Journal of Wuhan University of Technology-Mater. Sci. Ed. Apr.

2013 215

DOI 10.1007/s11595-013-0667-8

Preparation and Characterization of Hydroxyapatite/

-Fe2O3 Hybrid Nanostructure

SUN Ruixue, CHEN Kezheng*, XU Lei

(College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China)

Abstract: The hybrid particles composed of hydroxyapatite (HAp) and ferrite (γ-Fe2O3) were synthesized
by two-step precipitation method. The effect of reaction temperature on the morphology of the hybrids was
also studied. The resultant hybrids were characterized by transmission electron microscopy (TEM) and X-ray
diffraction analysis(XRD). It was found that γ-Fe2O3 nanoparticles dispersed within the HAp matrix and these
hybrids had a feather-like or spherical morphology when synthesized at 90 ℃ or room temperature, respectively.
The magnetic properties of the hybrid showed good superparamagnetic feature, and they could be controlled by
the external magnetic field.
Key words: hydroxyapatite; γ-Fe2O3; hybrid nanostructure; superparamagnetism

1 Introduction as nanowires, nanoneedles, and nanospheres, have

Hydroxyapatite (Ca 10(PO 4) 6(OH) 2, HAp) is a
well-known biomaterial due to its excellent bioactivity
and biocompatibility, and has been widely used
as bone substitutes and tooth implants in clinical
applications [1-3]. Particular adsorbability for various
ions and organic molecules of HAp nanoparticles
(NPs) makes them good candidates as delivery vehicles
of anticancer drugs as well as growth factors and
enzymes for controlled release[4-7]. Drug release and
catalytic behavior of HAp have been also reported
by many researchers. In these practical applications,
HAp exhibits an obvious drawback, namely
difficulty in targeting and recycling[8]. On the other
hand, magnetic nanopowders of Fe 3O 4 and γ-Fe 2O 3
have been extensively used in targeted delivery of
drugs, magnetic resonance imaging (MRI) reagent,
hyperthermia treatment, and many other fields [9-12].
In recent years, various nanostructures of them, such
©Wuhan University of Technology and SpringerVerlag Berlin Heidelberg 2013
(Received: Feb. 19, 2012; Accepted: Apr. 8, 2012)
SUN Ruixue(孙瑞雪): Assoc.Prof.; E-mail: sunruixue@qust.edu.cn
*Corresponding author:CHEN Kezheng(陈克正): E-mail: kzchen@qust.
edu.cn
Funded by the Project of Shandong Province Higher Educational
Science and Technology Program (No. J09LC13) and the Promotive
Research Fund for Excellent Young and Middle-Aged Scientists of the
Shandong Province (No. BS2010CL018)
been successfully fabricated by many researchers[13,14].
However, pure magnetic nanoparticles are prone
to aggregation and rapid biodegradation when they
are directly exposed to a biological system[11,15]. For
biological applications, magnetic nanoparticles shall
be prepared or loaded with other materials, such as
silica, polymer, and HAp vesicles to enhance their
other desirable properties such as colloid dispersion,
drug loading, and biocompatibility[16]. Among these,
HAp encapsulated ferrite nanoparticle is one of the
most promising materials because of the merits of
these two kinds of materials mentioned above. Webster
and co-workers [17] reported the synthesis of HAp-
coated Fe3O4 nanoparticles by using a wet chemical
method. The Fe3O4 nanoparticles were embedded in
the rod-shaped HAp particles with the average size
of 170 nm. Wakiya et al[18] reported the synthesis of
HAp-ferrite composite particles by the combination
of co-precipitation and ultrasonic spray pyrolysis.
The composite particles have round shape with some
dimples with the average particle size of around 1.8
m. Xia et al[19] prepared HAp coated ultrafine and
uniform γ-Fe2O3 core-shell particles by co-precipitation
method for selective oxidation of alkene with H2O2 in
the presence of acetonitrile. Liu et al[8] prepared Fe3O4/
HAp nanoparticles with magnetism and photocatalytic
property by homogeneous precipitation. These particles
are almost spherical in shape with well-defined core-
shell structure, rather monodisperse and have a unique
216 Vol.28 No.2 SUN Ruixue et al: Preparation and Characterization of Hydroxyapatite/γ-Fe2...
size of about 25 nm in diameter. Heydari et al [20]
prepared hydroxyapatite-encapsulated-γ-Fe2O3 by the
same method as reference[8], and studied its potential
application in the formylation of amines and amine
derivatives.
In this work, HAp/γ-Fe2O3 hybrid particles with
two different morphologies were synthesized by two-
step precipitation synethsis. First step was to synthesize
γ-Fe2O3 nanoparticles by coprecipitation method, and
second step was the synthesis of HAp/γ-Fe2O3 hybrid
particles by wet chemical precipitation method. These
magnetic apatite nanoparticles can be employed as
reusable catalysts as well as targeted delivery vehicles
of drugs.
2 Experimental
2.1 Materials
Diammonium hydrogen phosphate [(NH4)2HPO4]
and calcium nitrate tetrahydrate [Ca(NO3)2•4H2O] were
supplied by Sinopharm Chemical Reagent Corporation
(Shanghai, China). Iron (Ⅱ) sulfate heptahydrate
(FeSO 4•7H 2O), ferric chloride (FeCl 3•6H 2O), and
sodium hydroxide (NaOH) were purchased from
Shanghai Chemical Corporation (Shanghai, China).
All the reagents were of analytical grade. All glassware
used were cleaned with acetone, followed by copious
rinsing with deionized water under ultrasonication
before drying in an oven at 120 ℃.
2.2 Synthesis of -Fe2O3 nanoparticles
The aqueous γ-Fe2O3 suspension was synthesized
by precipitation from iron chlorides. Briefly, the Fe3O4
precipitate was firstly obtained by alkalinization of the
FeCl3 and FeSO4 (Fe2+/Fe3+ = 1/2) aqueous mixture.
Then, it was successively oxidized with 1 M HNO3 (50
mL) and 0.17 M Fe(NO 3)3•9H2O solutions (50 mL)
at 100 ℃. The brown dispersion was washed with a
0.5 M HNO3 solution for four times. After that, 0.1
M sodium citrate (15 mL) was added into the brown
precipitate at 90 ℃ under vigorous stirring for 15
mins in order to make the prepared particles disperse
steadily in water through surface modification. N2 was
bubbled throughout the reaction. The final precipitate
product was washed with acetone for several times, and
dispersed in water for use.
2 . 3 S y n t h e s i s o f H A p /  - F e 2O 3 h y b r i d
nanostructure
The hybrid nanoparticles of HAp/γ-Fe2O3 were
prepared by a well-established wet chemical process.
Briefly, a 0.5 M Ca(NO3)2•4H2O solution was added
dropwise to a 0.3 M (NH4)2HPO4 solution containing
the prepared iron oxide nanoparticles whose pH was
adjusted to 11. The reaction was conducted at room
temperature or at 90 ℃ in water bath with vigorous
mechanical stirring. After 2 h, the mixture was cooled
to room temperature and aged overnight. The resultant
brown hybrid were separated magnetically and washed
with deionized water and ethanol several times.
2.4 Characterization
X-ray diffraction (XRD) studies were conducted
on a Rigaku D/max-2500 X-ray powder diffractometer
using Cu K radiation ( = 1.5406 Å), with a scan
speed of 4°/min between 10 and 70° (2θ angle),
operated at 40 kV and 100 mA. The morphologies
of the products were examined in a field-emission
scanning electron microscope (FESEM, JEOL JSM-
6700F) and a transmission electron microscope
(TEM, JEOL JSM-2000EX). The samples were
ultrasonically dispersed before the analysis. The
particle size distribution and mean particle size were
measured using the dynamic light scattering (DLS)
by a nanoparticle size analyzer (Nano ZS, Malvern)
and distilled water was employed as the dispersion
medium. The magnetic properties were measured on a
superconducting quantum interference device (SQUID)
magnetometer (Quantum Design, MPMS XL-5) at 300
K.
3 Results and discussion
The crystalline phase of HAp/γ-Fe 2O 3 hybrid
nanoparticles prepared at 90 ℃, together with that of
the original HAp as reference sample were examined
by the XRD as shown in Fig.1. It indicates that
predominant phase of the resultant hybrid nanoparticles
is HAp, and small amount of ferrite is also found
(Fig.1(b)). The peaks marked by triangles (at around
30.2°, 35.6°and 57.3°) can be indexed as γ-Fe 2O 3
 Journal of Wuhan University of Technology-Mater. Sci. Ed.
(JCPDS No. 39-1346). Other iron oxide phases are
apparently not involved. The XRD result reveals the
coexistence of the γ-Fe2O3 phase and HAp phase in
the hybrid products. The relative low crystallinity of
the products is due to the low temperature used in the
whole process of preparation.
T E M i m a g e o f t h e a s p r e p a r e d γ - F e 2O 3
nanoparticles is shown in Fig.2. It can be seen that
the prepared γ-Fe2O3 has a spherical-like morphology
with a diameter of 10-20 nm. Figs.3(a) and 3(b) show
Apr.2013 217
TEM images with different magnification of the hybrid
HAp/γ-Fe2O3 prepared at 90 ℃ in water bath. The as-
synthesized hybrid HAp/γ-Fe2O3 has a special spindle-
shaped morphology, with a long axis of about 500
nm and a short axis of about 100 nm. Interestingly,
the hybrid HAp/γ-Fe2O3 also has a loosen feather-like
structure after magnification as shown in Fig.3(b). In
fact, it is an oriented array of bundled nanosheets with
about 20 nm in width, which can be further identified
by SEM observations in Fig.4. γ-Fe2O3 nanoparticles
are not observed in the TEM image, which is possibly
due to the smaller size of the nanocrystallites. In
Fig.4(b), some spherical particles of about 10 nm are
found dispersed between the nanosheets, probably
magnetic nanoparticles of γ-Fe2O3. The EDS spectrum
(Fig.4(c)) of HAp/γ-Fe 2 O 3 hybrids confirms the
presence of calcium (Ca), phosphor (P), oxygen (O),
and ferrum (Fe) in the HAp/γ-Fe 2O 3 sample. Fig.5
shows the particle size distribution curve of the HAp/
γ-Fe2O3 hybrids by DLS. The mean particle size of
the HAp/γ-Fe2O3 hybrids is about 600 nm, which is
corresponded to the TEM results.
In order to test whether this growth mode of HAp
is related to the addition of magnetic nanoparticles, we
also conducted the same experiment without γ-Fe2O3.
TEM images (Fig.6) demonstrate the same spindle-
shaped morphology of HAp, however, the structure
of the single HAp is not so loose as the HAp/γ-Fe2O3
composite with feather-like structure, and the size of
218 Vol.28 No.2 SUN Ruixue et al: Preparation and Characterization of Hydroxyapatite/γ-Fe2...
HAP is smaller than that of HAp/γ-Fe2O3 hybrids.
For comparison, the same experiments with
and without γ-Fe 2 O 3 were also repeated at room
temperature. It can be seen from Fig.7 that the HAp/
γ-Fe2O3 and single HAp prepared at room temperature
both have spherical morphology with the particle size
of 60-80 nm and 30-40 nm, respectively. Moreover,
some small spherical particles of about 10 nm dispersed
between large nanospheres can be seen in Fig.7(a),
which may be the γ-Fe2O3 nanoparticles.
As well recognized, HAp can be fabricated
to different morphologies, such as nanospheres,
nanorods, and nanofibers by using organic surfactant
as soft template[9,21]. However, no organic template
was added in our experiment. Many researches have
shown that the unstable amorphous calcium phosphates
(ACP) forms rapidly in the initial stage of the
reaction. Then, ACP will transform into HAp, a more
thermodynamically stable phase. At high temperature,
HAp will grow along its c direction and thus has a one-
dimensional morphology such as nano needles and
nano sheets. While at room temperature, HAp will
grow isotropically and has a spherical morphology.
At the same time, γ-Fe 2 O 3 nanoparticles will be
encapsulated into HAp matrix.
The magnetic properties of as-prepared HAp/
γ-Fe2O3 hybrid nanostructure were investigated using
a SQUID magnetometer at 300 K. As shown in Fig.8,
the isothermal magnetization curves of the HAp/
γ-Fe2O3 display a rapid increase with increasing applied
magnetic field due to superparamagnetic relaxation.
Hysteresis is absent with zero remanence and coercivity,
and the satruation magnetization (Ms) reached up to 2.6
emu・g1 for the HAp/γ-Fe2O3 hybrids with spherical
morophology, which is smaller than the theoretical Ms
for bulk γ-Fe2O3 at room temperature. This difference
can be explained by the defined size effects responsible
for the degradation of magnetic properties in iron oxide
nanoparticles [22]. Fig.8b shows a photograph of an
aqueous dispersion of the HAp/γ-Fe2O3 and illustrates
the magnetic manipulation ability. When an external
magnetic field is placed by the side of the glass vial,
the composite nanoparticles can be directed near to the
magnet (Fig.8(c)). These magnetic properties of HAp/
γ-Fe2O3 suggest its potential applications for targeting
and separation.
4 Conclusions
I n c o n c l u s i o n , t h e H A p / γ - F e 2O 3 h y b r i d
nanostructure with feather-like and spherical
morphology were fabricated through a simple method
without any organic template. The analyses of SEM
and XRD revealed that the obtained nanoparticles
were composed of γ-Fe 2 O 3 and HAp. These two
kinds of HAp/γ-Fe 2O 3 hybrids both exhibit good
superparamagnetic property. These magnetic apatite
nanoparticles can be employed as reusable catalysts as
well as targeted delivery vehicles of drugs.
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