid as an aromatic dicarboxylic acid (Fig. 1). The
flux of membranes (L/m2h): synthesized copolymer is a tough linear aromatic polymer and
possesses a number of attractive features, such as excellent high
V temperature resistance and good solubility in polar aprotic solvents
J¼ (2) such as NMP, DMSO, DMAc and DMF at room temperature.
A: t
The structural feature of this copolymer was verified by FTIR, 1H
where V is the volume of permeate (L), A is the effective area of the NMR spectroscopy and elemental analysis. Fig. 3 shows the FTIR
membrane (m2), and t is the permeation time (h). spectrum of the synthesized PSA. The IR absorption band at
The protein rejection capability of the membranes was esti- 3356 cm1 can be attributed to the NH stretching frequency
mated by BSA solution concentration measurement using UVeVis because the FT-IR spectrum of polyamides shows the NeH
spectrophotometer. The BSA rejection (R. (%)) was calculated as stretching frequency as a broad band around 3300 cm1 [31]. The
follows: amide band, associated with the stretching vibration of the
carbonyl group appeared at 1674 cm1. The combined NeH


Cp bending and CeN stretching vibration appeared at 1532 cm1 [31].
R ð%Þ ¼ 1  100 (3)
Cf To obtain more complete and reliable chemical characterization,
the PSA was also investigated using 1H NMR spectroscopy. Fig. 4
where cp is concentration of BSA in permeate solution and cf rep- shows a typical 1H NMR spectrum of the synthesized PSA, in
resents the concentration of the BSA in feed solution. which all protons are in good agreement with the proposed
The flux recovery ratio (FRR), as a parameter for compare the structure. The peak appearing in the most downfield region sup-
antifouling property of the membranes was calculated based on the ports the formation of amide linkages [32]. The resonance signals of
following equation: protons in this nitro-substituted PA affected by the nitro

Fig. 3. FTIR spectrum of PSA.

 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13 5

Fig. 4. 1H NMR spectrum of PSA in DMSO-d6.

substituent on the pendant phenyl ring and shifted to lower field hydrophilic surface was produced by increasing of PSA in the
region compared to the corresponding PA [31]. casting solution. The higher hydrophilicity of PES/PSA membrane
Elemental analysis results: calculated values for polymer compared to the bare PES membrane can be attributed to the polar
repeated unit (C26H14N6O6S3)n: C, 51.82%; H, 2.34%; N, 13.95%. The groups of the blended PSA polymer such as nitro groups, thiazole
found values: C, 51.70%; H, 2.46%; N, 13.85%. rings and thioether linkages that are strongly hydrophilic.
The elemental analysis values agreed with the calculated ones Comparing the contact angle of the PSA blended membranes by
for the proposed structure of the PSA. However, because of the the PVP blended showed that the PSA has induced better hydrophilic
hygroscopic nature of amide groups, the value for carbon was lower properties than the PVP. All the evidences prove that PSA has high
than the calculated one for the proposed structure. hydrophilicity and the PVP is a pore former which has high tendency
to leach out the polymer structure [34] and increase the porosity of
the resulted membranes. However, the PSA is a large chain polymer
3.2. Effect of PSA concentrations on the surface properties
and in the phase separation process is slightly leached out to the
non-solvent bath and trapped between the PES chains.
The polyethersulfone is intrinsically a hydrophobic polymer
To illustrate the better performance of PSA rather than PVP, a
with fouling tendency. There is a reverse relationship between
membrane containing 1 wt% PVP and 1 wt% PSA was prepared. The
fouling on the membrane surface and surface hydrophilicity [33].
contact angle and porosity analyses showed that the porosity of the
The hydrophilicity of the bare PES membrane and the membranes
resulted membrane is lower than the 2 wt% PVP blended mem-
blended with PSA or PVP estimated by contact angle measurement.
brane but its hydrophilicity is higher, indicating remaining of the
The effect of PSA concentration on the contact angle and porosity of
PSA in PES matrix and inducing its property to the PES.
the blended membranes are presented in Table 2. The highest
The porosity data in Table 2 shows that by addition of the
contact angle was obtained for the bare PES membrane without
polyamide additive to the PES casting solution, the porosity is
addition of PSA in the casting solution. This indicated the lowest
increased. This can be related to the fast exchange of solvent and
hydrophilicity for the bare PES. When the concentration of PSA in
non-solvent in the phase inversion process due to the hydrophilic
the casting solution was increased, the contact angle of the mem-
PSA presence. The hydrophilic PSA is highly effective on the
branes was decreased. The blended membrane containing 10 wt.%
physico-chemical properties of the casting solution over phase
PSA in the casting solution exhibited lowest contact angle and
inversion process that influences the thermodynamic and kinetic
therefore the highest hydrophilicity. This pointed out that a more
driving forces [35]. This increase of porosity was up to 5 wt% of the
PSA concentration and after that; the porosity was reduced due to
Table 2 overcoming of solution viscosity in higher concentrations of the
Effect of PSA on hydrophilicity and porosity. PSA on the kinetic forces [33,35]. As is shown in Table 2, the
porosity of PVP blended membranes was higher than the PSA/PES
Membrane Contact angle (◦) Porosity (%)
membranes, showing that the PVP is a better pore former than the
Bare PES 75.6 ± 1.6 77.6 ± 1.9
PSA. However, the contact angle results showed that the hydro-
PSA 1% 70.7 ± 3.4 79.5 ± 1.6
PSA 2% 68.3 ± 1.4 81.9 ± 2.1 philicity of the PSA blended membranes were better and it could be
PSA 5% 66.5 ± 2.2 82.5 ± 2.2 induce superior antifouling properties to the PES membrane.
PSA 10% 63.8 ± 1.1 77.4 ± 1.3 Fig. 5 shows the ATR-FTIR spectrum of the membranes which
PSA 1% þ PVP 1% 68.0 ± 2.4 82.9 ± 1.1 provides some information about chemical structures and func-
PVP 2% 70.7 ± 1.7 83.8 ± 1.9
tional groups on the surface of the membranes. The spectrum
6 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13

Fig. 5. ATR-FTIR spectra of the pure PES and the 10 wt% PSA blended membranes.

related to the bare PES shows absorption bands at 1294 and Also, the cross-sectional SEM images related to the PVP con-
1149 cm1 attributed to the asymmetrical and symmetrical vibra- taining membranes show that the porosity of these membranes are
tions of the sulfone group, respectively. The absorption bands at more than the PSA blended membranes, which have more big
1010 and 1240 cm1 were assigned to the stretching vibration of finger-like pores and tend to have macro-void structures.
diphenyl CeOeC bond in the PES polymer [36]. The strong ab- These changes in the membrane morphology can be explained
sorptions in 1480e1580 cm1 region are associated with the ben- by the phase separation mechanism during the immersion pre-
zene ring skeletal stretching mode [37]. These bands appeared in cipitation. As soon as immersing casting film into a bath containing
the spectra of PES/PSA blended membranes too. However, their non-solvent, due to immiscibility between polymer and non-
intensities were decreased showing that PSA concentration in the solvent in the bath (distillated water), film precipitation process
surface of the membrane is increased. The spectrum of the blended starts, and film thickness is reduced gradually over time. At the
membrane is different from that of the bare PES membrane. Fig. 3 same time, high miscibility between solvent and non-solvent lead
shows that the FTIR of the prepared PSA polymer presented three to a great amount of non-solvent permeate through various parts of
absorption bands at 1533, 1670 and 3334 cm1. These bands were the precipitating film and the solvent starts to get out of the film.
appeared in the spectrum of the PSA containing membrane. These Because of immiscibility between the polymer and the non-solvent,
observations indicate that the PSA is remained in the casting so- the polymers in the water infiltration path reject and therefore the
lution and leads to the highest surface hydrophilicity in the PSA 10% solvent/non-solvent-rich cores are created. It should be mentioned
blended membrane. that when the solvent starts to exit from water infiltration paths,
which lead to reduction of the presence of solvent in those paths,
3.3. Effect of PSA on the blended membrane morphology repulsion between the water and the polymer chains increases
largely. Finally, with increasing the compression of the polymer
There is a relationship between the membrane structure and chains and their freezing, the membrane is formed. Thus, reducing
composition of the casting solution. The nature and concentration the film thickness and solidification of polymers in the water
of additives play important roles in the modification of the mem- infiltration path both affects the compression of polymer chains
brane properties. To evaluate the morphology of the membranes, and thus formation of the membrane [38].
the cross-sections of different prepared ultrafiltration blended According to the above description, if the conditions for initial
membranes were characterized by SEM images and presented in penetration of water into the film and the excretion of polymers in
Fig. 6. The cross-sectional SEM images demonstrated an asym- water infiltration path (easier and faster growth of non-solvent/
metric structure contain of a dense skin layer, a porous sub-layer solvent rich cores) provides, it will be expected that formation of
and fully developed finger-like pores at the bottom layer for all of membrane as a result of high compression and eventually freezing
the prepared membranes. However, there are some different of the polymer chains, occurs in the shorter time (instantaneous
structures among them. The bare PES membrane showed thick skin demixing). Because the faster growth of these cores, in other
layer and low porous bottom layer with short finger-like structure, words, better excretion of polymers in water infiltration paths
that tend to be sponge. By addition of the low amount of 1 wt% caused the polymer chains compressed, and therefore accelerate
polysulfide-amide as a hydrophilic additive to the casting solution, the freezing of them, formation of membrane, and produce of the
the length of finger-like pores is extended and thickness of the skin membranes with more porosity [39]. After the arrival of the film
layer is reduced and the porosity is increased. Totally, the thickness consists of polymer (PES), solvents, and the additive (PSA copol-
of dense skin layer is decreased with addition of PSA content in the ymer) with non-solvent property into the non-solvent bath, the
casting solution and the porosity of top-layer and sub-layer is locations containing the additive are suitable for non-solvent to
increased with increase in PSA contents up to 5 wt%. penetrate quickly into the film structure. The polymer reluctance
 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13 7

Fig. 6. Effect of polymeric additive amount on cross-sectional SEM images of (a) Bare PES (0 wt% PSA), (b) 1 wt% PSA, (c) 2 wt% PSA, (d) 5 wt% PSA, (e) 10 wt% PSA, (f) 1 wt%
PVPþ1 wt% PSA and (g) 2 wt% PVP.

respect to the additive with non-solvent property causes the additive to be created which can be quickly attacked by water
polymer chains in the joint areas of this additive, even in small molecules which can lead to the formation of the membranes with
amounts, retreated and the small seams in the vicinity of the thinner skin layer [33].
8 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13

Fig. 6. (continued).

In other words, thermodynamics and kinetics as two effective enhancement of the viscosity of dope solution with increase of PSA
factors control the formation of phase inversion membranes. The copolymer more than 2%, caused the kinetic hindrance against
presence of PSA in the dope solution enhanced thermodynamic phase separation [24]. Also, the long chain length of PSA caused the
instability, which is in favor of the phase separation process while blend casting solution be prone to phase separation.
 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13 9

Fig. 6. (continued).

Fig. 7 shows the surface SEM images of the prepared mem- In the membrane with 1 wt% PAþ1 wt% PVP, the pure water flux
branes. As seen, by addition of 1 and 2 wt% PSA to the PES casting was increased more than only 2 wt% PSA blended membrane,
solution, density of the pores in the membranes surface is which can be attributed to more porosity increasing because of
increased. However, in 5 and 10 wt%, that is decreased, which can existence of PSA with polar functional groups with appropriate
be attributed to increase of the casting solution viscosity (kinetic concentrations and PVP as a pore former. The hydrophilicity of this
hindrance). Also, it can be seen that the membranes prepared by membrane is almost at the level of 2 wt% PSA membrane according
adding PVP have high density of pores in the membrane surface. It to Table 2. Therefore, to increase membrane permeability, both the
is well known that the addition of PVP as a pore former in the porosity and the hydrophilicity should be enhanced. However, the
casting solution mostly changes the surface porous structure. This BSA flux of the 2 wt% PSA blended membrane is higher than the
is because the interaction between NeC]O group in PVP and O] 1 wt% PAþ1 wt% PVP, showing its good antifouling properties.
S]O group in PES that may cause an increment of large pores in the Fig. 9 was indicated the changes in protein rejection of the
membrane surface [40]. membranes as a function of PSA concentration in the casting so-
lution. As shown in this figure, the BSA protein rejection of the
3.4. Effect of PSA on the blended membrane performance modified membranes was not changed significantly showing that
the addition of PSA was not induced any defect on the membrane
The performance of the prepared ultrafiltration membranes was body. In addition, these modified membranes can be used for
investigated by pure water flux, BSA flux and protein rejection. protein concentration, whey filtration and related industry.
Fig. 8 displays the effect of PSA concentration in the casting solution
on the pure water and BSA solution flux. With considering the re- 3.5. Antifouling properties
sults for the bare PES, PSA 1 wt%, and PSA 2 wt%, it can be found that
the flux of pure water and BSA solutions were increased with in- The BSA was applied as a model protein to examine the anti-
crease of amount of PSA in the casting solution. The permeability of fouling property and separation performance of the polymeric ad-
membranes is significantly affected by membrane surface pore size, ditive blended membranes. Usually, membrane fouling and
porosity, hydrophilicity and skin layer thickness [33]. concentration polarization are the two major factors for flux decrease
The surface SEM images (Fig. 7) showed that by addition of 1 and in protein ultrafiltration. The concentration polarization was mini-
2 wt% PSA, the pore density was increased, which can improve the mized due to the rigorous stirring (400 rpm) close to the membrane
membrane flux. The cross-sectional SEM images (Fig. 6) illustrated surface. Thus, the flux decline was mostly caused by the BSA fouling.
that the skin layer thickness of the PSA blended membranes was Fig. 10 shows the pure water flux, BSA solution flux and second
reduced. Also, the hydrophilicity and the porosity (Table 2) of these water flux after washing membrane with water related to time. As
membranes were increased, that all can be presented the improving shown, the PES membrane blended with 2 wt% PVP shows the
of the membranes properties to increase their permeability. highest fluxes. However, reduction of the fluxes versus time shows
In case of membranes with 5 and 10 wt% PSA copolymer, the flux that the 2 wt% PVP membranes has more rapid reduction in flux
of pure water and BSA solution decreased compared to PSA 2 wt%, presenting its higher fouling tendency. Also, because of higher
but they were many higher than the bare PES. This is because of the porosity of the 2 wt% PVP membrane, it is compressed by pressure
increase in the PSA concentration more than 2 wt%, result in in- during filtration and its water flux is also reduced.
crease of dope solution viscosity which caused the kinetic hin- Fig. 11 presented the flux recovery ratio (FRR) of the membranes.
drance against the phase separation that acts against the As shown, the highest FRR was for the bare PES membrane. How-
thermodynamic instability. ever, this comparison is not accurate. Because the water flux or
Comparing the hydrophilicity, the surface SEM images and the permeability of the blended membranes is almost ten times larger
porosity of 2 and 10 wt% PSA blended PES membrane presents that than the bare PES membrane. As well known, the fouling is related
although the hydrophilicity of the 10 wt% is higher than 2 wt% PSA to the membrane flux [41] and by increasing of membrane flux, its
membrane, its porosity and surface pore density are lower. There- fouling probability increases [42]. Therefore, the comparison
fore, these cause to reduction in flux of this membrane. should be carried out between blended membranes.
10 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13

Fig. 7. Effect of additive amounts on surface SEM images of (a) Bare PES, (b) 1 wt% PSA, (c) 2 wt% PA, (d) 5 wt% PA, (e) 10 wt% PA, (f) 1 wt% PAþ1 wt% PVP and (g) 2 wt% PVP.
 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13 11

Fig. 8. Effect of PSA concentration on pure water and BSA solution flux.

100

95

90

85
Protein rejecƟon (%)

80

75

70

65

60

55

50
PES PSA 1% PSA 2% PSA 5% PSA 10% PSA 1%+ PVP 1% PVP 2%

Fig. 9. BSA protein rejection of the prepared membranes.

As presented in Fig. 11, the FRR of the PSA blended membranes various concentrations in the casting solution. First, the fabricated
is higher than the 2 wt% PVP blended membrane, showing better PSA was characterized using FTIR and NMR techniques. Then, the
antifouling properties of them. The PVP is a pore former that most related membranes were prepared and characterized. The obtained
of it leaches out the polymer structure and increase of the results can be concluded as follows:
membrane porosity. Nevertheless, the PSA is a large chain polymer
and it is slightly leached out to the non-solvent bath in the phase ➢ The pure water flux of the blended membranes was significantly
separation process and trapped between the PES chains and in- increased by addition of the PSA to the PES casting solution. The
duces better hydrophilic properties from the PVP. Therefore, the flux was increased with the PSA content up to 2 wt% and next,
hydrophilicity of the PSA blended membranes is more than 2 wt% decreased with more content due to higher viscosity of the
PVP, which causes to better antifouling properties. casting solutions in higher concentration of the PSA.
As total results, the polysulfide-amide additive could improve ➢ The PSA additive improved membrane hydrophilicity, porosity,
membrane hydrophilicity, porosity, permeability and antifouling permeability and antifouling properties. However, the PVP had
properties. However, the PVP has better performance in case of better performance in case of porosity and permeability
porosity and permeability. Thus, for coupling of the effect of these enhancement. Therefore, the membrane with 1 wt% PVP and
two additives, the membrane with 1 wt% PVP and 1 wt% PSA was 1 wt% PSA was prepared to combine both additive effects. The
prepared. The results showed that the resulted membrane have resulted membrane showed good solution flux with good anti-
good solution flux with good antifouling properties. fouling properties.
➢ The morphological studies of PES/PSA blended membranes
indicated that the addition of PSA in the casting solution results
4. Conclusion in porous membranes and lower thickness of dense skin layer.
➢ The hydrophilicity of the membranes is enhanced for all con-
The high performance blended PES ultrafiltration membranes centrations of PSA. This is because of hydrophilic functional
were prepared by addition of synthesized polysulfide-amide in
12 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13

400
PVP 2%
350 PVP 1%, PSA 1%
PSA 2%
PSA 1%
300
PSA 5%
Bare PES
250
Flux (L/m2 h)

200

150

100

50

0
0 25 50 75 100 125 150 175 200 225 250 275

Time (min)

Fig. 10. Flux versus time for the blended PES membranes at 5 bar during three steps: pure water flux for 90 min, BSA solution (500 ppm) flux for 90 min, and second water flux after
20 min washing with distilled water.

100
90
76.0 71.4
80
63.3
70 59.1 60.2 60.2
54.6
60
FRR (%)

50
40
30
20
10
0
PES 18 PA 1% PA 2% PA 5% PA 10% PVP 2% PVP1%+
PA1%
Fig. 11. Flux recovery ratio of the prepared UF membranes.

groups of PSA copolymer, causing to better antifouling mechanism, structure and performance, J. Membr. Sci. 385e386 (2011)
110e122.
properties.
[3] M. Sivakumar, D.R. Mohan, R. Rangarajan, Studies on cellulose acetate-
polysulfone ultrafiltration membranes: II. Effect of additive concentration,
Acknowledgment J. Membr. Sci. 268 (2006) 208e219.
[4] B. Marrot, A. Barrios-Martinez, P. Moulin, N. Roche, Industrial wastewater
treatment in a membrane bioreactor: a review, Environ. Prog. 23 (2004)
The authors thank the Kharazmi University (KHU, Iran) for all of 59e68.
the supports provided. [5] S.S. Madaeni, S. Zinadini, V. Vatanpour, Convective flow adsorption of nickel
ions in PVDF membrane embedded with multi-walled carbon nanotubes and
PAA coating, Sep. Purif. Technol. 80 (2011) 155e162.
References [6] S.H. Ye, J. Watanabe, M. Takai, Y. Iwasaki, K. Ishihara, High functional hollow
fiber membrane modified with phospholipid polymers for a liver assist
[1] M. Peyravi, A. Rahimpour, M. Jahanshahi, A. Javadi, A. Shockravi, Tailoring the bioreactor, Biomaterials 27 (2006) 1955e1962.
surface properties of PES ultrafiltration membranes to reduce the fouling [7] J.C. Nunes, M.T.P. de Amorim, I.C. Escobar, J.A. Queiroz, A.M. Mor~ ao, Plasmid
resistance using synthesized hydrophilic copolymer, Microporous Meso- DNA/RNA separation by ultrafiltration: modeling and application study,
porous Mater. 160 (2012) 114e125. J. Membr. Sci. 463 (2014) 1e10.
[2] S. Zhao, Z. Wang, X. Wei, X. Tian, J. Wang, S. Yang, S. Wang, Comparison study [8] D. Zavastin, I. Cretescu, M. Bezdadea, M. Bourceanu, M. Dra gan, G. Lisa,
of the effect of PVP and PANI nanofibers additives on membrane formation I. Mangalagiu, V. Vasi
c, J. Savi
c, Preparation, characterization and applicability
 A. Jalali et al. / Microporous and Mesoporous Materials 228 (2016) 1e13 13

of cellulose acetateepolyurethane blend membrane in separation techniques, [27] A. Rahimpour, S.S. Madaeni, A. Shockravi, S. Ghorbani, Preparation and
Colloid. Surf. A Physicochem. Eng. Asp. 370 (2010) 120e128. characterization of hydrophile nano-porous polyethersulfone membranes
[9] H. Rabiee, M.H.D.A. Farahani, V. Vatanpour, Preparation and characterization using synthesized poly (sulfoxide-amide) as additive in the casting solution,
of emulsion poly(vinylchloride) (EPVC)/TiO2 nanocomposite ultrafiltration J. Membr. Sci. 334 (2009) 64e73.
membrane, J. Membr. Sci. 472 (2014) 185e193. [28] A. Rahimpour, S.S. Madaeni, S. Ghorbani, A. Shockravi, Y. Mansourpanah, The
[10] S. Zinadini, A.A. Zinatizadeh, M. Rahimi, V. Vatanpour, H. Zangeneh, influence of sulfonated polyethersulfone (SPES) on surface nano-morphology
M. Beygzadeh, Novel high flux antifouling nanofiltration membranes for dye and performance of polyethersulfone (PES) membrane, Appl. Surf. Sci. 256
removal containing carboxymethyl chitosan coated Fe3O4 nanoparticles, (2010) 1825e1831.
Desalination 349 (2014) 145e154. [29] A. Javadi, A. Shockravi, M. Koohgard, A. Malek, F.A. Shourkaei, S. Ando, Nitro-
[11] A.P. Duarte, M.T. Cidade, J.C. Bordado, Cellulose acetate reverse osmosis substituted polyamides: a new class of transparent and highly refractive
membranes: optimization of the composition, J. Appl. Polym. Sci. 100 (2006) materials, Eur. Polym. J. 66 (2015) 328e341.
4052e4058. [30] N. Yamazaki, M. Matsumoto, F. Higashi, Studies on reactions of the Nphos-
[12] H. Susanto, M. Balakrishnan, M. Ulbricht, Via surface functionalization by phoniumsalts of pyridines. XIV. Wholly aromatic polyamides by the direct
photograft copolymerization to low-fouling polyethersulfone-based ultrafil- polycondensation reaction by using phosphites in the presence of metal salts,
tration membranes, J. Membr. Sci. 288 (2007) 157e167. J. Polym. Sci. Polym. Chem. Ed. 13 (1975) 1373e1380.
[13] H. Susanto, M. Ulbricht, Characteristics, performance and stability of poly- [31] A. Javadi, A. Shockravi, M. Kamali, A. Rafieimanesh, A.M. Malek, Solution
ethersulfone ultrafiltration membranes prepared by phase separation method processable polyamides containing thiazole units and thioether linkages with
using different macromolecular additives, J. Membr. Sci. 327 (2009) 125e135. high optical transparency, high refractive index, and low birefringence,
[14] Y.-Q. Wang, Y.-L. Su, X.-L. Ma, Q. Sun, Z.-Y. Jiang, Pluronic polymers and J. Polym. Sci. Part A Polym. Chem. 51 (2013) 3505e3515.
polyethersulfone blend membranes with improved fouling-resistant ability [32] A. Javadi, Z. Najjar, S. Bahadori, V. Vatanpour, A. Malek, E. Abouzari-Lotf,
and ultrafiltration performance, J. Membr. Sci. 283 (2006) 440e447. A. Shockravi, High refractive index and low-birefringence polyamides con-
[15] H.Y. Hwang, D.J. Kim, W.J. Yim, S.Y. Nam, PES/SPAES blend membranes for taining thiazole and naphthalene units, RSC Adv. 5 (2015) 91670e91682.
nanofiltration: the effects of sulfonic acid groups and thermal treatment, [33] V. Vatanpour, S.S. Madaeni, R. Moradian, S. Zinadini, B. Astinchap, Fabrication
Desalination 289 (2012) 72e80. and characterization of novel antifouling nanofiltration membrane prepared
[16] A.L. Ahmad, A.A. Abdulkarim, B.S. Ooi, S. Ismail, Recent development in ad- from oxidized multiwalled carbon nanotube/polyethersulfone nano-
ditives modifications of polyethersulfone membrane for flux enhancement, composite, J. Membr. Sci. 375 (2011) 284e294.
Chem. Eng. J. 223 (2013) 246e267. [34] B. Chakrabarty, A.K. Ghoshal, A.K. Purkait, Preparation, characterization and
[17] C. Zhao, J. Xue, F. Ran, S. Sun, Modification of polyethersulfone membranes e a performance studies of polysulfone membranes using PVP as an additive,
review of methods, Prog. Mater. Sci. 58 (2013) 76e150. J. Membr. Sci. 315 (2008) 36e47.
[18] G.-d. Kang, Y.-m. Cao, Application and modification of poly(vinylidene fluo- [35] K.-W. Lee, B.-K. Seo, S.-T. Nam, M.-J. Han, Trade-off between thermodynamic
ride) (PVDF) membranes e a review, J. Membr. Sci. 463 (2014) 145e165. enhancement and kinetic hindrance during phase inversion in the prepara-
[19] Y. Ma, F. Shi, J. Ma, M. Wu, J. Zhang, C. Gao, Effect of PEG additive on the tion of polysulfone membranes, Desalination 159 (2003) 289e296.
morphology and performance of polysulfone ultrafiltration membranes, [36] S.S. Madaeni, M. Mohammadi Sarab Badieh, V. Vatanpour, Effect of coating
Desalination 272 (2011) 51e58. method on gas separation by PDMS/PES membrane, Polym. Eng. Sci. 53 (2013)
[20] S. Loeb, S. Sourirajan, Sea water demineralization by means of an osmotic 1878e1885.
membrane, in: Saline Water ConversiondII; Advances in Chemistry, Amer- [37] N. Ghaemi, S.S. Madaeni, A. Alizadeh, P. Daraei, M. Mohammadi Sarab Badieh,
ican Chemical Society, Washington, DC, 1963. M. Falsafi, V. Vatanpour, Fabrication and modification of polysulfone nano-
[21] S. Loeb, S. Sourirajan, High flow porous membranes for separating water from filtration membrane using organic acids: morphology, characterization and
saline solutions. US patents, US3,133,132A; 1964. performance in removal of xenobiotics, Sep. Purif. Technol. 6 (2012) 214e228.
[22] I.-C. Kim, K.-H. Lee, Effect of poly (ethylene glycol) 200 on the formation of a [38] P. Radovanovic, S.W. Thiel, S.-T. Hwang, Formation of asymmetric polysulfone
polyetherimide asymmetric membrane and its performance in aqueous sol- membranes by immersion precipitation. Part II. The effects of casting solution
vent mixture permeation, J. Membr. Sci. 230 (2004) 183e188. and gelation bath compositions on membrane structure and skin formation,
[23] M.K. Sinha, M.K. Purkait, Preparation of fouling resistant PSF flat sheet UF J. Membr. Sci. 65 (1992) 231e246.
membrane using amphiphilic polyurethane macromolecules, Desalination  Stropnik, V. Musil, M. Brumen, Polymeric membrane formation by wet-
[39] C.
355 (2015) 155e168. phase separation; turbidity and shrinkage phenomena as evidence for the
[24] R.M. Boom, I.M. Wlenk, Th van den Boomgaard, C.A. Smolders, Microstruc- elementary processes, Polymer 41 (2000) 9227e9237.
tures in phase inversion membranes. Part 2. The role of a polymeric additive, [40] L. Lafreniere, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Effect of PVP additive on
J. Membr. Sci. 73 (1992) 277e292. the performance of PES ultrafiltrationmembrane, Ind. Eng. Chem.Res. 26
[25] Y. Su, C. Li, W. Zhao, Q. Shi, H. Wang, Z. Jiang, S. Zhu, Modification of poly- (1987) 2385e2389.
ethersulfone ultrafiltration membranes with phosphorylcholine copolymer [41] D.C. Sioutopoulos, A.J. Karabelas, The effect of permeation flux on the specific
can remarkably improve the antifouling and permeation properties, J. Membr. resistance of polysaccharide fouling layers developing during dead-end ul-
Sci. 322 (2008) 171e177. trafiltration, J. Membr. Sci. 473 (2015) 292e301.
[26] E. Eren, A. Sarihan, B. Eren, H. Gumus, F.O. Kocak, Preparation, characterization [42] M.A.H. Johir, J. George, S. Vigneswaran, J. Kandasamy, A. Sathasivan,
and performance enhancement of polysulfone ultrafiltration membrane using A. Grasmick, Effect of imposed flux on fouling behavior in high rate membrane
PBI as hydrophilic modifier, J. Membr. Sci. 475 (2015) 1e8. bioreactor, Biores. Technol. 122 (2012) 42e49.