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Procedia Materials Science 11 (2015) 342 – 346

5th International Biennial Conference on Ultrafine Grained and Nanostructured Materials,

UFGNSM15

Synthesis and Surface Characterization of Magnetite-Titania

Nanoparticles/Polyamide Nanocomposite Smart RO Membrane
A. Tayefeha,c, S. A. Mousavib, M. Wiesnerc, R. Poursalehia,*
a
Nanomaterials Group, Materials Engineering Department, Tarbiat Modares University, Tehran, P.O.Box:14115-111, Iran
b
Polymer Group, Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran
c
Center of Environmental Implications of Nanotechnology (CEINT), Duke University, Durham, USA

Abstract

In the water desalination technology, utilizing nanocomposite membranes have been an interesting approach to improve the water
permeability and rejection properties of conventional reverse osmosis (RO) membranes. In this research, effects of magnetite
(Fe3O4) and titania (TiO2) nanoparticles by loading in trimesoyl chloride (TMC) organic solution and in metaphenylene diamine
(MPD) aqueous solutions on the surface characteristics of polyamide layer have been investigated. Also, the morphology and
EDS line and map analysis of Fe3O4 coated PSf layer and in-situ reduced Fe3O4 by impregnation of precursors inside PSf layer
after formation of PA top coat, have been considered. The morphology, dispersion of nanoparticles, surface bonds of magnetite
and titania nanoparticles with polyamide and hydrophilicity of magnetic nanocomposite RO membrane has been taken into
account in each method by scanning electron microscopy (SEM) , attenuated total reflection Fourier transform infrared
spectroscopy (ATR-FTIR), X-ray diffraction (XRD) and contact angle measurement. Trace of nanoparticles inside membrane
cross section has been analyzed by energy dispersive spectroscopy (EDS) method. The samples were implemented to the
different magnetite nanoparticle weight percent caused to the variation of surface energy, contact angle, roughness and
polyamide layer free bonds. In addition the optimum concentration of magnetite nanoparticles for improvement in surface
properties of high efficiency reverse osmosis membrane was obtained. The results can provide a versatile technique for
fabrication of high efficiency magnetic responsive nanocomposite smart RO membranes.
© 2015Published
© 2015 The Authors. Published
by Elsevier Ltd. by Elsevier
This Ltd.access article under the CC BY-NC-ND license
is an open
Peer-review under responsibility of the organizing committee of UFGNSM15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of UFGNSM15
Keywords: Reverse osmosis; nanocomposite; magnetite and titania nanoparticles; smart membrane.

* Corresponding author. Tel.: +98-21-82883997; fax: +98-21-82884390.

E-mail address: poursalehi@modares.ac.ir

2211-8128 © 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of UFGNSM15
doi:10.1016/j.mspro.2015.11.114
 A. Tayefeh et al. / Procedia Materials Science 11 (2015) 342 – 346 343

1. Introduction

Preparing fresh water from seawater or wastewater is known to be one of the most important issues and challenges in
the environmental engineering, because of the current water shortage problems, mainly caused by the rapid growth
of the world population and environment pollution, Paul (2012). Currently, polyamide membranes are widely used
in the commercial RO systems because they offer a combination of high water flux and high rejections of the ions,
Paul (2012). Recently, nanocomposite membranes containing nanomaterials such as metal oxide, silica nanoparticle,
zeolite, graphene, graphene oxide, and carbon nanotube have been prepared to improve membranes properties and
performances, Paul (2012), Fathizadeh et al. (2011), Li et al. (2009), Hu et al. (2013), J. Li et al. (2007), Lu et al.
(2006). For instance, titanium dioxide and silver nanoparticles were incorporated into the membranes to increase
antifouling and antibiofouling properties, Li et al. (2009), Dror-Ehre et al. (2012), and zeolite was embedded into
RO membranes to improve the water flux, Fathizadeh et al. (2011). In this research magnetite (Fe3O4) and titania
(TiO2) nanoparticles was incorporated to a thin film polyamide membrane via interfacial polymerization by two
different route for preparing a new stimuli responsive smart TFN (thin film nanocomposite) RO membrane.
Furthermore, effect of coating of PSf layer and also in-situ formation of magnetite by impregnation of precursors
inside PSf layer on the morphology and EDS analysis of membrane cross section, as a new method for synthesis of
nanocomposite membranes have been considered. The surface characteristics and membrane structure and chemical
alteration were characterized by SEM, ATR-FTIR and contact angle measurement. The results can provide a
versatile technique for fabrication of high efficiency magnetic nanocomposite smart RO membranes.

2. Experimental

Polysulfone ultrafiltration membrane provided from Sharif University of Technology Membrane Center, used for
fabrication of the TFN membranes, as substrate. 1,3-Phenylenediamine (MPD, 99%, Merck) and trimesoyl chloride
(TMC, 98%, Merck) were the monomers used for the synthesis of the polyamide selective layer for thin film
nanocomposite (TFN) membranes. Titanium dioxide nanoparticles (TiO2, Degussa P25) were used for modifying
substrate properties. Furthermore, magnetite nanoparticles were synthesized by co-precipitation method as
mentioned in Lu et al. (2007) also used. The RO substrates were fabricated by interfacial polymerization of
polyamide on the polysulfone backing layer using a. TMC solutions in hexane containing 0 wt%, 1 wt%, 2wt% and
3wt% Fe3O4 nanoparticles, b. MPD solutions containing 0 wt% nanoparticle, 1 wt% TiO2, 1wt% Fe3O4, 1 wt% TiO2
together with 1 wt% Fe3O4. To make a. TMC organic and b. MPD aqueous colloidal suspensions, an appropriate
amount of Fe3O4 nanoparticles and Fe3O4 together with TiO2 nanoparticles was first added into the TMC or MPD
solutions. Then this solution underwent 30 min ultrasonication. In the method (a) At first, 50 ml of 2% (w/v) MPD
aqueous solution was poured onto the top of polysulfone substrate surface and the solution was held on the surface
for 2 min to ensure the penetration of MPD monomer in the pores of substrate followed by pouring 50 ml of 0.15%
(w/v) TMC in n-hexane solution containing magnetite nanoparticles onto the substrate surface. And in the second
method (b) At first, 50 ml of 2% (w/v) MPD aqueous solution containing nanoparticles was poured onto the top of
polysulfone substrate surface and the solution was held on the surface for 2 min to ensure the penetration of MPD
monomer in the pores of substrate followed by pouring 50 ml of 0.15% (w/v) TMC in n-hexane solution onto the
substrate surface. Heat treatment was performed in an oven at 85oC for 5 min. Also, for coating the PSf layer with
different weight percents of magnetite, an aqueous colloid of Fe3O4 poured on the pre-weighted PSf layer. Then by
weighting the membrane 0.15 and 0.3 gr nanoparticles after rinsing membrane by DI water remained on the PSf
layer. And for in-situ synthesis of magnetite inside and on top of the PSf layer we poured a specific amount of Iron
chloride solutions on layer and after some minutes it was washed. Then by adding ammonium hydroxide the
magnetite nanoparticles formed in and on the PSf layer. And finally, ATR-FTIR spectroscopy (Mode: FTLA 2000
series, ABB) was used to identify the functional groups. The IR-FTIR spectra for pure TiO2 and Fe3O4 powder was
obtained from work of Cui and Murashkevich (2008). The membrane morphology studies were conducted with a
SEM (Model: TM3000, Hitachi). The contact angle of substrate was measured by the sessile drop technique using
digital microscope B005 model.
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3. Results and discussion

The scanning electron microscopy images of membranes synthesized by adding nanoparticles to MPD and TMC
aqueous and organic solutions in fig. 1, revealed nanocomposite membrane surfaces demonstrate the presence of
external phase in the PA layer, the surface tend to more rough condition and also surface coverage lowered as the
TiO2 or Fe3O4 or both of them are present in the PA layer.
a b c d

e f g h

Fig. 1. SEM images of surface and cross section of the thin film nanocomposite membranes synthesized by adding nanoparticles to MPD solution
(a) and (e) PA/TiO2 layer; (b) and (f) PA/Fe3O4 layer and by adding to TMC solution; (c) and (g) 1wt% Fe3O4/polyamide layer; (d) and (h) 2wt%
Fe3O4/polyamide layer.

Also as in the figures more entangled and lower rough surface in respect to low loadings in specimen results from
TMC loaded nanocomposites. The nanocomposite membrane surfaces demonstrate the presence of external phase in
the PA layer, the surface tend to more rough condition and also surface coverage lowered as the Fe 3O4 nanoparticles
are present in the PA layer. Furthermore, the cross sections of specimens show the penetration of MPD suspension
in the polysulfone layer and therefore polymerization in depth of polysulfone layer that caused to a rougher cross
section. From the SEM images, it can be clearly observed that nanoparticle agglomeration took place on the top
surface of membrane as the nanoparticles added.

a b cc dd
c d

Fig. 2. SEM images of membrane as (a) and (b) are 0.3 gr Fe3O4 coated PSf membrane surface and cross section; (c) and (d) are the surface and
cross section of in-situ synthesized magnetite on and in the PSf layer.
 A. Tayefeh et al. / Procedia Materials Science 11 (2015) 342 – 346 345

The permanent attachement of these nanoparticles to the polysulfone substrate matrix could be due to the
combined effects of physical and chemical interactions. Also, as in fig. 2 by coating PSf layer with different
amounts of magnetite nanoparticles and then PA formation of it, and by in-situ formation of magnetite on and in the
PSf layer before PA formation, we can have different morphologies. By using EDS analysis in the cross section of
synthesized membranes as in fig. 3, it was concluded that with magnetite coating we a concentrate region on top of
the PSf membrane. However, in the in-situ synthesized magnetite in and on the PSf layer, we have a high
concentrate and high penetrated region. Therefore it can be used as a method to embed such stimuli responsive
nanoparticles inside the membrane.
a b
4
c c d
4
Fe line scan
Fe line scan

3 3
Weight percent

Weight percent
2 2

1 1

0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22

Distance from surface (micrometer) Distance from surface (micrometer)

Fig. 3. SEM EDS map and line scane of Iron atoms in (a) and (b) 0.3 gr Fe3O4 coated PSf and then PA formation on it; in (c) and (d) map and line
scan of in-situ synthesized magnetite nanoparticles in the PSf layer.

Figure 4 presents the changes in the PA layer properties upon addition of different nanoparticles. As can be seen
from thin bar diagram, the hydrophilicity of polysulfone substrate was significantly increased by the addition of
hydrophilic TiO2 and Fe3O4 nanoparticles. And also, heat treatment caused to a slightly improvement in contact
angle. However seawater as droplet test, showed higher contact angles in comparison to DI (deionized) water.

a b

Fig. 4. Contact angle measurement of thin film nanocomposite membranes of the thin film nanocomposite membranes synthesized by adding
nanoparticles to (a) MPD; (b) TMC solutions with sea water and DI water.

a b

Fig. 5. ATR-FTIR spectra of thin film nanocomposite membranes synthesized by adding nanoparticles to (a) MPD; (b) TMC solutions.
346 A. Tayefeh et al. / Procedia Materials Science 11 (2015) 342 – 346

An additional cause might be that the higher hydrophilicity of the MPD aqueous colloidal solution with the
incorporation of nanoparticles, the inflow of water into the membrane during the interfacial polymerization favors.
According to the contact angle experiments showed at fig. 4 for TMC loaded nanocomposites, with increasing the
polymerization time contact angle increased. Also, the optimized condition for minimum contact angle can be in
specimen with 2wt% Fe3O4 with 57o angle respect to deionized water. In all tests, sea water as droplet have 10 o
lower contact angle in relation to deionized water, which it is due to lower surface energy of electrolyte water. Fig. 5
illustrates the ATR-FTIR spectra of neat PA layer and thin film nanocomposite membranes contained of TiO 2 and
Fe3O4 nanoparticles. Following three typical characteristic peaks of formation of the polyamide layer can be seen in
spectrums: in 1654 cm-1 corresponds to C=O bonds stretching vibration (amide I), 1545 cm -1 corresponds to N-H
bonds of amide group (amide II), 1612 and 1488 cm -1 aromatic ring breathing in terms of C=C bond vibrations, and
finally 1243 cm-1 (amide III). In specimen containing Fe3O4 nanoparticles due to decrease of specific bonds of
polyamide as a barrier effect, there is a lower number of bonds and in the most of the regions absorbance of
membrane was lower. In addition, there are following characteristic peaks which are corresponded to Fe-O bonds:
635 cm-1 for magnetite nanoparticles which is related to symmetrical tensional vibration of Fe-O bond. In addition
as can be seen from Fig. 5 for TMC loaded nanocomposites, absorbance curve of the specimens between 600 to
2000 cm-1 has not a lot of bonds in comparison to polysulfone neat membrane. Thus presence of nanoparticle
principally hindered the polyamide polymerization. According to the work of Cui (2008), 520, 500, 450, 430, 422
cm-1 are the characteristic peaks of the Fe3O4, which are exist in the infrared spectrum. In addition with increasing
the Fe3O4 loading, the peaks related to Fe3O4 are amplified.

4. Conclusions

From the experiments that was done, following results attained: by interfacial polymerization process we can
synthesize nanocomposite membrane whether in colloid in TMC organic solution or in MPD aqueous one.
Controlling the amount of nanoparticle loading affects on degree of polymerization of polyamide layer. The type of
the nanoparticle can be a controlling factor to manipulate the characteristics of membrane surface. As it showed, by
increasing the nanoparticles loading the surface roughness decreases and hydrophilicity can be better. It seems that
by adding nanoparticles in MPD solution we have more control on dispersion, agglomeration and loading of them.

Acknowledgements

We are grateful for the Lab-support received from the Sharif University of Technology Membrane Center.

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