Desalination 419 (2017) 79–87

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

Self-antifouling properties of magnetic Fe2O3/SiO2-modified poly MARK

(piperazine amide) active layer for desalting of water: Characterization and
performance
Yaghoub Mansourpanaha,e,⁎, Ahmad Rahimpourb, Meisam Tabatabaeic,d, Landry Bennette
a
Membrane Research Laboratory, Lorestan University, Khorramabad 68137-17133, Iran
b
Membrane Research Laboratory, School of Chemical Engineering, Babol University of Technology, Babol, Iran
c
Microbial Biotechnology Department, Agricultural Biotechnology Institute of Iran (ABRII), Agricultural Research, Education, and Extension Organization (AREEO),
31535-1897 Karaj, Iran
d
Membrane Separation Technology (MST) Group, Biofuel Research Team (BRTeam), Karaj, Iran
e
Department of Chemistry, Michigan State University, East Lansing, MI, USA

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, changes in structure and performance of poly (piperazine amide) thin layer membranes in-
Polyamide thin film corporated with Fe2O3/SiO2 nanoparticles to fabricate new modified thin films were investigated. Thin films
Nanocomposite membrane incorporated with Fe2O3/SiO2 offered enhanced performance and antifouling properties compared with un-
Magnetic iron oxide modified thin layers. AFM and SEM images clearly illustrated that the morphology and structure of the surface of
Heavy metals
thin layers varied in the presence of the nanoparticles. Moreover, the rejection capability of the thin films toward
NaCl (from 13.2 to 30.1%), Na2SO4 (from 58.5 to 85.0%), PbNO3 (from 33.3 to 64.0%), and CuSO4 (from 57.1 to
80.0%) showed favorable changes, leading to improved performance of the Fe2O3/SiO2-modified poly (piper-
azine amide) thin film composite membranes. Increasing of the flux recovery ratio (FRR) to about 96% proved
that the employed modification procedure was successful. It should be highlighted that a thinner poly (piper-
azine amide) layer containing more eCOOH functional groups was obtained at a proper concentration of Fe2O3/
SiO2. On the contrary, higher concentrations of the nanoparticles led to undesired properties for the Fe2O3/SiO2-
modified thin films.

⁎
Corresponding author at: Membrane Research Laboratory, Lorestan University, Khorramabad 68137-17133, Iran.
E-mail address: mansourpanah.y@lu.ac.ir (Y. Mansourpanah).

http://dx.doi.org/10.1016/j.desal.2017.06.006
Received 5 March 2017; Received in revised form 19 May 2017; Accepted 6 June 2017
Available online 19 June 2017
0011-9164/ © 2017 Elsevier B.V. All rights reserved.
Y. Mansourpanah et al.
1. Introduction
In the 1970s, Cadotte et al. reported the formation of thin film
composite (TFC) membranes by the interfacial polymerization (IP)
technique in which polymerization took place at an interface between
an organic solution consisting of a carboxyl chloride reagent and an
aqueous solution containing a diamine [1]. Accordingly, an active layer
of cross-linked polyamide was deposited as a thin film on the porous
layer. TFC membranes include a dense and thin layer that controls the
performance of the membranes (including permeability and se-
lectivity), and a thicker porous moiety which provides mechanical
properties to the thin layer. Hence, a thin layer with lower thickness
and more hydrophilicity could result in valuable permeability and se-
lectivity [2]. Overall, the performance of the top polyamide thin layer
membrane can be significantly influenced by some physiochemical
properties such as selectivity, permeability, surface roughness, charge
and hydrophilicity.
Recently, many studies have been focused on the development and
improvement of the thin layer properties to achieve the best perfor-
mance conditions. These research activities include a wide range of
changes such as alterations in monomer types, temperature, organic
media, different additives (organic or inorganic), incorporated nano-
particles, etc. [3–14]. Several studies have reported the benefits of
adding different inorganic nanoparticles to the polyamide thin layers to
enhance their performance. A high flux reverse osmosis nanocomposite
polyamide membrane was prepared by Cruz-Silva et al. by interfacial
polymerization to incorporate multi-walled carbon nanotubes [15].
They reported increased performance and chlorine resistance for the
membranes. In a different study, Ratto et al. [16] compared membranes
fabricated with and without embedded carbon nanotubes. They argued
that in the presence of carbon nanotubes, water flux was increased by
two times. Hegab et al. also showed that the selectivity, mechanical
strength, antifouling, water flux and thermal properties of the mem-
branes fabricated were remarkably improved after the incorporation of
graphene oxide [17]. Al-Hobaib et al. [6] added silver oxide nano-
particles into the polyamide thin film via interfacial polymerization
process. As a result, 0.003 wt% Ag2O nanoparticle-embedded mem-
branes showed a significant change in the flux from 26 to 40 L/m2 h
and a desired alteration in salt rejection to about 99%. Mansourpanah
et al. investigated modified polyamide thin layer in the presence of
PEG-modified grapheme oxide. They claimed increased antifouling
properties and rejection capabilities of the thin film membranes [18].
Combination of Fe2O3 and its derivatives nanoparticles with dif-
ferent organic and inorganic materials showed favorable changes in
structure and morphology of the nanocomposite products [19–22]. In
the current work, the effect of SiO2-covered Fe2O3 nanoparticles, as
additive, on the performance and characteristics of nanoparticle-mod-
ified poly (piperazine amide) thin layers was investigated. Two con-
centrations of Fe2O3/SiO2 nanoparticles were added to the aqueous
phase to evaluate the observed alterations in the morphology and
performance of the thin layers. The goal was to determine how the
presence of nanoparticles causes new conditions affecting on the in-
terfacial polymerization process, making different changes in structure
and performance (water flux and salt rejection) of the thin layers.
Different salts (NaCl, Na2SO4, PbNO3, and CuSO4) were employed to
study the desalting properties of the fabricated thin film membranes.
The reason behind the utilization of heavy metal salts was to study the
structural changes of the thin films by tracking the alterations in the
functional groups. Field emission-Scanning electron microscope (FE-
SEM), atomic force microscope (AFM), attenuated total reflectance-in-
frared spectroscopy (ATR-IR), zeta potential, water contact angle as
well as a membrane set-up were employed to determine the char-
acteristics of Fe2O3/SiO2-embedded poly (piperazine amide) thin
layers.
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Desalination 419 (2017) 79–87
2. Experimental
2.1. Materials
FeCl2.4H2O, FeCl3.6H2O, ammonium, ethanol, and tetra-
ethylortholsilicate (TEOS) were purchased from Merck (Germany) and
were used for synthesizing Fe2O3/SiO2 nanoparticles. Poly (ethersul-
fone) (PES Ultrason E6020P with MW = 58,000 g/mol) was obtained
from BASF Co. (Germany), and poly(vinylpyrrolidone) (PVP, 25,000 g/
mol), acrylic acid (AA), dimethylformamide (DMF), and poly (etyle-
neglycole) (PEG-600) (Merck, Germany) were used in this work. 1,3,5-
benzenetricarbonyltrichloride (TMC, 98%), n-hexane, piperazine (PIP)
and triethylamine (TEA, 99.5%) (Merck, Germany) were employed to
prepare poly (piperazine-amide) thin films. NaCl, Na2SO4, PbNO3, and
CuSO4 salts (Merck, Germany) were utilized for the investigation of ion
rejection capability. Bovine Serum Albumin powder (some properties
are as follows: assay > 96%; mol wt., 66 kDa; solubility > 40 mg/mL
in H2O) were obtained from Sigma-Aldrich (Germany) and was used for
the evaluation of antifouling properties of the membranes. Deionized
water (DI) was used throughout the study.
2.2. Preparation of the polymeric substrate
PES, PVP, AA, and PEG-600 with 17, 2, 3, and 5 wt%, respectively,
were dissolved in DMF. PVP, AA, and PEG-600 were added to the
casting solution as pore formers [18]. To obtain a homogeneous solu-
tion, the polymeric solution was stirred in 300 rpm for 24 h at 50 °C.
Then, to remove all air bubbles, the dope solution was kept at the
ambient temperature for about 24 h. Afterwards, the homogeneous
polymeric solution was cast on a glass plate at 200 μm thickness using a
film applicator without evaporation at room temperature and in 30%
humidity. Finally, the resulting film was subsequently and immediately
immersed into a coagulation bath (distilled water) for at least 24 h to
guarantee phase separation.
2.3. Preparation of magnetic Fe2O3/SiO2 nanoparticles
Iron oxide nanoparticles were synthesized by co-precipitation of
two salts of FeCl3·6H2O and FeCl2·4H2O at the molar ratio of (2:1)
[23,24]. The salts were dissolved in deionized water under nitrogen
atmosphere. After adequate time of stirring, ammonium solution was
added to the mixture dropwise. Fe3O4 precipitate was separated by a
magnet and was rinsed with deionized water. Silica coated iron oxide
nanoparticles were prepared by the hydrolysis of TEOS. For this pur-
pose, 2 mL distilled water, 0.8 mL ethanol, and 0.1 g iron oxide nano-
particles were sonicated for 1 h. The mixture solution was stirred slowly
followed by dropwise addition of ammonium (0.5 mL) and tetra-
ethylorthosilicate (TEOS, 0.2 mL) solutions. Fig. 1 schematically shows
the structure of the silica-modified iron oxide.
2.4. Preparation of Fe2O3/SiO2 nanoparticle-containing poly (piperazine-
amide) thin films
Poly (piperazine-amide) thin layers were formed by interfacial
polymerization process on a PES support. An appropriate flat sheet of
the PES support was placed between two Teflon frames 0.7 cm in height
with inner cavity of 7.5 cm × 20 cm and the poly (piperazine-amide)
thin films were prepared using two aqueous and organic solutions as
follows:
A 30 min sonicated (to avoid the aggregation of nanoparticles)
aqueous phase containing PIP (0.15 wt%), TEA (0.4 wt%), and different
concentrations of the magnetic nanoparticles (0.01 and 0.05 wt%) were
added on the top of the support and were allowed to wet the surface.
Then, the surface of the PES support was rolled by a soft rubber roller to
eliminate any tiny bubbles formed. After 5 min, the excess of aqueous
solution was discharged. Afterwards, the TMC-containing n-hexane
Y. Mansourpanah et al. Desalination 419 (2017) 79–87

Fig. 1. Schematic structure of the silica-modified iron oxide.

OH
O Si O
HO
Si Si OH
O O
HO Si Si OH
O O
Si Si
HO Si O OH
O
OH

Table 1 average values were reported. Droplets (2 μL) were inserted onto the
Composition of the thin layer membranes. membrane surface with the rate of 1 μL/s and a side view image was
taken after 10 s [25].
TFC membrane Nanoparticle TMC SDS TEA PIP Fe Si
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)

M0 – 0.1 0.1 0.4 0.15 0.0 0.0 2.5.5. Filtration performance

M0.01 0.01 0.1 0.1 0.4 0.15 0.6 0.7 An aluminum batch stirred cell with 90 mL volume capacity with an
M0.05 0.05 0.1 0.1 0.4 0.15 0.8 2.34
effective area of 12.5 cm2 was used for all filtration tests. A piece
(~ 12 cm2) of the membranes was prepared and loaded in the filtration
solution was poured into the Teflon frames and was maintained for cell. Filtration continued at room temperature for 1 h to obtain a con-
5 min for the conventional interfacial polymerization reaction to occur. stant flux. The cell was equipped with a nitrogen gas inlet to impound
Subsequently, the excess of organic solution was discharged from the the liquid in the cup under a fixed operating pressure of 0.6 MPa. The
frames and the prepared poly (piperazine-amide) thin layer membrane filtration cell was filled with 80 mL of the feed solution with different
was kept in an oven at 70 °C. Table 1 summarizes the composition of ion solutions (NaCl, Na2SO4, PbNO3, and CuSO4 at 1000 mg/L con-
the fabricated poly (piperazine-amide) thin layer membranes. centration). The permeated water was accumulated, weighed in 10 min
intervals, and analyzed for the determination of various ion con-
centrations. Water flux (J) and rejection (R) were calculated using Eqs.
2.5. Characterization of the membranes
1 and 2:

2.5.1. FTIR
An Equinox 55 Bruker FT-IR spectrometer (Germany) was utilized
to investigate the chemical alterations of Fe2O3 and Fe2O3/SiO2 nano-
particles. The resolution of the spectrometer was 4 cm− 1 and 32 scans
were taken for each spectrum.
2.5.2. Scanning electron microscopy–energy dispersive X-ray spectroscopy
(SEM-EDX)
FE-SEM was employed to investigate the surface properties of the
membranes. More specifically, small pieces of the membranes were
frozen in liquid nitrogen and were then fractured. Afterwards, the
membrane samples were sputtered with gold and were observed by a
field emission scanning electron microscope (FESEM-MIRA3 LMU,
TESCAN, Czech) coupled with an energy dispersive X-ray spectroscopy
(EDX) at 5 kV. The non-woven substrate could not be broken in liquid
nitrogen which resulted in no observation of the cross-section of the
thin layer membranes.
2.5.3. Atomic force microscopy (AFM)
To analyze the surface morphology, smoothness and roughness of
the membranes, atomic force microscopy (AFM, non-contact mode) was
utilized. The AFM apparatus was a Dual Scope™ scanning probe-optical
microscope (DME model C-21, Denmark). Small pieces of the prepared
membranes (1 cm2) were cut and glued on a glass substrate. Scan size of
5 μm × 5 μm was chosen to analyze of the membrane surfaces. The
roughness parameters of the surface were measured by SPM-DME
software.
2.5.4. Dynamic water contact angle
A liquid contact angle measuring equipment (G10, KRUSS,
Germany) was used to study the hydrophilicity of the poly(piperazine-
amide) multilayer membranes. Distilled water, as probe liquid, was
employed in all measurements. To minimize the experimental error, the
contact angles were measured at seven random locations and the
m
J=
AΔt (1)
λp ⎤
R% = ⎡1 − × 100
⎢ λf ⎥
⎣ ⎦ (2)
where m is the weight of the permeated water, A (m2) is the membrane
area, Δt is the permeation time and λf and λp denote ion conductivity in
the permeate and feed, respectively [26]. Ion rejections were assessed
with measuring the feed and permeate conductivities using a con-
ductivity meter (Hanna 8733 model, Italy).
3. Results and discussions
3.1. IR and EDX
Fig. 2 shows the spectra of Fe2O3 and Fe2O3/SiO2nanoparticles. The
peaks appearing at 578 and 3400 cm− 1 were attributed to the
stretching vibrations of the FeeO and eOH of Fe2O3 nanoparticles,
respectively (Fig. 2a). On the other hand, a distinguished strong peak at
1087 cm− 1 belonging to the SieOeSi vibrations, proved that the
Fe2O3/SiO2 nanoparticles were successfully fabricated (Fig. 2b). On the
other hand, the presence of the related elements inside the nano-
particles in the structure of poly (piperazine amide) thin layer was
proven by EDX elemental analysis. The data presented in Table 1
clearly revealed the alteration in mass percentage of the Fe and Si
elements in poly (piperazine amide) layer. As shown, the values of mass
percentage of Fe and Si elements were elevated by increasing the na-
noparticles. The values of mass percentage of Fe and Si elements for the
PES support and the unmodified thin layer membrane were nearly zero
which were increased to 0.8 and 2.34% for M0.05 after modification,
respectively. For M0.01, the values of Fe and Si elements at approxi-
mately 0.6 and 0.7%, respectively.

81
Y. Mansourpanah et al.
Fig. 2. FT-IR spectra of (a) iron oxide and (b) the silica-modified iron oxide nanoparticles.
3.2. Morphological investigation (SEM and AFM)
FE-SEM was employed to investigate the surface morphology of the
prepared membranes, and the results are shown in Figs. 3 and 4. An
even and smooth surface was clearly observed for the PES membrane
(Fig. 3a). After the fabrication of the polyamide thin layer, a shrunk and
uneven surface appeared on the PES support which proved the suc-
cessful fabrication of poly (piperazine amide) thin layer on the substrate
(Fig. 3b, c, d). Fig. 3c and d, obviously showed the presence of the
nanoparticles in and on the structure of the poly (piperazine amide)
thin layer. In M0.01, as presented in Fig. 3c, the nanoparticles were well-
distributed in the structure of the poly (piperazine amide) layer which
led to the formation of a rougher and more uneven surface than the
unmodified poly (piperazine amide) layer. Increasing of the con-
centration of nanoparticles notably increased the distribution of the
nanoparticles in the structure of the poly (piperazine amide) and also
caused the agglomeration of the nanoparticles in some places on the
surface (Fig. 3d). Although the SEM images in low magnification
showed rougher surfaces in the presence of nanoparticles, higher
magnifications showed that the original structure of the polyamide thin
layer (Fig. 4a) had lost its shrinkage feature (see Fig. 4b and c in
comparison with Fig. 4a). Moreover, the nanoparticles were covered by
a very thin layer of poly (piperazine amide), resulting in the formation
of a relatively rough polymeric structure of the nanocomposite on the
surface which undoubtedly influenced the performance of the mem-
branes. Increasing of the specific area along with formation of thinner
layer probably changed the performance and characteristics of the thin
layer.
AFM micrographs provided further information on the micro-
structure and surface morphology of the fabricated thin layers. In fact,
when the surface includes deep valleys (holes) and high peaks (no-
dules), the AFM tip moves up and down over the surface and the surface
roughness values are evaluated. As shown in Fig. 5, the dark areas
appearing on the surface of the AFM images represent the membrane
surface holes (valleys). Surface roughness parameters of the poly (pi-
perazine amide) membranes, i.e., mean roughness (Sa), root mean
square height (Sq), and mean difference between the highest peaks and
lowest valleys (Sz), as well as surface hole sizes were calculated by SPM
DME software and were tabulated in Table 2 [27–29].
As shown in Fig. 5 and Table 2, the values of Sa, Sq, and Sz for M0
thin layer membrane were 29.5, 39.4 and 239 nm, respectively, but
were increased to 39.7, 48.4, and 248 nm for M0.01 thin layer
82
Desalination 419 (2017) 79–87
membrane. The highest Sa, Sq, and Sz values of 107, 137, and 952 nm
were obtained for M0.05 thin layer membrane, respectively. According
to the data presented in Table 2, the presence of the nanoparticles in the
body of the poly (piperazine amide) increased the roughness and un-
even properties of the surface in comparison with the unmodified poly
(piperazine amide) membrane.
According to the literature, the polymerization reaction takes place
in the interface of aqueous phase and organic phase. Two steps have
been suggested for the formation of poly (piperazine amide) layers as
follows [30]:
• The first step is film formation which is fast.
• The second step is diffusion-controlled which is slow.
After the first step, the polymerization takes place slowly because of
the low permeability of the initially formed poly (piperazine amide)
layer. On the other hand, in the second step, the thickness of poly
(piperazine amide) layer is increased until the monomers diffusing
through the formed layer are consumed by the remaining monomers in
the opposite phase and/or un-reacted groups of poly (piperazine amide)
layer film. Further reactions between the two monomers in the diffu-
sion-controlled step take place in the organic phase due to highly un-
desired partition coefficient of acyl chloride in water [31]. Due to the
intrinsic hydrophilic properties of Fe2O3/SiO2 nanoparticles and based
on the above statements, the presence of the hydrophilic nanoparticles
decreased the polymerization degree and consequently the thickness
and roughness parameters of the formed thin layers were changed. In
fact, the initial film which was formed in the first step during the in-
terfacial polymerization process, controlled the separation properties
and morphology of the poly (piperazine amide) membrane. As can be
seen in the SEM and AFM images (Figs. 3, 4, and 5) and the values
tabulated in Table 2, the presence of the nanoparticles increased the
roughness and uneven properties of the formed thin layers. Future
loading of the nanoparticles caused more alterations in the surface
morphology of the thin layer due to the agglomeration of the nano-
particles in some areas, further influencing the polymerization process.
Fig. 6 shows the Si elemental maps of the surface of the modified thin
layers by EDX. According to the maps, Fig. 6b clearly illustrates the
presence of higher amounts of Si on the surface of M0.05 thin layer
compared with M0.01 thin layer (Fig. 6a) while also indicate the ag-
glomeration of the nanoparticles in some places of the surfaces. The
EDX maps also clearly reveal that the nanoparticles were distributed in
the structure of the poly (piperazine amide) thin layers, leading to al-
terations in the morphology and structure of the poly (piperazine
amide) thin layers.
3.3. Performance of the modified thin layers
The impressive changes in the flux and rejection of the prepared
thin layers are summarized in Table 3. The PES support showed a flux
value of about 54 L/m2 h which was decreased to 19 L/m2 h when the
poly (piperazine amide) was formed on the PES support. The changes in
the flux values clearly showed that the poly (piperazine amide) thin
layer was successfully formed on the support. On the other hand, no-
table alterations in the performance of the prepared membranes were
observed after loading the nanoparticles into the structure of the poly
(piperazine amide) layer. The flux values for M0.01 and M0.05 mem-
branes stood at approximately 33 and 48 L/m2 h, respectively. As for
the rejection, the ability of the membranes to reject salt solutions was
obviously enhanced. NaCl rejection values for the PES support, M0,
M0.01, and M0.05 were 13.2, 26.5, 30.1, and 27%, respectively. The
Na2SO4 rejection values increased from 72.1% to 85.0% and then de-
creased to 78.0% once the nanoparticles were loaded into the thin films
structure. Also, the rejection capability of the prepared thin layers to-
ward PbNO3 and CuSO4 salts first increased from 50 to 64% and from
60 to 80%, respectively. For M0.05, the rejection values against PbNO3
Y. Mansourpanah et al.
(a)
(c)
Fig. 3. SEM images of (a) the PES substrate, (b) the unmodified polyamide, (c) M0.01 and (d) M0.05.
and CuSO4 salts decreased to 57 and 73%, respectively.
It is usually expected that once the flux of a membranes is increased,
the rejection would be decreased. It could be concluded that in the
present study, due to the presence of nanoparticles in the structure of
the poly (piperazine-amide), the thickness of Fe2O3/SiO2-loaded thin
layer was decreased [32,33]. On the other hand, the hydrophilicity
properties of the nanoparticles could have affected the hydrophilicity
characteristics of the modified thin layers. As shown in Fig. 7, the water
contact angle value of the PES support was about 65° which was
changed to about 39° for the unmodified thin layer. After loading the
nanoparticles into the poly (piperazine amide) thin layers, the hydro-
philicity of the modified thin films was significantly elevated. The water
contact angle values of M0.01 and M0.05 thin layer membranes were
found to be approximately 18 and 11°, respectively. A sharp decrease in
water contact angle proved the increased hydrophilicity of the Fe2O3/
SiO2-modified thin layers.
83
Desalination 419 (2017) 79–87
(b)
(d)
It has been reported that three different types of thin film structures
are produced during the reaction of TMC and PIP as follows [34]:
• Whole cross-linking; in which all three COCl groups of TMC are
involved in the crosslinking reaction process
• Linear structure with a remaining eCOOH group, in which one COCl
group of TMC monomer is unreacted and one COOH group is
formed.
• Linear structures with two remaining eCOOH groups in which two
eCOCl groups are unreacted and two eCOOH groups were formed.
As explained above, the presence of the Fe2O3/SiO2 nanoparticles in
the aqueous phase changed the polymerization conditions. We believe
that in the presence of the nanoparticles, the formation of linear
structures was dominant. Accordingly, more eCOOH functional groups
would exist in the structure, resulting in the formation of a thinner poly
Y. Mansourpanah et al.
(a)
(c)
(piperazine amide) layer containing more eCOOH functional groups.
As a result, the surface charge of the modified thin layers would be
more negative than that of the unmodified thin layer. Table 3 clearly
illustrates the surface charge of the prepared thin layers in the presence
of the Fe2O3/SiO2 nanoparticles. Accordingly, the surface charge of the
unmodified thin layer was about −7.6 mV which was changed to
− 8.4 mV in M0.05 thin layer membrane. Hence, not only the order of
the rejection of the membranes was Na2SO4 > NaCl but also the
ability of the membranes to reject Na2SO4 salt was increased by loading
the nanoparticles into the structure of the modified thin layers. On the
other hand, eCOOH functional groups along with un-reacted diamines
in the body of the thin layers can make chelates with Pb and Cu ions,
leading to more rejection of heavy metal ions. In thin film membranes,
the major mechanisms of separation are Donnan exclusion effect, steric
size effect, and mobility of ions [35].
By increasing the nanoparticles to 0.05%, not only the poly-
merization process slowed down but also the agglomeration of the
nanoparticles occurred in some places (see Figs. 3 and 4). Accordingly,
undesirable changes in the structure of the poly (piperazine amide)
layer would occur which would fairly decrease the rejection capability
84
Desalination 419 (2017) 79–87
Fig. 4. SEM images (larger magnification)
of the unmodified polyamide (a; 3.00 kx)
the silica-modified iron oxide polyamide
(b; 3.00 kx and c; 20.00 kx).
(b)
of the membranes. The AFM image of M0.05 membrane clearly showed
an uneven surface with large valleys and holes on the surface, resulting
in increased surface roughness of the modified membrane (see Fig. 5).
In spite of the explained changes in M0.05, increased negative charge
along with the existence of higher chelation sites on the surface of the
modified membranes caused decreased rejection against ions. Accord-
ingly, it seemed that in M0.05 thin layer the Donnan exclusion effect
played an important role in preventing sharp decreases in rejection
despite increased flux.
3.4. Antifouling properties
The flux recovery ratio and irreversible and reversible resistance
properties of the prepared thin films were evaluated by bovine serum
albumin to estimate the antifouling specifics of the formed thin layers.
As can be observed in Fig. 8, the values of FRR, Rir, and Rr of the PES
support were 65, 35, and 5% respectively. After the formation of the
poly (piperazine amide) thin layer, these values were increased to 90,
10, and 23%, respectively. The changes in the antifouling properties of
the fabricated thin layer were another reason revealing the successful
Y. Mansourpanah et al. Desalination 419 (2017) 79–87

Fig. 5. AFM micrographs of (a) the PES substrate, (b) the un-
modified polyamide, (c) M0.01 and (d) M0.05.

Table 2
Roughness parameters of the prepared thin layer membranes.

TFC membrane Sa nm Sz
Sq

M0 29.5 39.4 239

M0.01 39.7 48.4 248
M0.05 107 137 952

formation of the thin layer on the PES substrate. The results showed
that the antifouling properties of the fabricated thin layers were sig-
nificantly enhanced in the presence of 0.01 wt% nanoparticles. Ac-
cordingly, the FRR value of M0.01 thin layer was increased to 96% while
the Rir value was decreased to 4%. The enhanced antifouling properties
of the prepared thin layers could be attributed to the increase in the (a) (b)
hydrophilicity and changes in the structure of the modified thin layer in Fig. 6. EDX elemental maps of the surface of (a) M0.01 and (b) M0.05.
the presence of 0.01 wt% nanoparticles (see Fig. 7) as well as alteration

85
Y. Mansourpanah et al. Desalination 419 (2017) 79–87

Table 3
Flux and rejection capability of the membranes against different salt solutions.

Membrane Flux NaCl Na2SO4 PbNO3 CuSO4 Zeta potential (mV)

(L/m2 h) Rejection (%) Rejection (%) Rejection (%) Rejection (%)

PES support 54 13.2 58.5 33.3 57.1 –

M0 19 26.5 72.1 50.0 60.0 −7.6
M0.01 33 30.1 85.0 64.0 80.0 –
M0.05 48 27.1 78.0 57.0 73.0 −8.4

Fig. 7. The contact angle values of the prepared membranes.

antifouling properties of the thin layers. On the other hand, further

loading of nanoparticles caused undesirable alterations (as mentioned
above) in the structure of the poly (piperazine amide) thin layer which
decreased the antifouling properties of the modified membranes.

4. Conclusion

Alterations in the morphology and the structure of the poly (pi-

perazine amide) thin layer membranes was obviously observed in the
presence of Fe2O3/SiO2 nanoparticles. The results obtained illustrated
that the presence of low amounts of nanoparticles could enhance the
flux and rejection capability of the membranes. The nanoparticles can
influence on the polymerization process, resulting in decreased thin
layer thickness and increased negative charge of the modified mem-
branes. In the presence of nanoparticles, the formation of linear struc-
tures of poly (piperazine amide) was dominant. Accordingly, higher
number of eCOOH functional groups would be available, resulting in
the formation of a thinner poly (piperazine amide) layer containing
more eCOOH functional groups. Further loading of the nanoparticles
(up to 0.05 wt%) diminished the favorable changes in the thin layer
properties by suppressing the salt rejection and antifouling properties of
the membranes.

References

Fig. 8. The antifouling properties (FRR, Rir, and Rr) of the fabricated membranes.
in catalytic activity of nanoparticles [36]. By increasing nanoparticles
loading in M0.05 thin layer, due to increases in the surface roughness
and agglomeration of the nanoparticles (see Figs. 3 and 4 and data in
Table 2), the antifouling properties of M0.05 thin layer decreased. More
specifically, the FRR value was decreased to 70% while Rir was in-
creased to 30%. Rr values for M0.01 and M0.05 thin layers were found to
be about 31 and 16%, respectively. However, the results showed that
the presence of low amounts of the Fe2O3/SiO2 nanoparticles in the
structure of the poly (piperazine amide) thin layer increased the
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