Preparation and Characterizations of Iron Oxide Nano
Particles Reinforced Polymeric Thin Films
R. Mahendran1*, E. Varadarajan2, K. Suresh3 and J. Palanivel4
1Department of Chemistry, Anjalai Ammal Mahalingam Engineering College, Anna University, Chennai, India.
2Defense Research and Development Organization, Research & Innovation Centre, IITM Research Park, Chennai, India.
3Department of Physics, Anjalai Ammal Mahalingam Engineering College, Anna University, Chennai, India.
4Electronics and Communication Engineering Department, Anjalai Ammal Mahalingam Engineering College, Anna University, Chennai, India.
Rajagopalan Mahendran, Department of Chemistry, Anjalai Ammal Mahalingam Engineering College, Anna University, Kovilvenni- 614 403, Chennai, India. E-mail:
Received: 22 June, 2017; Accepted: 15 July, 2017; Published: 05 August, 2017
Citation: Mahendran R, Varadarajan E, et al. (2017) Preparation and Characterizations of Iron Oxide Nano-Particles Reinforced Polymeric Thin Films. Nanosci Technol 4(2): 1-6.
The aim of this study is to investigate the influence of Iron
oxidenano-particles (IONPs) on the physico-chemical properties
of poly(vinyl alcohol) (PVA) - poly(2-acrylamido-2-methyl-1-
propanesulfonic acid) (PAMPS) polymer matrix. The IONPs were
synthesized from ferric chloride using NaBH4 as reducing agent
in distilled water, and the IONPs were characterized by FT-IR and
TGA. Thinnano-composite films were fabricated by blending IONPs
colloidal suspension with PVA / PAMPS solution by Thermally
Induced Phase Separation technique. The reinforcement of the IONPs
in the PVA / PAMPS matrix was also confirmed by FT-IR and TGA, and
water uptake measurements revealed the hydrophilic nature of the
IONPs. The cross-sectional and surface morphologies of the films were
analyzed by High-Resolution Scanning Electron Microscopy, and the
results showed that the surface roughness of the films and size of the
IONPs enhanced with respect to their content in the polymer matrix.
Keywords: Polyvinyl Alcohol; Nanoparticles; Iron Oxides; Water
Uptake; Morphological Studies; Thermal Analysis;
Magnetic nano-particles, which can be stimulated under
magnetic field gradients, consist mainly iron, cobalt, nickel and
their compounds [1-4]. The magnetic nano-particles have been
attracted due to the thermal, magnetic and optical properties
. Thus, the particles are being potentially used in photonics,
electronics, biomedical, magnetically tunable materials, micro and
nanofluidics, magnetic particle imaging, data storage and sensors
[6,7]. In particular, iron oxide (Fe2O3) nano-particles (IONPs)
are widely used such applications due to their biocompatible
and biodegradable nature and they can be easily controllable by
magnetic field [8,9]. Further, the IONPs have very large surfaceto-
volume ratio, thus they possess high surface energies .
However, they are in powdery form and possess less mechanical
stability, protects their practical applications. In order to utilize
this precious material practically, it could be blended with
polymeric materialsin order to enhance their applications as well
as physico-chemical properties of the host polymer [10,11].
Recently, chemically cross-linked poly (vinyl alcohol) and poly
(2-acrylamido-2-methyl-1-propanesulfonic acid) (PVA-PAMPS)
films are effectively used in the mechanical devices, attributable
to their biocompatibility and cost-effectiveness [12,13]. Notably,
the PVA has been widely utilized in the fabrication of tablet
coating, artificial tears, drug delivery and tissue replacement,
owing to their specific characteristics of toxicologically safe,
high oxygen permeability and biodegradability , conversely
they possess very less mechanical stability. To overcome this
major drawback, it should be chemically cross-linked / blended
with other hydrophilic materials to acquire mechanically stable
materials. Specifically, the PAMPS, a sulfonic acid acrylic monomer
has high proton conductivity and well hydrated due to presence
of sulfonic acid groups in its backbone, and they are effectively
applied infuel cells, medical devices and actuators [7,15]. In order
to improve their mechanical and thermal stabilities of these PVA
and PAMPS polymers, they could be blended / chemically crosslinked
for obtaining flexible, mechanically and thermally stable
material [12,13]. Generally, the reinforcement of nano-particles
into the polymer matrix enhances the mechanical, dimensional
and thermal stabilities of the host polymer matrix. Very recently,
Guo et al.  fabricated IONPs reinforced PVA composites with
superior thermal stability, and the IONPs have robust interaction
with the PVA matrices by hydrogen bonding between their
In this study, based on the above merits of IONPs in the
polymer matrix, PVA/PAMPS / IONPs nano-composite films were
fabricated by Thermally Induced Phase Separation technique.
The major function of the IONPs is to enhance the thermomechanical
properties, magnetic activity (superparamagtic) and
dimensional stabilities of the PVA/PAMPS matrix. The physicothermal
properties of the PVA/PAMPS/IONPs films were studied
by thermo gravimetric analysis (TGA) and water-uptake ratio. The
reinforcing effect of the IONPs on the micro structural property
of the PVA/PAMPS matrix was extensively investigated by High
Resolution-Scanning Electron Microscopy (HR-SEM).
Materials and Methods
PVA (Mw = 61,000), PAMPS (Mw = 2,000,000), NaBH4 and
FeCl3.6H2Owerepurchased from Sigma Aldrich, India, and used as
received. Distilled Water (DW) was used as solvent to prepare the
PVA and PAMPS solutions and IONPs suspension.
Synthesis and characterizations of IONPs
The IONPs(α-Fe203, hematite) were synthesized using
sodium borohydride as reducing agent . Figure 1 shows
the schematic representation of synthesis of the IONPs. Firstly,
FeCl3.6H2O (7.5 g) was dissolved in 100 mL distilled water and
stirred for 4 hrs, and NaBH4 (1 g / 100 mL) solution was added
to the ferric chloride solution drop wise for an hour at room
temperature. The color of solution changed from yellowish to
black color, and the nano-particles dispersion were stirred for
additional 10mins, and centrifuged, finally. The IONPs were dried
in an oven at 100°C for 24 hrs, and stored ina desiccator until
used, and they were characterized by FT-IR and TGA.
Figure 1: Synthesis of Fe2O3 nano-particles
Preparation of PVA/PAMPS/IONP films
The PVA/PAMPS/IONP nano-composite films were prepared
by Thermally Induced Phase Separation technique . Figure
2 shows the schematic representation of the fabrication of
PVA/PAMPS/IONP films. Firstly, the PVA solution(solventdistilled
water)was heated to 80°C with stirring until to obtain
a homogeneous and transparent solution. Additionally, the
PAMPS aqueous solution was poured into the PVA solution and
stirred for additional 3 hour to attain homogeneity. Furthermore,
the IONPs were dispersed in distilled water by ultrasonication
for 10 min, and the IONPs dispersion was added to the PVA/
PAMPS mixture, and stirred in a mechanical stirrer for 5 hours to
acquirea homogeneous mixture. Then, the solution was poured in
a Teflon coated mold and dried in anoven at 90 °C for 24 hours to
evaporate the solvent, utterly. The PVA/PAMPS/IONP films were
prepared with various weight ratios, which are shown in the table
1. Furthermore, the PVA/PAMPS film was prepared at the weight
ratio of 10:2 in distilled water to compare the influence of the
IONPs on the PVA/PAMPS matrix.
Figure 2: Fabrication of PVA-PAMPS-IONPs nano-composite film
Table 1: Properties of PVA/PAMPS and PVA/PAMPS/IONP 1-4 films
PVA/PAMPS/ IONP -1
PVA/PAMPS/ IONP -2
PVA/PAMPS/ IONP -3
PVA/PAMPS/ IONP -4
Structural analysis of the PVA, PAMPS, IONPs and PVA/PAMPS/
IONP composite was carried out by Fourier Transform Infrared
Spectroscopy (FT-IR,SHIMADZU, IR Prestige-21), and thermal
stability of the samples was also analyzed by thermogravimetric
analysis (TGA/SDTA851e, Mettler Toledo) under nitrogen
atmosphere at heating rate of 10°C / min. Further, the hydrophilic
nature of the as-prepared films was measured by water uptake
measurement by gravimetric method [18,19]. The cross-sectional
and surface morphologies of the PVA / PAMPS and PVA/PAMPS/
IONP 1-4 thin films were observed by HR-SEM (FEI Quanta, FEG
200). For the analysis, the dried films were fractured, mounted
on a stub and sputter-coated with gold.
Results and Discussion
The thickness of the films increased with respect to the
content of IONPs in the PVA/PAMPS matrix, and the films were
flexible in nature. The thickness of the PVA/PAMPS/IONP-1, PVA/
PAMPS/IONP -2, PVA/PAMPS/IONP -3 and PVA/PAMPS/IONP -4
were 210, 230, 310 and 325 μm, respectively. The FT-IR spectra
of PVA, PAMPS, IONPs and PVA/PAMPS/IONP composite are
shown in the figure 3. In the PVA spectrum, large bands between
3350 - 3000 cm-1 are linked to the stretching O-H vibration of
intermolecular and intramolecular hydrogen bonds, and the band
in the region of 2980 - 2710 cm-1 refers to the stretching C-H
of alkyl groups . In the PAMPS spectrum, the characteristics
bands around For convenience, PVA/PAMPS/IONP-1 (0.5 wt%),
PVA/PAMPS/IONP -2 (1.0 wt%), PVA/PAMPS/IONP -3 (1.5 wt%)
and PVA/PAMPS/IONP -4 (2.0 wt%) is denoted as PVA/PAMPS/
IONP 1-4 films.
1556 and 1650 cm-1 were showed the vibrational mode of
amide groups, the two sharp peaks at 1039 and 1221 cm-1 were
observed for the S–O stretching of sulfonate groups, and the band
around 3400 - 3000 cm-1owing to the O-H stretching vibration
[12,13]. In the IONPs spectrum, the broad band at 3700–3000
cm−1 indicated the stretching vibration mode of surface hydroxyl
groups of the pristine IONPs . In the PVA/PAMPS/IONP
spectrum, the stretching absorption band attributed to the C-N
of PAMPS decreases with more cross-linking, followed by an
increased sharp peak due to the C=O from PAMPS. The broad
peak observed around 3500-3000 cm-1 due to the O-H stretching
vibration of the PVA, PAMPS and IONPs in the nano-composite
films. Hence, the incorporation of IONPs in the polymer matrix
was concluded by the FT-IR.
Figure 3: FT-IR spectra of PVA, PAMPS, IONPs and PVA/PAMPS/IONP
Figure 4: TGA of PVA, PAMPS, IONP and PVA/PAMPS/IONP composite
Figure 4 shows the Thermo Gravimetric Analysis (TGA)
curves of PVA, PAMPS, IONPs and PVA/PAMPS/IONP composite.
The mass loss of the PVA occurred in two stages: The first mass
loss around100-150°C was attributable to the loss of water
molecules and the second mass loss around 250–350°C owing
to the thermal degradation of the PVA backbone [12,13]. In the
PAMPS, the decomposition temperature occurred at 100°C due
to moisture loss, and around 300°C was the decomposition of
sulfonate and propenyl groups. Finally, ~380 - 430°C was the
degradation of the PAMPS backbone . In the IONPs, two
major mass losses at about 100°C and 200-250°C were observed.
At 100°C, it could be attributed to the evaporation of moisture,
and the mass of the IONPs becomes gradually decreased until the
temperature reaches 380°C. The mass loss around 200 – 300°C
correspond to the thermal decomposition of oxygen-containing
functional groups from the IONPs [21,22]. In the degradation
curve of PVA/PAMPS/IONP composite, minute mass loss at 100°C
due to moisture content, and the mass of the sample gradually
decreased to 600°C. The mass loss around 170-200°C,could be
attributed to the removal of labile oxygen functional groups from
the PVA/PAMPS/IONP nano-composite. The mass loss between
240-400°C, owing to the decomposition of sulfonic acid groups
from the PAMPS, and the mass loss after 400°C belongs to the
breaking of the polymer backbone.
The addition of IONPs changed the water uptake property
of the as prepared nano-composite films, significantly (Table 1)
Figure 5: HR-SEM image of PVA/PAMPS/IONP-1 (a and b), PVA/PAMPS/IONP-2 (c and d), PVA/PAMPS/IONP-3 (e and f) and PVA/PAMPS/IONP-4(g and h) films
[23,24]. It can be elucidated by the interaction of the hydrophilic
IONPs and the hydrophilic PVA/PAMPS matrix with the water
molecules [12,13]. The water content of the PVA/PAMPS (66.06
%), PVA/PAMPS/IONP-1 (68.58 %), PVA/PAMPS/IONP -2 (70.13
%), PVA/PAMPS/IONP -3 (71.23%) and PVA/PAMPS/IONP -4
(73.83 %) were observed. Hence, the incorporation of IONPs
enhances the water absorption capacity of the nano-composites
with respect to their content in the polymer matrix.
The surface and cross-sectional morphologies of the PVA/
PAMPS/IONP 1-4 films are shown the in figure 5 (a-h). The
surface roughness and particle size of the IONPs in the nanocomposite
films improved with respect to the concentration (0.5
to 2.0wt%) of the IONPs in the polymer matrix of PVA/PAMPS/
IONP 1-4 films, respectively, which was clearly identified from the
figure. 5 a, c, e and g, respectively.
Iron oxide nano-particles reinforced poly (vinyl alcohol) and
poly 2-acrylamido-2-methyl-1-propanesulfonic acid based nanocomposite
were fabricate dutilizing distilled water as solvent
(“Green” route method) by TIPS. The IONPs were effectively
synthesized by chemical reduction of FeCl3.6H2O using sodium
borohydride as reducing agent. The reinforcement of IONPs in
the PVA/PAMPS matrix was clearly validated by FT-IR and TGA.
Further, the water uptake capacity of the PVA/PAMPS/IONP
films increased with respect to the IONPs content, which might
be due to the hydrophilic nature of IONPs. The HR-SEM images
clearly revealed the agglomeration of IONPs on the surface of the
films by increasing their content in the polymer matrix. Thus, the
fabricated mechanically and thermally stable PVA/PAMPS/IONPs
nano-composite films can be effectively applied in magnetic
actuators and sensors, energy harvesters, and spintronic devices,
owing to their light weight, hydrophilicity, cost effective and
Conflict of Interest
The authors declare that they have no competing interests.
- Lu AH, Salabas EL, Schuth F. Magnetic Nanoparticles: Synthesis, Protection, Functionalization and Application. Angew Chem Int Ed Engl. 2007;46(8):1222-1244. doi: 10.1002/anie.200602866
- Arzadeh A, Samiei M, Davaran S. Magnetic nanoparticles: preparation, physical properties, and applications in biomedicine. Nanoscale Res Lett. 2012;7:144-157. doi: 10.1186/1556-276X-7-144
- Stanicki D, Elst LV, Muller RN. Synthesis and processing of magnetic nanoparticles. Curr Opin Chem Eng. 2015;8:7–14.
- Sundaresan V, Menon JU, Rahimi M, Nguyen KT, Wadajkar AS. Dual-responsive polymer-coated iron oxide nanoparticles for drug delivery and imaging applications. Int J Pharm. 2014;466(1-2):1-7. doi: 10.1016/j.ijpharm.2014.03.016
- Tang SCN, Lo IMC. Magnetic nanoparticles: Essential factors for sustainable environmental applications. Water Res. 2013;47(8):2613-2632. doi: 10.1016/j.watres.2013.02.039
- Saeid Zanganeh, Gregor Hutter, Ryan Spitler, Olga Lenkov, Morteza Mahmoudi, Aubie Shaw, et al. Iron oxide nanoparticles inhibit tumour growth by inducing pro-inflammatory macrophage polarization in tumour tissues. Nat Nanotechnol. 2016;11:986–994. doi: 10.1038/nnano.2016.168
- Kim SJ, Lee CK, Kim SI. Electrical / pH responsive properties of poly (2-acrylamido-2-methylpropane sulfonic acid) / hyaluronic acid hydrogels. J ApplPolym Sci. 2004;92(3):1731–1736. doi: 10.1002/app.20133
- Guskos N, Glenis S, Likodimos V, J. Typek, M. Maryniak, M. Kwiatkowska, et al. Matrix effects on the magnetic properties of γ-Fe2O3 nanoparticles dispersed in a multiblock copolymer. J Appl Phys. 2006;99:084307.
- Rafi MM, Ahmed KSZ, Nazeer KP, D. Siva KumarM. Thamilselvan. Synthesis, characterization and magnetic properties of hematite (α-Fe2O3) nanoparticles on polysaccharide templates and their antibacterial activity. Appl Nanosci. 2015;5(4):515–520.
- Baker C, Shaha S, Hasanain SK. Magnetic behavior of iron and iron-oxide nanoparticle / polymer composites. J Magn Magn Mater. 2004;280(2-3):412–418.
- Novakova AA, Lanchinskaya VY, Volkova AV, Gendler TS, Moskvina MA, Zezin SB, et al. Magnetic properties of polymer nanocomposites containing iron oxide nanoparticles. J Magn Magn Mater. 2003;258:354–357.
- Erkartal M, Aslan A, Erkilic U, Seyma Dadi, Ozgur Yazaydin, Hakan Usta, et al. Anhydrous proton conducting poly (vinyl alcohol) (PVA) / poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) /1.2.4-triazole composite membrane. Int J Hydrogen Energy. 2016;41(26):11321–11330.
- Erkartal M, Usta H, Citir M, Unal Sen. Proton conducting poly(vinyl alcohol) (PVA) / poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) / zeoliticimidazolate framework (ZIF) ternary composite membrane. J Membr Sci. 2016;499:156–163.
- Halima NB. Poly(vinyl alcohol): review of its promising applications and insights into biodegradation. RSC Adv. 2016;46:39823-39832.
- Florjańczyk Z, Zygadło-Monikowska E, Wielgus-Barry E, Kuźwaet K, Paśniewski J. Proton conducting electrolytes based on poly(2-acrylamido-2-methyl-1-propanesulfonic acid). Electrochim Acta. 2003;48(14-16):2201–2206.
- Guo Z, Zhang D, Wei S, Zhe Wang, Amar B. Karki, Yuehao Li, et al. Effects of iron oxide nano-particles on polyvinyl alcohol: interfacial layer and bulk nanocomposites thin film. J Nanopart Res. 2010;12(7):2415-2422.
- Farahmandjou M,Soflaee F. Synthesis of Iron Oxide Nano-particles using Borohydride Reduction. Int J Bio-Inorg Hybr Nano mater. 2014;3(4):203-206.
- Hyojin K, Dowon S. Influence of water saturation on fracture toughness in woven natural fiber reinforced composites. Adv Composite Mater. 2007;16(2):83–94.
- Gonga C, Zheng X, Liu H, Wang G, Cheng F, Zheng G, et al. A new strategy for designing high-performance sulfonated poly(ether ether ketone) polymer electrolyte membranes using inorganic proton conductor-functionalized carbon nanotubes. J Power Sources. 2016;325:453–464.
- Kaushik A, Khan R, Solanki PR, Pandey P, Alam J, Ahmadet S, et al. Iron oxide nanoparticles–chitosan composite based glucose biosensor. Biosens Bioelectron. 2008;24(4):676–683.
- Sharma G, Jeevanandam P. Synthesis of self-assembled prismatic iron oxide nanoparticles by a novel thermal decomposition route. RSC Adv. 2013;3(1):189-200.
- Masthoff IC, Kraken M, Menzel D, LitterstG FJ, Garnweitner G. Study of the growth of hydrophilic iron oxide nanoparticles obtained via the non-aqueous sol–gel method. J Sol-Gel Sci Technol. 2016;77:553–564.
- Gupta AK, Gupta M. Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications. Biomaterials. 2005;26:3995–4021.
- Laurent S, Forge D, Port M, Roch A, Robic C, Robert N, et al. Magnetic Iron Oxide Nanoparticles: Synthesis, Stabilization, Vectorization, Physicochemical Characterizations and Biological Applications. Chem Rev. 2008;108:2064–2110.