Journal of Industrial and Engineering Chemistry 20 (2014) 15171522

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Journal of Industrial and Engineering Chemistry

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

Preparation and characterization of polyvinyl chloride based

nanocomposite nanoltration-membrane modied by iron oxide
nanoparticles for lead removal from water
A. Gholami a, A.R. Moghadassi a,*, S.M. Hosseini a, S. Shabani a, F. Gholami b
a
b

Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak 38156-8-8349, Iran
Department of Chemistry, Faculty of Science, Arak University, Arak 38156-8-8349, Iran

A R T I C L E I N F O

Article history:
Received 6 February 2013
Accepted 23 July 2013
Available online 6 August 2013
Keywords:
Nanocomposite membrane
Nanoltration
Membranes hydrophilicity
Iron oxide nanoparticle
Lead removal

A B S T R A C T

In this research (polyvinyl chloride-blend-cellulose acetate/iron oxide nanoparticles) nanocomposite

membranes were prepared by casting technique to lead removal from wastewaters. The effect of blend
ratio of polymer binder (PVC to CA) and Fe3O4 nanoparticles concentration on physico-chemical
characteristics of membranes were studied. Water permeability and ionic rejection tests, water content
and mechanical properties measurements and SEM analysis were carried out in membranes
characterizations. Obviously, modied membrane containing 10 wt% CA and 0.1 wt% Fe3O4 nanoparticles showed better performance in lead removal compared to other modied membranes and also
pristine ones.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
Wastewaters which contain heavy metals have attracted global
attention because of their harmful effects on the environment and
human health, certainly to be a risk for human beings [1]. Lead is
one of the heavy metal that is non-essential and occurs naturally in
the environment. But some physical and chemical properties of
lead such as ductility, softness, malleability, poor conductivity and
resistance to corrosion have led to wide use of this metal since
ancient times in variety of applications. Today, the maximum
concentrations found in environment are the result of human
actions, while it is demonstrated that lead can cause dangerous
health effects, even at trace level, such as nephrotoxicity,
neurotoxicity and adverse effects on the hematological and
cardiovascular systems [1,2]. So, it is very important to remove
Lead from wastewaters effectively before their discharge into the
environment. Several treatment techniques such as adsorption,
electrochemical oxidation, coagulation-occulation, and membrane ltration are used to eliminate pollutants from wastewater.
Membrane process has veried to be very attractive and effective
for the treatment of efuents. The main advantage of membranebased technologies is that they do not need the addition of

* Corresponding author. Tel.: +98 861 262 5422; fax: +98 861 262 5423.
E-mail addresses: A_Moghadassi@yahoo.com, A-Moghadassi@araku.ac.ir
(A.R. Moghadassi).

chemicals [3]. One of membrane techniques is Nano ltration (NF),

that is becoming progressively universal in concentration and
purication, pharmaceutical and chemical industries, water
treatment and desalination [4,5]. NF has some good advantages,
such as relatively low investment, low energy consumption, high
permeation ux and singular separation capability for ions of
different valences [6].
In NF membranes, two mechanisms affect the rejection
behavior of solutes, surface charge and sieving, that are usually
characterized using high rejection of bivalent ions, lower rejection
of monovalent ions, and higher uxes than reverse osmosis (RO)
membranes [5,7,8]. NF membranes are increasingly known as one
of the best procedures for water treatment and production of
portable water [9].
Among the various polymeric materials which are used in
preparation of membranes, polyvinyl chloride (PVC) is exible and
durable polymer with suitable biological and chemical resistance
[1012]. CA is also one of the most applicable polymers in
fabrication of membranes due to its high hydrophilicity, good
toughness, high biocompatibility, good desalting, high potential
ux, good resistance to chlorine and solvent and it is cheap [13].
Use of these polymers (PVC/CA) and their blends as membrane
binders can dedicate special selective characteristics into the
prepared membranes and improve the separation properties of
them [14].
One of the best modication techniques for enhancing
membrane performance is blending with inorganic nanoparticles

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.07.041

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A. Gholami et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 15171522

Table 1
Structure of used polymers.
Polyvinyl chloride (PVC)

Cellulose acetate (CA)

such as TiO2 [5], Al2O3 [15,16], bentonite [17], and carbon

nanotubes [3,5,6,1031]. Inserting inorganic nanoparticles in the
membrane matrix can improve the strength and stiffness, the
hydrophilicity, the water permeability and rejection and the
antifouling properties of polymer based Nano composite membranes [5,1821]. Among these, nano-sized ferric oxides are used
for the removal of heavy metals from aqueous systems [1]. This is
because of some good features such as excellent thermal and
chemical stability, magnetic performance and good biodegradation and biocompatibility. These features caused wide use of this
particle in different separation techniques such as preparing
magnetic targeting medicine and magnetic uids, preparing
magnetic microspheres for the quick separation of cellular,
biomedical and bioengineering products [22].
The aim of this research is fabrication of novel nanoltration
membrane combined with absorbents particles by using nanosized ferric oxides in membrane matrix to increase in lead removal
efciency from water. For the purpose, polyvinyl chloride-blendcellulose membrane was prepared by solution casting technique.
Nano-sized ferric oxide was also used as adsorbent in various
concentrations to achieve nanocomposite nanoltration membrane with high rejection and ux. The effect of blend ratio of
polymer binder (PVC to CA) and Fe3O4 nanoparticles concentration
on physico-chemical characteristics of membranes were studied.
2. Experimental

After a 60 s delay membranes were immersed into distillated

water bath with the temperature about 26 8C. The polymeric skin
layer was taken out after 15 min and then immersed in distillated
water for 24 h to ensure complete elimination of residual solvent.
The nal membranes thickness was also measured by a digital
caliper device (Electronic outside Micrometer, IP54 model OLR)
between 135 and 150 mm.
To achieve nal membrane two steps must be carried out: First,
optimization on CA concentration to obtain membrane with
maximum rejection and ux, and second step, investigation effect
of various concentration of the nanoparticle adsorbent to improve
rejection of lead. Two stages are presented by different colors in
Table 2.
2.3. Membrane characterization
2.3.1. Permeability and rejection
For characterization permeability of the home-made nanoltration membranes, a dead-end system was designed. This system
consists a ltration cell with a stirrer in it and a nitrogen gas
cylinder. Model of Filtration cell is 8200 Millipore Co. with inner
diameter of 40 mm and volume capacity of 150 mL and effective
area of the membrane was 12.566 cm2. Fluid that reserved in cell
was pressed by nitrogen gas. Fig. 1 shows symbolic view of
apparatus.
The water ux (Jw) that resulted by this pressure was calculated
by the following equation:

2.1. Materials
Polyvinyl chloride (PVC, Bandar Imam Petroleum Company,
grade S-7054) and cellulose acetate (CA, Acros company,
MW = 100,000 g/mol) as polymers their structures presented
in Table 1 and tetrahydrofuran (THF, DAE Jung) as solvent and
Fe3O4 nanoparticles (MW = 213.53 g/mol, APS = 60 nm, SSA >
55 m2/g, purication = 99.2%) as a adsorbent and lead(yy)nitrate
(Pb(NO3)2, Fulka company, MW = 331.2 g/mol, analysis number:
334371.1 41497) and distilled water from Alborz company were
used throughout this study.
2.2. Membrane preparation
The asymmetric membranes were prepared by phase inversion
method. The solution containing Polyvinyl Chloride (PVC) and
Cellulose Acetate (CA) as polymer, Tetrahydrofuran (THF) as
solvent and iron oxide nanoparticles was shaken for 24 h at 60 8C
[22] (according to Table 2) and cast on a clean glass plate at
ambient temperature by manual casting knife with 150 mm
thickness. The membrane surface was exposed to air at ambient
temperature (about 26 8C) for free-convective solvent evaporation.

Jw

V
ADt

(1)

V (L) is volume of permeated water from membrane that is

collected in a graduated cylinder and A (m2) is effective area of the
membrane and t (h) is the time in which permeate is collected in
the graduated cylinder.
Table 2
Composition of casting solution for the fabrication of homemade membranes.
Sample no.

Used polymer

Solvent (wt%) THF

PVC (%w/w)

CA (%w/w)

Fe3O4 (%w/w)

1
2
3
4
5

100
97.5
95
92.5
90

0
2.5
5
7.5
10

0
0
0
0
0

88
88
88
88
88

6
7
8

90
90
90

10
10
10

0.01
0.1
1

88
88
88

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3. Results and discussion

3.1. Water ux and Pb(II) rejection

Fig. 1. The dead end ltration setup for evaluation membrane performance: 1,
nitrogen cylinder; 2, pressure gage; 3, nitrogen entrance; 4, feed entrance; 5,
reservoir; 6, permeate; 7, collector.

For measurement of Pb rejection following equation was

used:
R



Cp
1
 100%
Cf

(2)

where Cp and Cf are concentrations of lead ions in permeate and

feed, respectively. Concentrations of Pb ions in permeate and feed
were measured by electrical conductivity (Digital conduct-meter,
Jenway, Model: 4510).

In the rst step we tried to optimize concentration of cellulose

acetate (CA) as additive polymer in base polymer polyvinyl
chloride (PVC). What we expected from this addition was high
water ux, because the special feature of CA is its hydrophilicity
[13] so various concentrations of CA (2.5, 5, 7.5, 10, 15, 25, 50, and
75 wt%) were used to choose best concentration. The membranes
having CA concentration more than 10% were broken at 5 bar
pressure; therefore, these were eliminated from all tests and
further studies were done only on CA 2.5, 5, 7.5, and 10%
concentrations.
Fig. 2 shows the water ux of membranes against volume
passed through membrane at different CA concentrations. When
CA concentrations increase the pure water uxes of membranes
also increase. We expected this behavior because of the special
feature of CA [13]. Increased CA concentration in dope solution
increases hydrophilic characteristic of membranes, so high amount
of water is adsorbed by membranes [14] and more water can pass
through membranes.
As we know, usually with increasing ux, rejection decreases
because ions easily pass through membrane. Fig. 3 investigates
how rejection changes by increasing CA concentration. This gure
reveals that by increasing CA, at rst rejection does not show the
corresponding change but at 10% of CA the rejection improves. This
is due to negative charge of CA [26], which increases the negative
charge of membranes and causes improvement of lead ions
adsorption of positive ion (Pb2+). As seen in Fig. 3, there was a quick
decline in rejection in the rst 12 cc which then decreases slowly. It
seems this occurs when the adsorption sites in the membrane are

2.3.2. Scanning electron microscopy (SEM) analysis

The SEM analysis provides the visual data of the top surface
and also cross-sectional morphology of the membrane. This test
was done by Kyky (EM-3200). The unused membrane samples
were divided into smaller size samples. The samples were
submerged in liquid nitrogen for 6070 s to freeze membranes.
The frozen pieces were broken and kept in ambient temperature
for drying. The dried pieces were silver-coated for producing
electric conductivity. Then, they were viewed with the microscope and all details presented in pictures.
2.3.3. Water content
The water content test reveals membrane hydrophilic property
and measures the difference between wet and dry weight of the
membrane. Eq. (3) shows how to calculate water content values
[24]:
WC%

W wet  W dry
 100
W wet

Fig. 2. The effect of CA concentration (2.5, 5, 7.5, and 10) on ux.

(3)

Where Wwet is weight of wet membrane (after 48 h immersion in

distillated water) and Wdry is weight of dry membrane which dried
in oven until the constant weight was reached.

2.3.4. Mechanical strength

The tensor strength was tested to investigate effect of
nanoparticles on mechanical characterization of the membranes.
This test was done according to ASTM1922-03 and samples were
prepared in the standard shape in the ambient temperature (about
26 8C) and humidity (28%). The result was reported as the average
of three tests for each sample.

Fig. 3. The effect of CA concentration (2.5, 5, 7.5, and 10) on rejection.

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A. Gholami et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 15171522

Fig. 4. Rejection verses ux to comparison and selection best concentration of

polymer matrix.

lled up by positive ions; this behavior is already reported by other

researchers too, when the adsorption sites are lled up by ions,
other ions pass through membrane easily [27]. Fig. 4 presents the
membrane containing 10 wt% CA in comparison with others, so in
rst step membrane with 10% of CA is chosen as best membrane.
In second stage, Fe3O4 nanoparticles in three different
concentrations (0.01, 0.1 and 1 wt%) added to best membrane in
rst stage (PVCCA 10 wt%).
Fig. 5 shows the effect of different concentrations of Fe3O4
nanoparticles on ux of membranes. Some researchers [28,29]
reveal that nanoparticles cause some changes in membranes
structures and improve their porosities, what we saw in SEM
pictures, Fig. 6(ad), nanoparticles increase channels in membranes too, but in membrane with 1 wt% nanoparticles, ux decline
in comparison by membrane with 0.1 wt% nanoparticles.
As you see in SEM gures nanoparticles ll up majority of holes
and channels so the ux reduced. Similar behavior has been

Fig. 5. The effect of Fe3O4 nanoparticles concentration (0.01, 0.1, and 1) on ux.

reported by Daraei et al., too [28]. Certainly some particles are

wrapped by polymer and this reduces real efciency of membrane.
Fig. 7 display the Salt Rejection against volume passed through
membrane in different Fe3O4 nanoparticles concentrations. When
nanoparticles concentration increases the salt rejection also
increases. This behavior is because of nature of nanoparticles that
act as an adsorbent, so we expected this behavior but last
membrane (PVCCA 10 wt%) treats in different way from others. As
shown in Fig. 6(d) the increase of nanoparticles concentration led
to nanoparticles accumulation and agglomeration and creates
hunks. These hunks reduce effective area of particles, so rejection
decreases. Similar behavior has been conrmed by Daraei and
Zheng researches [28,29].
As shown in Fig. 7 nanoparticles (0.01% and 0.1 wt%) caused
100% increasing lead rejection at steady state condition and more
than 200% in unsteady state type. The reusability of the
membranes was examined using EDTA as eluting agent in many

Fig. 6. SEM images from cross section of (a) PVC/CA (9:1 w/w), (b) PVC/CA (9:1 w/w)Fe 0.01 wt%, (c) PVC/CA (9:1 w/w)Fe 0.1 wt% and (d) PVC/CA (9:1 w/w)Fe 1 wt%.

A. Gholami et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 15171522

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The swelling in prepared membranes was less than 5% in

thickness. Moreover this was negligible in length and width. The
loss of molecules solvent in preparation stage causes voids
formation which are sufcient to accommodate the water
molecules. Hence, the solvation does not change membrane
dimensions manifestly.
3.3. Membrane tensor strength

Fig. 7. The effect of Fe3O4 nanoparticles concentration (0.01, 0.1, and 1) on lead
removal.

As you see in Fig. 9 the mechanical strength of pristine

membrane (sample 1) and modied membrane containing
0.01 wt% nanoparticles was almost same. As mentioned before
increase of nanoparticles concentration causes to more channels
formation in membranes matrix which decreases membrane
mechanical strength. Also channels lling by nanoparticles can
increase the mechanical strength abruptly.
4. Conclusion
Novelty of this study is using ferrosoferric oxide (Fe3O4)
nanoparticle to remove Lead from water. A series of polyvinyl
chloride (PVC)cellulose acetate (CA)Ferrosoferric oxide (Fe3O4)
Nano ltration membranes were prepared by phase inversion
method. In rst step different concentrations (2.5, 5, 7.5, 10, 15, 25,
50, and 75 wt%) of CA were used as additive to improve
hydrophilicity of membranes and nally 10% of CA was picked
as best concentration. Membrane containing 40% wt CA showed
suitable Lead rejection. In Second step different concentrations
(0.01, 0.1 and 1% wt) of Fe3O4 were used to improve membrane
rejection. Membrane with 0.1% of Fe3O4 showed better ux and
rejection compared to others.

Fig. 8. The effect of Fe3O4 nanoparticles concentration (0.01, 0.1, and 1) on water
content.

Acknowledgment
The authors gratefully acknowledge Arak University for the
nancial support during this research.
References

Fig. 9. The effect of Fe3O4 nanoparticles concentration (0.01, 0.1, and 1) on tensor
strength (mechanical properties).

researches. The result showed good performance for regenerated

membrane [16].
3.2. Water content
Obtained results (Fig. 8) showed that membrane water content
increased by increase of nanoparticles concentration up to 0.1 wt%
in prepared membranes. The membrane water was decreased
again by more increase in nanoparticles content to 1 wt% because
of pores and channels lling by nanoparticle at high additive
concentration which decrease the voids and cavities in membrane
matrix [28].

[1] M. Hua, S. Zhang, B. Pan, W. Zhang, L. Lv, Q. Zhang, Journal of Hazardous Materials
211212 (2012) 317.
[2] J. Garca-Leston, J. Mendez, E. Pasaro, B. Laffon, Environment International 36
(2010) 623.
[3] M. Amini, M. Arami, M.M. Niyaz, A. Akbari, Desalination 267 (2011) 107.
[4] N. Ghaemi, S.S. Madaeni, A. Alizadeh, P. Daraei, F. Rahimpour, A.A. Zinatizadeh,
Separation and Purication Technology 85 (2012) 147.
[5] V. Vatanpour, S.S. Madaeni, R. Moradian, S. Zinadini, B. Astinchap, Separation and
Purication Technology 90 (2012) 69.
[6] S. Yua, M. Maa, J. Liua, J. Tao, M. Liua, C. Gao, Journal of Membrane Science 379
(2011) 164.
[7] E.M. Vroenhoek, J.J. Waypa, Desalination 130 (2000) 265.
[8] B.B. Tang, C. Zou, P. Wu, Journal of Membrane Science 365 (2010) 276.
[9] H.S. Lee, S.J. Im, J.H. Kim, H.J. Kim, J.P. Kim, B.R. Min, Desalination 219 (2008) 48.
[10] E.S. Wiks, Industrial Polymers Handbook: Products, Processes, Application,
Wiley-VCH Press, Germany, 2001.
[11] J.E. Mark, Polymer Data Handbook, Oxford University Press Inc., New York,
1999 .
[12] C.A. Harper, Handbook of Plastic and Elastomers, McGraw-Hill, New York, 1975.
[13] R. Abedini, S.M. Mousavi, R. Aminzadeh, Desalination 277 (2011) 40.
[14] S.M. Hosseini, A. Gholami, S.S. Madaeni, A.R. Moghadassi, A.R. Hamidi, Desalination 306 (2012) 51.
[15] L. Yan, Y.S. Li, C.B. Xiang, Polymer 46 (2005) 7701.
[16] F. Liu, M.R. Moghareh Abed, K. Li, Journal of Membrane Science 366 (2011) 97.
[17] M.A. Al-Anber, Desalination 250 (2010) 885.
[18] I. Soroko, M.P. Lopes, A. Livingston, Journal of Membrane Science 381 (2011) 152.
[19] I. Sorokoa, M. Makowskia, F. Spill, A. Livingston, Journal of Membrane Science 381
(2011) 163.
[20] X.-Z. Wei, L.-P. Zhua, H.-Y. Denga, Y.-Y. Xua, B.-K. Zhu, Z.-M. Huang, Journal of
Membrane Science 323 (2008) 278.
[21] A.Z.M. Badruddoza, A.S.H. Tay, P.Y. Tan, K. Hidajat, M.S. Uddin, Journal of Hazardous Materials 185 (2011) 1177.
[22] Z.-Q. Huang, K. Chen, S.-N. Li, X.-T. Yin, Z. Zhang, H.-T. Xu, Journal of Membrane
Science 315 (2008) 164.

1522

A. Gholami et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 15171522

[23] X. Zhang, Y. Chen, A.H. Konsowa, X. Zhu, J.C. Crittenden, Separation and Purication Technology 70 (2009) 71.
[24] S.M. Hosseini, S.S. Madaeni, A.R. Heidari, A.R. Moghadassi, Desalination 279
(2011) 306.
[25] J. Huang, K. Zhang, Desalination 282 (2011) 1926.
[26] N. Ghaemi, S.S. Madaeni, A. Alizadeh, P.D.V. Vatanpour, M. Falsa, Desalination
290 (2012) 99.
[27] S.S. Madaeni, F. Heidary, Applied Surface Science 257 (2011) 4870.

[28] P. Daraei, S.S. Madaeni, N. Ghaemi, E. Salehi, M.A. Khadivi, R. Moradian, B.

Astinchap, Journal of Membrane Science 415416 (2012) 250.
[29] Z.-H. Zhang, Q.-F. An, T. Liu, Y. Zhou, J.-W. Qian, C.-J. Gao, Desalination 297 (2012)
59.
[30] S.M. Hosseini, S.S. Madaeni, A.R. Khodabakhshi, Preparation and characterization
of PC/SBR heterogeneous cation exchange membranes lled with carbon nanotube, Journal of Membrane Science 362 (2010) 550559.
[31] Y.H. Lia, J. Dinga, Z. Luan, Z. Di, Y. Zhu, C. Xu, D. Wu, B. Wei, Carbon 41 (2003) 2787.