Applied Clay Science 137 (2017) 135142

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Applied Clay Science

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

Research paper

Synthesis, characterization and efciency of new organically modied

montmorillonite polyethersulfone membranes for removal of zinc ions
from wastewasters
Caprarescu Simona a, Ianchis Raluca b,, Radu Anita-Laura b, Sarbu Andrei b, Somoghi Raluca b, Trica Bogdan b,
Alexandrescu Elvira b, Spataru Catalin-Ilie b, Fierascu Radu Claudiu b, Ion-Ebrasu Daniela c, Preda Silviu d,
Atanase Leonard-Ionut e, Donescu Dan b
a
Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, Inorganic Chemistry, Physical Chemistry and Electrochemistry Department, 1-7 Polizu Street, 011061
Bucharest, Romania
b
Polymer Department, National Research and Development Institute for Chemistry and Petrochemistry ICECHIM, Splaiul Independentei, no. 202, 060021 Bucharest, Romania
c
National Research & Development Institute for Cryogenics and Isotopic Technologies-ICSI-Rm, Valcea P.O. Box Raureni 7, 240050 Ramnicu Valcea, Romania
d
Institute of Physical Chemistry Ilie Murgulescu, Romanian Academy, Spl. Independentei 202, 6th district, P.O. Box 194, 0600021 Bucharest, Romania
e
University Apollonia, Acad. Ioan Haulica Research Institute, Iasi, Romania

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

Article history: The goal of the present paper was to study the separation efciency of zinc ions of new synthesized polymer
Received 9 March 2016 membranes based on polyethersulfone (PES) and organically (unmodied and modied) montmorillonite
Received in revised form 6 December 2016 (Mt). The membranes were prepared by a combination of solution dispersion and wet-phase inversion methods.
Accepted 8 December 2016
Further, the membranes were used in the removal of zinc ions at concentrations of 2 g/L and 4 g/L from aqueous
Available online xxxx
model solution, at an applied voltage of 10 V, via a laboratory-scale electrodialysis system. The presence of mod-
Keywords:
ied montmorillonite inuenced the thermal behavior of the samples as evaluated by thermogravimetrical anal-
Montmorillonite ysis. The XRD data indicated that partially exfoliated and/or intercalated montmorillonite PSf (nano) composite
Heavy metals membranes were obtained. The presence of advanced modied montmorillonite inuenced the water evapora-
Wastewater tion enthalpy calculated by DSC, the water contact angle, as well as the silicon peak according to XRF plots. The
Electrodialysis pore size decreased with montmorillonite addition according to SEM pictures while TEM photomicrographs
showed that mostly intercalated nanocomposites were obtained. The performance of electrodialysis cell was
evaluated in terms of mass ow (J) and rejection (R) of zinc ions, which increased with the increase of concen-
tration of zinc ions. J and R values were higher, at 4 g/L (45.40 0.12 g2 h1, 94.59 0.25%), for the membranes
that incorporated the Mt functionalized with octadecyl chain which favored the dispersibility of the ller in the
PSf membrane. Finally, advanced modied montmorillonite improved the separation efciency of the nal
membranes.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Discharge of wastewaters that contain different heavy metal ions
(i.e. Zn2+, Cu2+, Ni2+, Cd2+), which are toxic, persistent and non-bio-
degradable, from various industrial activities of chemical processing
(i.e. catalysts, photographic paper, ceramics, textiles, fertilizers, pig-
ments and batteries) causes signicant problems in the environment
and public health (Caprarescu et al., 2015; Ge et al., 2012; Petcu et al.,
2015). Zinc ions are one of the metal ions that are frequently released
into the environment. Levels of zinc ions (Zn2 +) (in excess of
200 ppm) in rivers owing through industrial or mining areas are highly
Corresponding author.
E-mail address: ralumoc@yahoo.com (I. Raluca).
toxic for plants and sh (Emsley, 2001; Megateli et al., 2009). As a trace
element, zinc is essential to maintain the metabolism of the human
body (24 g of zinc), but high concentrations can lead to diseases of
the liver, kidney and prostate cancer (Megateli et al., 2009; Caprarescu
et al., 2015; Petcu et al., 2015). Different methods such as chemical pre-
cipitation, ion-exchange, reverse osmosis, membrane separation, elec-
trodialysis, advanced oxidation processes and adsorption procedures
have been developed for the removal of heavy metal ions from sewage
and industrial wastewater (Lu et al., 2007; Ijagbemi et al., 2009; Ge et al.,
2012).
Electrodialysis is a membrane process during which ions are
transported from one solution to another through polymer membranes
under the inuence of an applied electric potential difference and is
widely used for removal of various heavy metal ions from sewage and

http://dx.doi.org/10.1016/j.clay.2016.12.013
0169-1317/ 2016 Elsevier B.V. All rights reserved.
136 C. Simona et al. / Applied Clay Science 137 (2017) 135142
industrial wastewater (Ho Choi and Jeoung, 2002; Mohammadi et al.,
2005; Sadrzadeh et al., 2007; Caprarescu et al., 2015).
The most common method for the preparation of nanocomposite
membranes is a combination of solution dispersion and the immersion
step of the wet-phase inversion (Anado et al., 2010; Ghaemi et al.,
2011; Ma et al., 2012). Incorporation of clay mineral layers (hectorite,
montmorillonite (Mt), and synthetic mica) has been considered to be
an effective method to improve the mechanical strength in porous
membrane supports (Ray and Okamoto, 2003; Anado et al., 2010; Ma
et al., 2012).
Recently, various studies have been devoted to the synthesis of
nanocomposite membranes with protonated Mt (Alonso et al., 2009),
with bio-functionalized Mt (Hasani-Sadrabadi et al., 2009), and with
sulfonated Mt (Bbin et al., 2006) and by using sulfonated
poly(etherether ketone) with organophilic Mt (Jaafar et al., 2009;
Sanporean et al., 2014) and with sulfonated Mt (Gosalawit et al.,
2008). Monticelli et al. (2007) prepared porous membranes and dense
lms from polysulfone solutions in N-methyl-2-pyrrolidone (NMP)
containing unmodied clay (Cloisite Na) or organically modied clay
(Cloisite 30B and Cloisite 93A). Cloisite containing Na ions did not
swell in NMP. Cloisite Na and Cloisite 93A formed microaggregates
while Cloisite 30B yielded nanostructures composed of both single
sheets. Also, Cloisite 30B improved the wettability and mechanical
properties of dense lms. Anado et al. (2013) prepared nanocomposite
membranes containing polysulfone (PSf) and sodium montmorillonite
(Mt). Mt addition improved the membrane hydrophilicity, thermal sta-
bility and mechanical resistances. Ma et al. (2012) prepared a at sheet
asymmetric polysufone (PSf) membrane and clay/PSf nanocomposite
membranes with different clay contents. The addition of clay improved
the separation efciency and increased the rejection (extraction remov-
al degree) of heavy metals.
Polysulfone (PSf) membranes have been widely used as
microltration and ultraltration membranes in many industrial elds
because of their low cost, good mechanical properties, and strong chem-
ical and thermal stabilities (Summers et al., 2003; Ma et al., 2011).
Among various modiers, polyethylene glycol (PEG) or polyethylene
oxide (PEO) and their derivatives were widely used in the preparation
of membranes as the pore forming agent (Monticelli et al., 2007; Ma
et al., 2011, 2012).
In this paper, the performances and zinc separation efciency of
novel (unmodied and modied) Mt/PSf composite membranes were
investigated. The montmorillonites used in the synthesis were modied
commercial montmorillonites (Cloisite 30B) by edge covalent bonding
with several alkoxysilanes with different lengths of alkyl chain-vinyl
(Cl 30B-Vy), octyl (Cl 30B-C8) and octadecyl (Cl 30B-C18) (Ianchis et
al., 2012). Although several montmorillonite types were used for sepa-
ration purposes as described above, these systems with advanced mod-
ied montmorillonites have not been studied before. The membranes
were prepared by a combination of solution dispersion and wet-phase
inversion methods. N,N-dimethyl acetamide (DMAc), deionized water
and PEG 350 were used as solvent, coagulant and pore forming agent re-
spectively. These prepared membranes were used for zinc ions removal
from a model waste water system, by new electrodialysis system (own
construction device). The performance of the membranes was evaluat-
ed in terms of rejection (R, extraction removal degree) and mass ow
(J) of zinc ions. The polymer membranes were characterized using
FTIR-ATR, TGA, XRD, SEM and TEM.
2. Experimental
Polyethersulfone (PSf) (Sigma-Aldrich) was used as the base poly-
mer in the membrane casting solution. Dimethyl acetamide (DMAc)
(Merck, = 0.94 g/cm3) was used as solvent. Poly(ethylene glycol)
methyl ether (PEG 350) (Fluka Sigma-Aldrich, = 1.08 g/cm3) was
used as the nonsolvent pore forming additive in the casting solution.
All chemicals were used as received.
Cloisite 30B was kindly offered from Southern Clay Products Inc.
Cloisite 30B is a commercial montmorillonite modied with a ternary
ammonium salt ((MT2EtOH: methyl, tallow (~65% C18, ~30% C16; ~ 5%
C14), bis-2-hydroxyethyl, quaternary ammonium, 90 meq/100 g clay).
Three types of advanced modied Mt with different organosilyl groups
(vinyl (Cloisite30B-Vy), octyl (Cloisite30B-C8), and octadecyl
(Cloisite30B-C18)) were obtained by silylation of the commercial
Cloisite 30B. Silylating agents were monoalkoxysilanes with different
organic groups: vinyl dimethylethoxysilane (VyMe2ES), octyl dimethyl
methoxysilane (C8Me2MS), and octadecyl dimethylmethoxysilane
(C18Me2MS) (Aldrich, USA). The synthesis of the advanced modied
Mt is described in detail in another paper (Ianchis et al., 2012). For ex-
ample, 4 g of dried Cl 30B in 250 ml CH2Cl2 (from Chimreactiv, Roma-
nia) was sonicated for 10 min on an ice bath. The suspension was
introduced in a three-neck round bottom ask and was stirred at
300 rpm under puried nitrogen gas for 30 min. The alkoxysilanes
were added drop wise and then the reaction mixture was heated to
40 C and reuxed for 24 h. The reaction product was centrifuged and
washed with 300 ml CH2Cl2, then was dried in a vacuum oven at 60 C
for 12 h (Ianchis et al., 2012; Donescu et al., 2012).
Deionized water was used as the nonsolvent in the coagulation bath.
Below, the notation of membrane with/without Mt as they appear in the
study is presented.
2.1. Analyses
The structure of the samples was determined using an X-ray dif-
fractometer (Rigaku Ultima IV, Japan) with CuK radiation ( =
1.5406 ), operated at 40 kV and 30 mA. The equipment was set in
parallel beam geometry system, with DS (divergence slit) = 1, SS
and RS (scattering and receiving slits) = open, and receiving side
Soller slit 0.5. Data were collected over the 2 range 330, with a
step width of 0.02, in continuous mode and a scanning speed of
1/min, at room temperature and atmospheric pressure. The samples
were measured as-received, as a bulk material. No sample prepara-
tion was necessary, because of their at surface and rigidity, which
allowed their accurate aligned mounting into the standard sample
holder.
TGA analyses were performed with a TGA Q5000 instrument at a
heat rate of 10 C/min under air atmosphere with a ow of 50 ml/min.
Differential scanning calorimetry (DSC) thermographs were recorded
with SDT Q600 instrument at a heating rate of 10 C/min in helium
atmosphere.
X-ray uorescence (XRF) analyses were performed on a PW4025-
MiniPal2-PANalytical type EDXRF Spectrometer. The determinations
have been carried out in helium atmosphere, for 300 s, at a voltage of
20 kV and by automatically adjusting the current intensity; a 3.6 m
Mylar lm was used for the sample cuvette.
SEM images were recorded using a FEIQuanta 200 electron micro-
scope. All of the samples were sputter-coated with gold to make the sur-
face conductive. SEM images were recorded in low vacuum mode using
LTD detector. Micrographs were taken in vacuum conditions operating
at 20, 25 and 30 kV using magnications in range of 10,000 for top sur-
face of the membranes.
The morphologies of polysulfone nanocomposites were obtained by
transmission electron microscopy using TEM, Tecnai G2 F20 TWIN
Cryo-TEM, FEI Company, at 200 kV acceleration voltages. Samples
were embedded in AGAR100 and cut in thin sections (~ 100 nm) at
room temperature, using a Leica EM UC7 ultramicrotome, and then de-
posited on carbon lm grids
The wettability of the membranes was determined using a
DataPhysics OCA 15 + Contact Angle Tensiometer, equipped with a
digital camera connected to PC. The reported values of contact
angle were obtained as average of ve measurements (liquid droplet
10 l).
 C. Simona et al. / Applied Clay Science 137 (2017) 135142 137

Table 1
Notation of membrane with/without modied Mt.

Sample Notation

Membrane without Cloisite 30B M1

Membrane with Cloisite 30B M2
Membrane with Cloisite 30B-Vy M3
Membrane with Cloisite 30B-C8 M4
Membrane with Cloisite 30B-C18 M5

disadvantages such as membrane burning, electrolysis on the electrode

Fig. 1. Scheme of mini-electrodialysis system.
2.2. Methods
2.2.1. Preparation of organomontmorillonite polymer (nano) composite
membranes
Montmorillonite PSf polymer membranes were prepared by phase
inversion method. A typical run consisted of the following steps: disper-
sion of clay in the solvent assisted by ultrasonication; obtaining the
casting solution by polymer and pore forming additive adding
in the premixed solution. Primarily, a specic quantity of
organomontmorillonite (3 wt.% of PSf dosage) was mixed with
65.5 ml of DMAc and magnetically stirred at ambient temperature for
20 min. Afterward, PSf and PEG 500 were added to premixed solutions,
dissolved at 60 C and continuously magnetically stirred for 24 h until
becoming a homogeneous and viscous solution. Similar procedures
were applied for obtaining the PSf membrane, used as reference.
These solutions were kept 24 h without stirring at room temperature
to stabilize their structure and remove air bubbles. The homogeneous
casting solutions were cast uniformly onto a glass substrate by means
of a hand-casting knife with a knife gap set at 200 m. Finally, the ob-
tained membranes were immersed in a deionized water bath for 24 h.
The thickness of the dried membranes, in a range of 0.0150.025 cm
was measured with a stainless steel digital caliper with Metric/SAE/
Inch-Fractions (China).
2.2.2. Electrochemistry determinations
All experiments were carried out at room temperature (25 2 C) in
a mini-electrodialysis cell with three compartments made of Plexiglas
with an inside diameter of 47 mm. The compartments were separated
from each other by two parallel pure graphite electrodes and two mem-
branes. The electrodes (anode and cathode) were disposed at the ex-
tremities of the electrodialysis cell. The membranes were positioned
between the compartments (anodic, central and cathodic). The thick-
ness of each compartment was 7.6 mm, thickness of each compartment
with O-rings was 12 mm (the leaks are prevented by the use of acid re-
sistant O-rings placed on each side of the compartment body) (Fig. 1).
The effective area of each membrane and each electrode was approxi-
mately 17.34 cm2. The distance between the membranes was approxi-
mately 12 mm and that between electrodes was approximately 35 mm.
All experiments were accomplished with simulating wastewater so-
lutions, prepared using zinc chloride (ZnCl2) (Sigma-Aldrich), hydro-
chloric acid (HCl) (33%, = 1.16 g/cm3, Merck) and deionized water
to produce different solutions containing 2 g/l and 4 g/l, respectively,
each of Zn2+. Mass molar ratio between ZnCl2:HCl was 1:1. Increasing
the applied voltage over the limiting value (10 V) and concentration
over 4 g/l is not convenient in this study due to the occurrence of
plate, which eventually increases the total cost. In this study the waste-
water concentration with zinc ions must be limited at 4 g/l; after this
value the cell acts as electrolysis cell (90%) and only in part as electrodi-
alysis cell (10%).
The electrodialysis experiments were carried out at potentiostatic
control; the total applied voltage imposed between electrodes by a
power supply (Protek, Germany) was 10 V and current intensity ranged
from 0.27 A to 1.13 A. The operation time was 1 h for each experiment.
The liquid volume was approximately 20.8 cm3 in each of the three
compartments. All experiments were carried out at room temperature
(22 1 C) and without recirculation. The zinc ion content from the dif-
ferent stimulated electroplating wastewater was determined by titra-
tion method (Caprarescu et al., 2015). The titration procedure for
determination of concentration of zinc ions from solutions was per-
formed four times and data were presented as means standard devi-
ation. In order to ensure highly reproducible conditions, the tests were
carried out with the cells that maintained the same conditions and en-
sured that no unwanted perturbations took place. In the electrodialysis
cell each type of membrane was used only one time and then was char-
acterized by various techniques.
3. Results and discussion
3.1. Characterization of membranes
The thermal properties and the stability of the polymer and nano-
composite membranes were evaluated by TGA. Regarding the samples
prepared in the presence of organomontmorillonite, the onset temper-
ature of degradation increased at 515 C compared with neat polymer
(Table 1). Many studies showed improvements in the thermal proper-
ties of polymer (nano) composites in comparison with the pure poly-
mer, the clay mineral layers acting as a barrier in the diffusion of
oxygen molecules (Ianchis et al., 2010; De Maria et al., 2011; Anado
et al., 2014).
The maximum degradation temperatures T1 and T2 of all nanocom-
posite samples shifted toward higher temperatures in comparison with
the pure polymer sample increasing the membrane thermal stability
even at such low amounts of clay (3% wt.). No signicant changes
were observed for the samples prepared with silylated Mt in compari-
son to the commercial Mt, the amount of alkyl chain grafted onto Mt
layers being unable to produce major changes in the thermal stability
of the nal membranes. The mass losses around 450 C and 560 C, ob-
served only for the composite samples, are due to the olen and amine
degradation (Qian et al., 2009) but could be also due to the degradation
Table 2
TGA data obtained for the membranes with/without modied Mt.
Sample Tonset (C) T1 (C) T2 (C) Residue at 900 C (%)
M1 blank 491 519 620 2.02
M2-Cl 30B 495 530 620 3.67
M3-Cl 30B-Vy 501 532 625 2.70
M4-Cl 30B-C8 504 533 623 2.61
M5-Cl 30B-C18 507 534 624 2.72
138 C. Simona et al. / Applied Clay Science 137 (2017) 135142
Fig. 2. TGA curves obtained for the membranes with/without modied Mt.
of silane moieties (Herrera et al., 2004; Zhang et al., 2006) or Mt dehy-
droxylation (Horvath and Galikova, 1979).
The presence of the inorganic partner into the polysulfone matrix
was supported by the increase of the nal residue of the composite sam-
ples against neat polymer (Table 2). Due to the organic amount from
silylation, the residue values of the silylated samples were lower than
the commercial Cl 30B samples.
The membranes resulted after electrodialysis processes remain un-
affected during the separation as observed from TGA analysis (see Fig.
2.). The main weight losses intervals but also the maximum
decomposing temperatures didn't show signicant changes, the mem-
branes being suitable for high temperature procedures.
The XRD patterns of polymer and organomontmorillonite polymer
(nano) composite membranes are compared in Fig. 3(a,b). The reec-
tions appeared at ~ 5.5, 18 and 23 in all XRD patterns related to the
PSf structure (Fig. 3a). As shown in a previous study (Ianchis et al.,
2012), the characteristic reections of commercial organomodied
Cl30B were found as follows: a strong reection at 2 = 4.7 specic
to the basal spacing and two small reections at around 2 = 19.8
and 2 = 24.5 specic to the 2:1 layer's crystalline structure. The char-
acteristic reection 001 shifted toward higher 2theta values, namely
around 2 = 6 (d-spacing ~ 1.4 nm). This shift reects a decrease in
the interlayer space. The intensity of the rst reection diminished in
the case of polymer-inorganic membranes, the curve returned to the
PSf curve shape. This behavior was attributed to delaminated and/or in-
tercalated structures of Mt (Dorigato et al., 2011; Kusmono and Ishak,
2013). During membrane preparation inorganic layers are dispersed
Fig. 3. XRD patterns obtained for the membranes with/without modied Mt.
Table 3
DSC data and water contact angle values for the prepared membranes.
Sample Retained water after 5 days (%) G (J/g) Water contact angle ()
M1 23 131.50 60.60
M2 108 586.21 71.18
M3 122 1063.05 73.04
M4 120 810.96 72.07
M5 117 910.41 74.96
in the solvent and then the polymer was dissolved. The polymer mole-
cules penetrate between organomontmorillonite layers and due to sol-
vent evaporation, the layers tend to a multi-layer reordered structure
(Anado et al., 2013). Only in the case of polymer-Cl30B-Vy membrane,
a small reection at 2 = 4.04 (2.19 nm) was observed (Fig. 3b). This
is probably because of agglomerated organomontmorillonite layers in
the polymer matrix due to the grafted vinyl chains.
Because the electrochemical measurements were performed in
water, study of water absorption capacity of the obtained membranes
was followed. The results are shown in Table 3.
Firstly, the presence of Cloisite B ller in the hybrid membrane af-
fected the absorbed water which increased substantially after ve
days. The explanation for this behavior lies in the polar character of
aluminosilicate inorganic ller. A second observation is the in-
creased amount of water absorbed in the presence of montmorillon-
ite modied with alkoxysilanes (sample M3-4-5). The largest
amount of water retained was observed in the presence of silicate
modied vinyltriethoxysilane. (Sample M3). This behavior can be
explained by the advanced ability of this ller to aggregate in the
polysulfone matrix.
In order to analyze the changes in water absorption capacity of the
membranes whose polarity modies in the montmorillonite presence,
water evaporation enthalpies were measured (Fig. 4, Table 3).
The enthalpy of water evaporation increases with increasing materi-
al hydrophilicity (Karmas, 1977; Pshezhetskii et al., 1990; Staszczuk et
al., 1993; Laporta et al., 1999; Presswala et al., 2008; Kusgens et al.,
2009). Water evaporation enthalpy grew in the presence of Cloisite B
reecting the increase of membrane polarity. The maximum value of
water evaporation enthalpy (1063.05 J/g) was obtained for the mem-
brane with the largest amount of water absorbed, so the most polar
membrane (sample M3). For Cloisite 30B samples functionalized with
octyl (sample M4) or octadecyl (sample M5) an increase in the enthalpy
of water evaporation was observed but not as great as compared to
membrane M3.
An effective characterization method of surface hydrophobicity of
the membranes is measuring the contact angle with water. The contact
Fig. 4. Water evaporation enthalpy-DSC analyses.
 C. Simona et al. / Applied Clay Science 137 (2017) 135142 139

angle of water on a surface increases with increasing hydrophobicity or

Fig. 5. EDXRF spectra of the obtained samples. Inset - focus on the specic intensity of
silicon.
roughness to it (Wang and Luo, 2012; Hayden and Gardner, 1963;
Wang and Xiong, 2014). The water contact angle is minimal for the
neat polymer membrane (sample M1) (Table 3). The increase of the
contact angle of water (~ 10) for the membranes containing Mt, so
the polar membrane, was a surprise. The explanation can only be the in-
crease of membrane roughness in the presence of aggregated montmo-
rillonite at the surface and inside the membrane (Hayden and Gardner,
1963). In the case of hybrid membranes, no signicant modications
were observed (one to three degrees).
In order to see if there are changes in specic peak of silicon at the
membranes surface, X-ray uorescence analysis of all samples was per-
formed. The data obtained are presented in Fig. 5.
As expected, specic peaks for the polymer (sulfur from
polysulfone) and for montmorillonite (silicon and iron), were observed.
The intensity of silicon peak increased in the following order
M1 b M3 b M4 b M5 b M2. The increase in the silicon peak is due to
the incorporation of modied Mt in the polymer matrix and the distri-
bution of functionalized layers at the membrane surface (Ianchis et al.,
2009a, 2009b). The most intense silicon peak is obtained for the

Fig. 6. SEM images of polymer composite membranes without (a-M1) and with different modied montmorillonite, before electrodialysis process (b-M2, c-M3, d-M4, e-M5), scale bar
10 m.
140 C. Simona et al. / Applied Clay Science 137 (2017) 135142

commercial organomontmorillonite. The change in the silicon intensity
is directly related to the change in the size/weight of the organic modi-
er in the organomontmorillonite (Ianchis et al., 2012). The Rh peak
present in the spectra represents a characteristic of the equipment
used (Rh being the anode of the X-ray tube).
SEM images of the upper surface of different PSf (nano) nanocom-
posite membranes before used in electrodialysis system are presented
in Fig. 6.
The surface of the membranes with Mt particles was very dense.
The composite membranes with Mt showed large number of small
pores and uniform pore distribution with thin skin layer compared
with the membrane without Mt. This is due to the preferential wet-
phase inversion due to the presence of modied Mt particles. The
pore sizes of membranes without Mt (M1) were between 1 and
5 m and pore sizes of membranes with Mt (M2-M5) were between
0.3 and 2.5 m (the pores were measured from the SEM pictures
without the use of image analysis software). More than 50 pores
were measured, the largest one reached 5 m and the average diam-
eter was about 3.7 m The change in the size of pores might be due to
high afnity of DMAc for water, instantaneous demixing of mem-
brane casting solution and rapid precipitation of polymer matrix.
Montmorillonite layers acted as a surfactant and decreased the ten-
sion of interface between the water and membrane polymer matrix
and affected the exchange rate of solvent and non-solvent during
wet-phase inversion process.
The composite membrane containing Mt showed a uniform struc-
ture with no large voids and cavities, which is favorable to the absorp-
tion and transfer of large amounts of wastewater solution that contain
zinc ions. This may lead to high ionic conductivity (Ma et al., 2012;
Anado et al., 2014).
Clays had a good dispersion in the polyethersulfone matrix and
mostly intercalated nanocomposites were obtained (Fig. 7, I and II; M3
and M5) (Monticelli et al., 2007; Ma et al., 2012). An inspection of
TEM micrographs of M3 membrane revealed agglomerated
organomontmorillonite layers in the polymer matrix very probably
due the grafted vinyl chain.

3.2. The performance of membranes

The performance of the membranes was evaluated in terms of mass

ow (J) and rejection (R) of zinc ions. The mass ow (J) and rejection
(R) of zinc ions were calculated according to formulas (1) and (2)
(Choi and Jeoung, 2002; Caprarescu et al., 2015):


V  C i C f
J 1
At
 
C
R% 1 i  100 2
Cf

where J is the mass ow (g m2 h1), V is the initial volume of so-

lution (L), A is the membrane area (m2), t is the time (h), Ci and Cf are
the concentrations of zinc ions in initial feed and after electrodialysis
process, respectively, (g/L).
The values of R in the cathodic compartment (Table 4) increased
with an increase in solution concentration values (from 73.2 0.43 to
94.59 0.25), due to the increase of transported amount of zinc ions.
The highest value of R (~ 95%, M4) was obtained at the concentration
of 4 g/l.
The presence of the modied Mt layers had a signicant inuence on
the values of J that increased from 17.57 0.10 g m2 h1 for mem-
brane without Mt to 22.28 0.08 g m2 h1 for the membranes with
Mt, tested at a concentration of 2 g/l and from 39.19 g m 2 h 1 to
45.40 0.12 g m2 h1 for the membranes tested at a concentration
of 4 g/l (Table 4). At higher zinc ion concentrations the values of J in
the cathode compartment are higher due to the relative mobility of
these coordinated ions in solution (Caprarescu et al., 2015; Petcu et al.,
2015).
The hydrophobicity of the modied Mt increased in the following
order: Cloisite30B b Cloisite30B-Vy b Cloisite 30B-C8Cloisite 30B-C18
as demonstrated in another paper (Ianchis et al., 2012). J and R values

Table 4
Mass ow (J) and rejection (R) of zinc ions for the obtained membranes.

J, g m2 h1 R, %

Sample 2 g/L 4 g/L 2 g/L 4 g/L

M1 17.57 0.10 39.19 0.06 73.20 0.43 81.69 0.12

M2 19.54 0.09 43.52 0.05 81.54 0.33 90.68 0.09
M3 20.55 0.07 45.05 0.05 85.62 0.28 93.86 0.09
M4 22.28 0.08 45.40 0.12 92.81 0.33 94.59 0.25
M5 20.35 0.12 43.39 0.10 84.80 0.49 91.63 0.21
Fig. 7. TEM images of M3 (I) and M5 (II) nanocomposite membranes.
 C. Simona et al. / Applied Clay Science 137 (2017) 135142
were higher, at 4 g/l (45.40 0.12 g2 h1, 94.59 0.25%), for the
membranes obtained in the presence of advanced functionalized Mt
(M4) than for the one obtained with commercial organomodied Mt
(M1) (39.19 0.06 g2 h1, 81.69 0.12%), the biggest values being
obtained in all of the cases for the membranes that incorporated the
Mt functionalized with octadecyl chain (M4). This is probably due to
the presence of octadecyl modied Mt that behaves like surfactants, as
observed in another study (Ianchis et al., 2009a, 2009b). Consequently,
Cl30B-C8 modied Mt favored the dispersibility of the ller in the PSf
membrane; the homogeneity of the composite membrane was im-
proved and led to a better separation process.
The alkyl groups that adhered to the membrane surface were hydro-
phobic. These groups have a good compatibility with the solvent
(DMAc) and restrained the exchange process between the non-solvent
(PEG 350) in the water bath and the solvent in polymer matrix. This in-
creased the porosity of membrane (Ma et al., 2012; Anado et al., 2014).
4. Conclusions
New synthesized polymer membranes based on polyethersulfone
(PES) and organically (unmodied and modied) montmorillonite
(Mt) were prepared and their efciency in the removal of zinc ions
was tested. The presence of modied Mt in the polymer membrane af-
fects its nal properties compared with the polymer membrane, such
as: improvements in thermal properties of polymer (nano) composites,
increased amount of water absorption capacity, increase of water con-
tact angle, and increased separation efciency. These results are strong-
ly related to the dispersion capacity of organically montmorillonite in
the polyethersulfone matrix respectively with the organomodiers
structure which directed the mostly intercalated structure of the nal
nanocomposites.
This type of polymer-organically modied Mt membranes could
represent a perfect choice for a better separation of zinc ions from
wastewater by electrodialysis.
Acknowledgements
This work was supported by a grant funded by the Romanian
National Authority for Scientic Research, project ERA-IB number 62/
2016.
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