J Nanopart Res (2010) 12:2415–2426
DOI 10.1007/s11051-009-9802-z
RESEARCH PAPER
Effects of iron oxide nanoparticles on polyvinyl alcohol:
interfacial layer and bulk nanocomposites thin film
Zhanhu Guo • Di Zhang • Suying Wei • Zhe Wang • Amar B. Karki
Yuehao Li • Paul Bernazzani • David. P. Young • J. A. Gomes •
David L. Cocke • Thomas C. Ho
Received: 9 July 2009 / Accepted: 3 November 2009 / Published online: 19 November 2009
Ó Springer Science+Business Media B.V. 2009
Abstract Iron oxide (a-phase) nanoparticles with
coercivity larger than 300 Oe have been fabricated at
a mild temperature by an environmentally benign
method. The economic sodium chloride has been
found to effectively serve as a solid spacer to disperse
the iron precursor and to prevent the nanoparticles
from agglomeration. Higher ratios of sodium chloride
to iron nitrate result in smaller nanoparticles (19 nm
for 20:1 and 14 nm for 50:1). The presence of
polyvinyl alcohol (PVA) limits the particle growth
(15 nm for 20:1 and 13 nm for 50:1) and favors
nanoparticle dispersion in polymer matrices. Obvious
physicochemical property changes have been
observed with PVA attached to the nanoparticle
Z. Guo (&)  D. Zhang  Y. Li  J. A. Gomes 
D. L. Cocke  T. C. Ho
Integrated Composites Laboratory (ICL), Dan F. Smith
Department of Chemical Engineering, Lamar University,
Beaumont, TX 77710, USA
e-mail: zhanhu.guo@lamar.edu
S. Wei  P. Bernazzani
Department of Chemistry and Physics, Lamar University,
Beaumont, TX 77710, USA
Z. Wang
Mechanical and Aerospace Engineering Department,
University of California Los Angeles, Los Angeles,
CA 90095, USA
A. B. Karki  David. P. Young
Department of Physics and Astronomy, Louisiana State
University, Baton Rouge, LA 70803, USA
•
surface. With PVA attached to the nanoparticle
surface, the nanoparticles are found not only to
increase the PVA cross-linking with an increase in
melting temperature but also to enhance the thermal
stability of the PVA. The nanoparticles are observed
to be uniformly dispersed in the polymer matrix.
Scanning electron microscopy (SEM) microstructure
also shows an intermediate phase with a strong
interaction between the nanoparticles and the poly-
mer matrices, arising from the hydrogen bonding
between the PVA and hydroxyl groups on the
nanoparticle surface. The addition of nanoparticles
favors the cross-linkage of the bulk PVA matrices,
resulting in a higher melting temperature, and an
enhanced thermal stability of the polymer matrix.
Keywords Nanoparticles 
Polymer nanocomposites  Thermal properties
Introduction
Antiferromagnetic a-Fe2O3 (hematite) nanoparticles
(NPs) have attracted much interest due to their wide
potential applications in many areas, such as pigments
(Feldmann 2001), catalysts (Glisenti 1998; Ren et al.
2009; Rofer-Depoorter 1981; Xie et al. 2009; Zhang
et al. 2009; Zheng et al. 2007), photocatalysts
(Kay et al. 2006), gas sensors (Fukazawa et al.
1993; Huo et al. 2005; Neri et al. 2002; Wang et al.
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2008), nonlinear optics (Yu et al. 2000), reinforcing
nano-fillers for multifunctional polymer nanocompos-
ites (Guo et al. 2008a, 2009a, b; Zhang et al. 2009),
and lithium ion batteries (Wu et al. 2006, 2008). In
addition, the small band gap (*2.1 eV), high-corro-
sion resistance, and low cost make iron oxide
nanoparticles suitable for serving as photoelectrodes
in solar energy conversions (Ohmori et al. 2000).
Various synthetic methods have been developed
for the preparation of hematite nanoparticles includ-
ing chemical precipitation (Glisenti 1998), hydro-
thermal reaction (Chen et al. 2002; Dhage et al. 2002;
Li et al. 1998, 2007; Wang et al. 2004), sol–gel
method (Dong and Zhu 2002; Huo et al. 2005),
solvothermal method (Zheng et al. 2007), ball milling
process (Bercoff et al. 2007; Wang and Jiang 2007),
and microemulsion technique (Nassar and Husein
2006; Santra et al. 2001). Iron oxides have strong
magnetic properties and aggregate/agglomerate spon-
taneously, resulting in nanoparticles with a wide size
distribution. In order to prevent nanoparticle agglom-
eration, various surfactants, polymers, or coupling
agents had been used. Unfortunately, organic sol-
vents, bases, and most of the surfactants are harmful
to the environment and expensive for the above
reported methods, especially, the wet chemical fab-
rications. In addition, most of the traditional methods
are conducted on a small batch scale, and are not
suitable for large-scale fabrication. Thermal decom-
position of iron nitrate has been investigated by
thermogravimetric analysis (TGA), and a-Fe2O3 was
reported (Wieczorek-Ciurowa and Kozak 1999).
However, there are no reports in the literature
regarding the nanostructural formation of a-Fe2O3
from decomposition, especially in the presence of an
inert salt. The development of a facile and economic
method for large-scale fabrication of hematite nano-
particles still remains a challenge.
One of the greatest challenges in fabricating high-
quality polymer nanocomposites is the lack of the
synergy between the polymer matrices and the
nanofillers. In principle, the polymers could serve
as a template for nanoparticle fabrication. The
nanoparticles can introduce unique physicochemical
properties into the polymer matrices, such as mag-
netism, non-linear optical properties, and improved
mechanical properties. However, the nanoparticle
materials could also have a deleterious effect on the
polymer matrix.
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J Nanopart Res (2010) 12:2415–2426
The effect of the nanoparticles on the polymers
attached to their surface, and on the bulk polymer
itself, has not been systematically investigated. Such
effects will play an important role in controlling the
quality and properties of the fabricated polymer
nanocomposites. In this article, a facile, economic,
and solvent-free method utilizing a mild annealing
process was developed to fabricate crystalline iron
oxide nanoparticles. Sodium chloride, which is envi-
ronmentally benign and easy to remove, was used as
the template/spacer to prevent the nanoparticles from
agglomerating. The biodegradable and water soluble
material, polyvinyl alcohol (PVA), was chosen as the
binding polymer. The ratio of the iron precursor to
sodium chloride and the presence of PVA in the
purifying solution were investigated for particle
growth. The effect of the nanoparticles on the phys-
icochemical properties of PVA was also explored, as
the PVA was chemically bound to or physically
entangled with the nanoparticle surface. The nano-
composites consisting of the PVA matrix, reinforced
with the fabricated Fe2O3 nanoparticles, were fabri-
cated by the drop casting method. The effects of
nanoparticles on the PVA, both on the nanoparticle
surface and on the bulk polymer, were investigated by
various analytical methods and discussed.
Experiment
Materials
Iron nitrite (Fe(NO3)39H2O, Alfa Aesar Company,
404.15 g/mol) and sodium chloride (NaCl, Alfa
Aesar Company) are used as the iron precursor and
the solid stabilizer to disperse the iron nitrate and
prevent the products from agglomerating.
Polyvinyl alcohol (PVA, MW = 88000–96800,
degree of polymerization = 2000–2200) was used
as the polymer nanocomposite matrix and the stabi-
lizer to prevent nanoparticle agglomeration. All the
chemicals were used as-received without any further
treatment.
Nanoparticle fabrication
Iron nitrate and sodium chloride were dissolved in de-
ionized water with a molar ratio of 1:50 and 1:20,
respectively. The homogeneous solid solution was
J Nanopart Res (2010) 12:2415–2426
obtained by drying at 70 °C under magnetic stirring.
The NPs were manufactured by annealing the solid
salt at 700 °C in a tube furnace for about 30 min and
cooled naturally to room temperature. The product
was washed thoroughly with de-ionized water to
remove sodium chloride and dried completely at
60 °C. In order to prevent particle agglomeration and
modify the surface chemistry of the NPs, 1 wt% PVA
aqueous solution was used to treat the NPs immedi-
ately after annealing. The particles were then washed
thoroughly with de-ionized water to remove NaCl.
Nanocomposite fabrication
The as-produced or functionalized Fe2O3 NPs with
specific amount were dispersed in 5 wt% PVA
aqueous solution (20 mL) for polymer nanocompos-
ite fabrication. The aqueous iron oxide nanoparticle
PVA solution was cast in a petri dish and dried
completely at 60 °C. It was found that the PVA-
treated iron oxide nanoparticles have a better disper-
sion quality than those washed with only de-ionized
water. Thus, only PVA-treated iron oxide nanoparti-
cles with an iron nitrate to sodium chloride ratio of
1:20 were used for PVA–Fe2O3 nanocomposite
fabrication and property characterization.
Characterization
The thermal decomposition of iron nitrate was
determined by TGA from 25 to 1000 °C with an air
flow rate of 50 cm3/min (ccpm) and a heating rate of
20 °C/min.
The phase structure of the produced iron oxide
nanoparticles was investigated by powder X-ray
diffraction. The powder X-ray diffraction analysis
of the samples was carried out with a Bruker AXS D8
Discover diffractometer with General Area Detector
Diffraction System (GADDS) operating with a Cu Ka
radiation source filtered with a graphite monochro-
mator (k = 1.5406 Å). The detector used was a HI-
STAR two-dimensional multi-wire area detector. The
samples were loaded onto double sided scotch tape,
placed on a glass slide, and mounted on a quarter-
circle Eulerian cradle (Huber) on a XYZ stage. The
X-ray beam was generated at 40 kV and 40 mA
power, and was collimated to about 800 lm spot size
on the sample. The incident x angle was 5°. A laser/
video system was used to ensure the alignment of the
2417
sample position on the instrument center. XRD scans
were recorded from 7 to 77° for 2h with a 0.050°
step-width and a 60 s counting time for each step.
The XRD data were analyzed using the DIFFRAC-
Plus EVA program (Bruker AXS, Karlsruhe, Ger-
many), and the patterns were identified using the
ICDD PDFMaint computer reference database.
Fourier transform infrared spectroscopy (FT-IR, a
Bruker Inc. Tensor 27 FT-IR spectrometer with
hyperion 1000 ATR microscopy accessory) was used
to characterize the surface chemistry of the nanopar-
ticles, as well as to characterize their interaction with
the polymer matrix.
Scanning electron microscopy (SEM, JEOL field
emission scanning electron microscope, JSM-6700F)
was used to investigate the fabricated nanoparticles
and its dispersion in the polymer matrix. A thin gold
layer was deposited to improve the electrical con-
ductivity for better imaging.
Magnetic properties of the nanoparticles at room
temperature were investigated in a 9 T physical
properties measurement system (PPMS) by Quantum
Design.
The differential scanning calorimetry (DSC) tem-
perature and heat flow values were calibrated with an
indium standard. The heating and cooling rate was
10 °C/min, and the experimental was performed in a
continuous flow of nitrogen gas with a flow rate of
20 cm3/min (ccpm). The temperature was in the
range of 25–250 °C.
Results and discussion
Nanoparticle fabrication and property
characterization
Figure 1a and b shows the thermal decomposition
study of iron nitrate under TGA with the temperature
changing from 20 to 800 °C, and isothermal decom-
position at 700 °C, respectively. The TGA was
carried out in air with a flow rate of 40 cm3/min.
Iron nitrate was observed to decompose in both cases.
A total of 60.2% was observed to lose sharply due to
the decomposition of the iron nitrate and additional
8.0% loss at higher temperatures was due to the loss
of the physicochemical adsorption of water. The total
weight residue in both cases is about 19.4 and 19.7%,
respectively. This is almost equivalent to the
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Fig. 1 a Thermal
decomposition study of iron
nitrate and b isothermal
thermal decomposition of
iron nitrate at 700 °C under
air condition
theoretical calculation (19.80%) of iron oxide (a-
Fe2O3) from iron nitrate. The residue after each TGA
run was observed to be stable at 400 °C during the
temperature sweep. The thermal decomposition of
iron nitrate in the isothermal (700 °C) reaction was
completed within 5 min. The iron oxide nanoparticle
fabrications were carried out at 700 °C with a
reaction time of 1 h. Sodium chloride was chosen
as a spacer to disperse iron nitrate and also as a
stabilizer to prevent agglomeration of the formed
nanoparticles.
Figure 2 shows the X-ray diffraction (XRD)
patterns of iron oxide nanoparticles fabricated with
different ratios of iron nitrate to sodium chloride (20
and 50) and treated with de-ionized water or 1 wt%
PVA aqueous solution, respectively. Although, the
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J Nanopart Res (2010) 12:2415–2426
peak width varies, all the samples have common peak
at 24.2°, 33.4°, 35.7°, 41.1°, 49.8°, 54.4°, 62.9°,
64.5°, and 72.5°. The d-spacing is calculated using
Bragg’s law (Rudel and Zite-Ferenczy 1971):
nk
d¼ ð1Þ
2 sin h
where n is chosen as 1 and k is 1.5406 Å for the
wavelength of Cu Ka radiation.
The calculated d-spacings are 3.67, 2.68, 2.51,
2.19, 1.83, 1.68, 1.48, 1.44, and 1.30 Å, respectively.
These d-spacings are in agreement with those of the
XRD PDF card #33-0664 (standard XRD pattern of
a-Fe2O3). This indicates that the formed dark reddish
brown iron oxide nanoparticles are a-Fe2O3. The
corresponding crystal planes are (0, 1, 2), (1, 0, 4),
J Nanopart Res (2010) 12:2415–2426 2419

Fig. 2 XRD patterns of

iron oxide nanoparticles
formed (a) with a ratio of
iron nitrate to sodium
chloride (1:20) and washed
with de-ionized water; (b)
with a ratio of iron nitrate to
sodium chloride (1:20) and
treated with PVA aqueous
solution; (c) with a ratio of
iron nitrate to sodium
chloride (1:50) and washed
with de-ionized water; and
(d) with a ratio of iron
nitrate to sodium chloride
(1:50) and washed with
PVA aqueous solution

(1, 1, 0), (1, 1, 3), (0, 2, 4), (1, 1, 6), (2, 1, 4), (3, 0, 0),
and (1, 0, 10), respectively.
The average particle size (L) was estimated from
the Debye–Scherrer equation (Eq. 2; Talapin et al.
2001a):
Kk
L¼ ð2Þ
bð2hÞ cos h
where b(2h) is the full width at half-maximum
(FWHM), K is a constant taken as the normal value
of 0.9, k is the wavelength of X-ray wavelength (for
copper, k = 1.5406 Å), and h is the Bragg angle. The
(1, 1, 0) crystal plane at 2h = 35.7° was used to
estimate the particle size. The calculated values are
about 19, 15, 14 and 13 nm, respectively. The
particle sizes are observed to decrease with an
Fig. 3 FT-IR spectra of iron oxide nanoparticles formed (a)
increase in the ratio of sodium chloride to iron with a ratio of iron nitrate to sodium chloride (1:20) and
nitrite. The solution containing PVA for salt removal washed with de-ionized water; (b) with a ratio of iron nitrate to
was also observed to inhibit the particle growth by sodium chloride (1:20) and treated with PVA aqueous solution;
serving as a stabilizer. The presence of PVA has (c) with a ratio of iron nitrate to sodium chloride (1:50) and
washed with de-ionized water; and (d) with a ratio of iron
effectively prevented the Ostwald ripening process nitrate to sodium chloride (1:50) and washed with PVA
(Guo et al. 2006a; Talapin et al. 2001b) and favors aqueous solution
smaller nanoparticle fabrication.
Figure 3 shows the FT-IR spectra of the as-
produced a-Fe2O3 nanoparticles and those function- in the nanoparticles washed with PVA aqueous
alized with PVA. The characteristic hydrogen-bonded solution. The absorption band at 1,142 cm-1 has
stretch bands (3,259 and 1,645 cm-1; Matveev et al. been used as an assessment tool of the PVA structure
2005; Okuno et al. 2003; Ping et al. 2001), C–H due to the semi-crystalline nature of the synthetic
stretch bands (1,373 and 1,319 cm-1; Carrillo et al. polymer (Mansur et al. 2004). Thus, the 1,142 cm-1
2004), and C–O bands (1,142 and 1,088 cm-1; vibration band observed in the spectra of the nano-
Carrillo et al. 2004; Okuno et al. 2003) are observed particles treated with PVA aqueous solution, clearly

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indicates the existence of PVA. The absorption bands
at 2,949 and 2,904 cm-1 represent the sp3 bonding in
–CH3 group.(Deschenaux et al. 1999) The peaks
around 831 cm-1 are attributed to C–H bending
(Mansur et al. 2004). No C–H group peak was
observed in the spectra of the nanoparticles washed
with de-ionized water, and the obvious hydroxyl
groups indicate the presence of physically absorbed
moisture or chemically hydrolyzed water, which
make the nanoparticles compatible with PVA, and
are responsible for the subsequent uniform particle
dispersion in the PVA nanocomposite fabrication.
Figure 4 shows the TGA curves of the nanopar-
ticles treated with de-ionized water and with the PVA
aqueous solution, respectively. The small weight
percentage loss in the iron oxide nanoparticles is due
to the evaporation of the moisture or the condensation
of the hydroxyl groups. The initial decomposition
temperature (sharp weight loss) was observed to
increase from 233 to 302 °C, when the ratio of iron
nitrite to sodium chloride increased from 20 to 50,
which is due to the smaller particle size in the latter
case. The stronger interaction between the iron oxide
nanoparticles and the PVA matrix, arising from the
higher specific surface area inherent with the smaller
nanoparticles improves the thermal stability of the
entangled polymer chains.
The interaction between the nanoparticles and the
attached polymer, i.e., the effect of the nanoparticles
on the thermal properties of the PVA, was further
Fig. 4 TGA curves of (a)
pure PVA, and iron oxide
nanoparticles washed with
(a) water, and (c) 1 wt%
PVA, respectively (ratio of
iron nitrate to sodium
chloride 1:20)
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J Nanopart Res (2010) 12:2415–2426
characterized with a differential scanning calorimeter
(DSC), which is sensitive to the thermal history of the
samples. The first heating and cooling run of the DSC
at a rate of 10 K/min and a nitrogen flow rate of
10 ccpm was used to characterize the thermal prop-
erties of all samples. The heating run was used to
obtain the melting temperature and melting enthalpy,
while the cooling run was used to characterize the
crystallization and fusion energy. The results are
presented in Fig. 5 and summarized in Table 1. The
thermograms show two endothermic peaks. The first
one at lower temperature is due to the melting of the
crystallites of the cross-linked network, and the
second peak in the range of 200–240 °C is attributed
to the melting of the PVA upon recrystallization
(Agrawal and Awadhia 2004). The melting temper-
ature arising from cross-linking decreased from
124 °C (pure PVA) to 88 °C (PVA attached to
nanoparticles fabricated with a ratio of 1:20) and
further down to 80 °C (PVA attached to nanoparticles
fabricated with a ratio of 1:50). This observation
indicates that the presence of the iron oxide nano-
particles prohibits the extent of the cross-linking
during the formation of solid PVA from the aqueous
polymer solution. The melting temperature upon
recrystallization decreased from 227.5 to 224.2 °C
after the PVA powders were processed into a thin
film structure by the aqueous drop casting. The
melting temperature of the PVA increased from 224.2
to 229 °C and 231 °C after it was attached to the iron
J Nanopart Res (2010) 12:2415–2426 2421

Fig. 5 DSC thermograms

of (a) pure PVA thin film,
and PVA attached to iron
oxide nanoparticles
fabricated with a ratio of
iron nitrite to sodium
chloride of (b) 1:20 and
(c)1:50, respectively

Table 1 Thermal properties and calculated crystallinity of pure PVA and bounded PVA
Tm (°C) Tc (°C) DHm (J/g) DHf (J/g) Crystallinity (%)

PVA powder 227.5 198.6 52.43 43.08 37.8

PVA film 224.2 201.7 38.93 41.11 28.1
a
PVA-NPs 229.0 204.6 85.75 49.69 35.8
PVA-NPsb 231.3 191.4 113.3 53.44 38.5
a
PVA on the surface of the nanoparticle surface, fabricated with a ratio of 1:20 (Na:Fe)
b
PVA on the surface of the nanoparticle surface, fabricated with a ratio of 1:50 (Na:Fe)

oxide nanoparticle surface fabricated with a ratio of
iron nitrate to sodium chloride of 1:20 and 1:50,
respectively. This observation is consistent with the
enhanced thermal stability with a higher initial
decomposition temperature (Fig. 5), and it is different
from the PVA in the hydroxyapatite (Hap)–PVA
composite system (Kim et al. 2008).
The melting enthalpy (DHm, based on the weight
of pure polymer rather than the total weight of
polymer nanocomposite) was observed to increase
significantly from 38.93 to 85.75 J/g and 113.3 J/g,
which is consistent with the nanocomposites com-
prised of silver nanoparticles reinforced with PVA
(Mbhele et al. 2003). This is due to the reduced
mobility of the polymer chains after being attached to
the nanoparticle surface. The dramatic difference in
melting temperature between the pure PVA and the
PVA attached to the nanoparticle surface indicates a
strong interaction between the PVA and the iron
oxide nanoparticles. The nanoparticle size was also
observed to have a significant effect on the melting
temperature and the melting enthalpy.
The degree of the relative crystallinity (Xc; Kim
et al. 2008; Peppas and Merrill 1976) of the PVA
attached on the nanoparticle surface was estimated
from the endothermic area (from cooling stage) using
Eq. 3:
DHf
Xc ¼ ð3Þ
DHf0
where DHf is the measured enthalpy of fusion from
the DSC thermogram (based on the weight of the
pure polymer rather than the total weight of the
polymer nanocomposites), and DHf0 is the enthalpy of
fusion of 100% crystalline PVA (DHm is 138.6 J/g;
Peppas and Merrill 1976). The crystallinity of PVA
decreased after the PVA powder was drop-casted into
the thin film structure. However, the crystallinity

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Fig. 6 Magnetic hysteresis
loop (M–H) of iron oxide
nanoparticles fabricated
with ratios of iron nitrate to
sodium chloride (1:50 and
1:20); left inset shows the
enlarged hysteresis loop at
low field, the right inset
shows the magnetization
over H-1 for Ms calculation
increased after PVA physicochemically bonded to the
nanoparticle surface.
Figure 6 shows the magnetic properties of the
nanoparticles fabricated with different ratios of iron
nitrate to sodium chloride. The saturation magneti-
zation (Ms) was not reached even at a high field of 9
Tesla. Ms was determined by the extrapolated satu-
ration magnetization obtained from the intercept of
magnetization versus H-1 at high field (Chen et al.
1994; Guo et al. 2006a). The calculated saturation
magnetization of the nanoparticles fabricated with the
ratio of iron nitrate to sodium chloride (1:50 and
1:20) was 3.3 and 3.0 emu/g, respectively. The
coercivity (coercive force, Hc) is 350 and 300 Oe
for the nanoparticles fabricated with the ratio of iron
nitrate to sodium chloride 1:20 and 1:50, respec-
tively. The difference is due to the particle size effect.
The coercivity is smaller than that (784.5 Oe) of the
a-Fe2O3 nanoparticles dispersed in a polystyrene
matrix (Zhang et al. 1989) and that (2,279.0 Oe) of
the cantaloupe-like Fe2O3 (Zhu et al. 2007). This
could be due to the morphological (shape and size)
difference (Zheng et al. 2007). The saturation mag-
netization (Ms) is much lower than that of c-Fe2O3
(74 emu/g; Guo et al. 2008a), and that of metallic
iron (218 emu/g; Guo et al. 2008b). However, it is
similar to the Ms observed in other nanoparticles with
different morphologies (Zheng et al. 2007; Zhu et al.
2007).
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J Nanopart Res (2010) 12:2415–2426
Polymer nanocomposites
Figure 7 shows the SEM microstructure of the PVA
nanocomposites reinforced with a particle loading of
10 wt%. The nanoparticles were observed to be
uniformly dispersed in the polymer matrix without
obvious agglomeration. No cracks or voids were
evident in the polymer nanocomposites. The high-
resolution SEM image (inset of Fig. 7) shows an
interface between a nanoparticle and the polymer
matrix, which is similar to that observed in nano-
composites of alumina nanoparticles reinforced vinyl
ester resin (Guo et al. 2006b). The fabricated
nanoparticles are surrounded by hydroxyl groups,
which form hydrogen bonding with the PVA, and
thus, lead to void- and crack-free structural polymer
nanocomposites. These strong hydrogen bonds are
responsible for the strong interaction between the
nanoparticles and the polymer matrix.
Figure 8 shows the TGA curves of the pure PVA
and its nanocomposites with a nanoparticle loading of
1, 6, and 10 wt%, respectively. The weight loss at
lower temperature (lower than 100 °C for pure PVA
and 116 °C for PVA reinforced with iron oxide
nanoparticles) is due to the evaporation of adsorbed
moisture. The loss at higher temperature is due to the
dehydration of the hydrogen bonding between the
PVA and the hydroxy groups in the nanoparticles.
The weight loss in the medium temperature range
J Nanopart Res (2010) 12:2415–2426
Fig. 7 SEM microstructures of the polymer nanocomposites
with a particle loading of 10 wt% (the inset shows the high
resolution of SEM)
Fig. 8 TGA curves of pure PVA and PVA nanocomposites
with nanoparticle loading of 1, 6, and 10 wt%, respectively
(120–247 °C) is due to the condensation of the
hydroxyl groups. The sharp weight loss at tempera-
tures higher than 247 °C is due to the thermal
decomposition of the PVA. A plateau in the range of
2423
Fig. 9 XRD patterns of pure (a) PVA and PVA nanocompos-
ites with an iron oxide nanoparticle loading of (b) 1 wt%, (c) 6
wt%, and (d) 10 wt%
C and D was observed in the polymer nanocompos-
ites, which is due to the degradation and carboniza-
tion of the PVA. The formed carbon further reacted
with iron oxide. In other words, the addition of the
iron oxide nanoparticles favors the thermal decom-
position of the PVA. A similar results is observed
with CuO nanoparticles (Guo et al. 2007) and Fe2O3
nanoparticles (Guo et al. 2008a), but different from
Al2O3 nanoparticles (Guo et al. 2006b) reinforced
vinyl ester resin nanocomposites.
Figure 9 shows the XRD patterns of the pure PVA
and its nanocomposites reinforced with different iron
oxide nanoparticle loadings. The peaks at 19.5° and
40.5° were observed in the pure PVA. The first peak
has a d-spacing of 0.454 nm, corresponding to the
typical doublet reflection of the (1, 0, 1) and (1, 0,
-1) planes of the semicrystalline atactic PVA. The
second peak is assigned to the (2, 2, 0) plane of the
PVA (Kim et al. 2008; Ricciardi et al. 2004). The
peak corresponding to the (1, 0, 1) plane of the PVA
becomes narrower and narrower as a function of the
particle loading. This indicates that the crystallite
sizes along the (1, 0, 1) lattice direction, as dictated
by Eq. 2, became larger with the addition of more
iron oxide nanoparticles. This suggests a higher
crystallinity of the PVA, which is in contrast to
hydroxyapatite (Hap) nanoparticles reinforced with
PVA (Kim et al. 2008). The presence of iron oxide
nanoparticles favors the recrystallization of PVA
during the polymer solution solidification process.
Concurrently, the standard Fe2O3 reflection peaks are
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observed, similar to Fig. 2. The difference in XRD
spectra between the iron oxide nanoparticles and the
polymer nanocomposites is evident in Fig. 9. The
iron oxide peak became broader, indicating a uniform
dispersion of nanoparticles, consistent with the SEM
observation (Fig. 8).
In order to investigate the effect of nanoparticle
loading on the thermal properties of the bulk polymer
matrices, such as melting and crystallization (forma-
tion of the crystalline structure), DSC measurements
were run, and the results are presented in Fig. 10 and
summarized in Table 2. The lower melting temper-
ature (123 °C) of the PVA nanocomposites with
1 wt% nanoparticle loading, as compared to the pure
PVA thin film, decreased slightly and then increased
to 161.5 °C for a particle loading of 6 wt% and
151.9 °C for a particle loading of 10 wt%. The higher
melting temperature decreased with the increase in
nanoparticle loading. Similarly, the melting temper-
ature and the melting enthalpy of the PVA matrices
decreased with the increase of the nanoparticle
Fig. 10 DSC thermograms of (a) pure PVA thin film, PVA
nanocomposites with a particle loading of (b) 1 wt%, (c) 6
wt%, and (d) 10 wt% (Exo, up)
Table 2 Thermal properties
Tm (°C)
and calculated crystallinity of
pure PVA and polymer
nanocomposites PVA powder 227.5
Pure PVA film 224.2
1 wt% 227.3
6 wt% 223.6
10 wt% 221.8
123
J Nanopart Res (2010) 12:2415–2426
loading, which is in stark contrast to the results when
the PVA is attached to the nanoparticle surface
(Fig. 5, Table 1). This behavior is similar to what
was observed in nanocomposites comprised of silver
nanoparticles embedded in PVA (Mbhele et al. 2003).
Conclusions
An environmentally benign method was developed to
fabricate iron oxide (a-phase) nanoparticles. Inexpen-
sive sodium chloride effectively serves as a solid
spacer to disperse the salt and prevent the iron oxide
nanoparticles from agglomerating. The nanoparticle
size increased with the increase of the ratio of iron
nitrate to sodium chloride. The presence of PVA in the
solution limits the particle size and favors a more
uniform particle-dispersed polymer nanocomposite
fabrication. Obvious changes of structural phase and
thermal properties, such as low-temperature cross-
linking, high-temperature recrystallization, melting
enthalpy, fusion enthalpy, and crystallinity have been
observed once the PVA was attached to the nanopar-
ticle surface. The presence of the nanoparticles
increased the cross-linking with an increase in the
lower melting temperature. The thermal stability was
enhanced when PVA was attached to the nanoparticle
surface. The nanoparticles fabricated showed that a
coercivity of 350 Oe and a lower saturation magneti-
zation. The nanoparticles were uniformly dispersed in
the polymer matrix as shown in the SEM microstruc-
ture analysis and the XRD pattern variation. SEM
images also indicated an intermediate phase, suggest-
ing a strong interaction between the nanoparticles and
the polymer matrix. In summary, the addition of
nanoparticles favored the cross-linkage of the PVA,
resulting in an increase in the lower temperature
melting point, and thus a subsequent improvement in
the thermal stability of the nanocomposite.
Tc (°C) DHm (J/g) DHf (J/g) Crystallinity
(%)
198.6 52.43 43.08 37.8
201.7 38.93 41.11 28.1
203.0 43.16 44.72 32.3
201.1 31.91 44.55 32.1
193.8 23.53 39.27 28.3
J Nanopart Res (2010) 12:2415–2426
Acknowledgments The project is partially supported by the
start-up grant and research enhancement grant from Lamar
University. The authors kindly acknowledge the support from
Northrop–Grumman Corporation. DPY acknowledges support
from the NSF under Grant No. DMR 04-49022. FT-IR analysis
done by Dr. Y. Mou from Department of Chemistry and
Physics at LU and financial support from the Welch
Foundation (V-1103) are kindly acknowledged.
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