Scripta Materialia 57 (2007) 441–444

[Link]/locate/scriptamat

Microwave-assisted combustion synthesis of

CoFe2O4 with urea, and its magnetic characterization
N. Kasapoğlu,a A. Baykal,a,* Y. Köseoğlub and M.S. Toprakc
a
Department of Chemistry, Fatih University, [Link], 34500 Istanbul, Turkey
b
Department of Physics, Fatih University, [Link], 34500 Istanbul, Turkey
c
Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106, USA
Received 21 February 2007; revised 13 April 2007; accepted 23 April 2007
Available online 7 June 2007

A microwave-assisted combustion method has been utilized to prepare nanophased powders of CoFe2O4 using urea as fuel. The
process takes only a few minutes to obtain as-received CoFe2O4. Structural and magnetic properties of the products were investi-
gated by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetom-
etry. Magnetization measurements showed that, at the lowest temperature investigated, the coercivity of Co–ferrite is much larger
than that of bulk and this is attributed to exchange anisotropy due to spin disorder at the particle surface.
Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Annealing; SEM; X-ray diffraction (XRD); Nanocrystalline materials; Coercivity

Recently metal–oxide nanoparticles have been the as fuel. An appropriate ratio of analytical-grade nickel
subject of much interest because of their unusual optical, nitrate (Ni(NO3)2 Æ 6H2O), ferric nitrate (Fe(NO3)3 Æ
electronic and magnetic properties, which often differ 9H2O) and cobalt nitrate (Co(NO3)2 Æ 6H2O), plus urea
from the bulk. Cobalt ferrite (CoFe2O4) is a well-known (CO(NH2)2), to serve as fuel, was dissolved in deionized
hard magnetic material with high coercivity and moder- water and poured into a crucible, which was then placed
ate magnetization. These properties, along with their in a microwave oven. The solution initially boils then
great physical and chemical stability, make CoFe2O4 undergoes dehydration followed by decomposition with
nanoparticles suitable for magnetic recording applica- the evolution of large amounts of gas. After the solution
tions such as audio and videotape and high-density dig- reaches the point of spontaneous combustion, it begins
ital recording disks, etc. [1,2]. burning and releases lots of heat, vaporizes all the solu-
The technological importance of CoFe2O4 has moti- tion instantly and becomes a solid, burning at a temper-
vated several studies on the synthesis as well as the phys- ature of over 1000 °C. The entire combustion process
ical properties of this material. The magnetic properties takes only 15 min to produce ferrite powders in a micro-
of CoFe2O4 have been studied using methods such as wave oven. The product was dried at 100 °C before
combustion [3], mechano-chemical [4]; in addition, the Fourier transform infrared spectroscopy (FTIR) mea-
variation in the magnetic properties of nanocrystalline surements.
CoFe2O4 powders as a function of particle size has been X-ray powder diffraction analysis was conducted on a
investigated by co-precipitation, citrate precursor and Huber JSO-Debyeflex 1001 diffractometer using Cu Ka
polymerized complex methods [5–7]. (operated at 40 kV and 35 mA). FTIR transmission
In this study, we present the synthesis of CoFe2O4 spectra were taken on a Mattson Satellite infrared
nanoparticles by a microwave-assisted combustion spectrometer from 4000 to 400 cm1. Room tempera-
method with urea as a fuel. ture magnetic measurements were carried out with the
This study is the first report of the synthesis of Co- Quantum Design Model 6000 vibrating sample magne-
Fe2O4 via microwave-assisted combustion using urea tometry (VSM) option for the physical property mea-
surement system (PPMS) and parameters such as
specific saturation magnetization (Ms), coercive force
* Corresponding author. Tel.: +90 212 866 3300/2061; fax: +90 212 (Hc) and remanence (Mr) were evaluated. An FEI
866 3402; e-mail: hbaykal@[Link] XL40 Sirion FEG digital scanning microscope was used

1359-6462/$ - see front matter Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/[Link].2007.04.042
442 N. Kasapoğlu et al. / Scripta Materialia 57 (2007) 441–444

to investigate the microstructure and morphology of the

sample. Samples were coated with gold at 10 mA for
2 min prior to scanning electron microscopy analysis.
Microwave processing of materials differs fundamen-
tally from conventional processing in terms of its heat

Intensity (a.u.)
mechanism. In a microwave oven, heat is generated
within the sample itself by the interaction of microwaves
with the material. In conventional heating, heat is gener-
ated by heating elements and then transferred to the
sample surfaces [8,9]. The expected combustion reaction
of metal nitrates with urea to form CoFe2O4 is as
follows: 583

Co(NO3 )2 +2 Fe(NO3 )3 +6.67 CO(NH2 )2 4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
! CoFe2 O4 +6.67 CO2 +10.67 N2 +13.34 H2 O
Figure 2. FTIR spectra of CoFe2O4, synthesized by microwave-
The evolution of large amounts of gases during the assisted combustion method with urea annealed at 300 °C.
thermal decomposition (H2O, CO2, NH3, HNCO and
NOx) helps to dissipate the heat, thereby preventing
the oxides sintering [10]. 600–550 cm1, corresponds to intrinsic stretching vibra-
In this study, urea is used as a precipitating/reducing tions of the metal at the tetrahedral site, Mtetra M O,
agent to promote a uniform base condition that avoids whereas the lowest band, m2, usually observed in the
localized precipitation and thereby which gives a wide range 450–385 cm1, is assigned to octahedral metal
particle size distribution. The decomposition reaction stretching, Mocta M O [16,17]. It is known that Ni2+ ions
is a function of temperature and is expressed as follows have octahedral-site preference, while Co2+ and Fe3+
[11,12]: ions can occupy both octahedral and tetrahedral sites
ðH2 NÞ2 CO þ 3 H2 O ! CO2 þ 2 OH þ 2 NHþ [18]. However, no clear peak due to octahedrally coordi-
4
nated metal ions has been observed, which is expected to
The X-ray diffraction patterns of the prepared be below 400 cm1. This may be due to the broadening
CoFe2O4 (Fig. 1) show reflection planes (1 1 1), (2 2 0), of this peak attributed to very small particles of spinel
(3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1) and (4 4 0), which indi- ferrites [19].
cate the presence of the spinel cubic structure [13]. The The scanning electron micrograph of CoFe2O4
lattice parameter was computed using the d-spacing val- (Fig. 3) shows that the sample has a large grain struc-
ues and the respective (h k l) parameters. The value of the ture, about 400 nm in size. Heating has resulted in
lattice parameter, a = 8.381 Å, agrees with that reported sintering of the well-faceted grains to form solid bodies.
in JCPDS Card No. 22-1086. The average crystallite There are also very small particles that did not differ
diameter, L, was estimated by Scherrer’s equation, chemically from the surrounding particles. It is a very
L = 0.9k/b cos hB, from the full-width at half maximum porous network of sintered bodies. The scanning elec-
(FWHM) of the most intense peak (3 1 1) [14,15]. The re- tron micrograph reveals a porous network, more like a
sult shows that the particle size of CoFe2O4 is around foam. The surface of the powders shows pores formed
66 nm. by the escaping gases during the combustion reaction.
Two main broad metal–oxygen bands are seen in the This type of porous network is typical of combustion-
IR spectra of all spinels, and ferrites in particular. The synthesized powders [20]. The porous powders are
highest one, m1 (Fig. 2), generally observed in the range highly friable, which facilitate easy grinding to obtain fi-
ner particles [21]. There are large pores, several micron
across, as well as smaller pores of around 20–40 nm.
(311)

(440)
Intenstiy (a.u.)

(511)
(220)

(400)
(111)

(422)
(222)

20 40 60
2θ

Figure 1. XRD patterns of CoFe2O4, synthesized by microwave- Figure 3. SEM micrographs of CoFe2O4, synthesized by microwave-
assisted combustion method with urea. assisted combustion method with urea annealed at 300 °C.
 N. Kasapoğlu et al. / Scripta Materialia 57 (2007) 441–444 443

Sintering has apparently taken place; however, individ- 18000

ual particles of the order of 60 nm are clearly ob- 16000
served. 14000

Coercive field, Hc (Oe)

Figure 4 shows the magnetization loops of the Co- 12000
Fe2O4 at various selected temperatures. From Figure
10000
4, it can be seen that, at room temperature, the sample
8000
has a coercivity (Hc) of 629 Oe. As the temperature de-
6000
creases, the coercivity of the sample increases, and to a
maximum of 17,145 Oe at the lowest temperature. While 4000

the room temperature coercivity of CoFe2O4 nanoparti- 2000

cles is less than that of bulk material, the coercivity at 0

the lowest temperature is much larger than that of bulk 0 50 100 150 200 250 300 350
[22]. The coercivity (Hc) of a magnetic material is gener- Temperature (K)

ally a measure of its magnetocrystalline anisotropy [23]. Figure 5. Temperature dependence of coercive field for CoFe2O4
However, the dramatic increase in low-temperature nanoparticles synthesized by microwave-assisted combustion method.
coercivity cannot be attributed only to magnetocrystal-
line anisotropy. It seems to originate from exchange
anisotropy due to spin disorder at the particle surface
1.1
at low temperatures. This effect is expected to be larger
for smaller particles due to the increase in the surface-to- 1.0

volume ratio as occurred in the present case. 0.9

Figure 5 shows that the coercive field of the sample
0.8
increases as the temperature is lowered. While the coer-
cive force is less at high temperatures, it reaches very Mr/Ms
0.7

high values at the lowest temperature. Since CoFe2O4 0.6

usually forms an inverse spinel structure and has very
high anisotropy energy constants, K1 and K2, and is sen- 0.5

sitive to temperature in the lower temperature region, 0.4

the increase in the coercive field of CoFe2O4 is much
0.3
greater. The large values of the coercive field is associ- 0 50 100 150 200 250 300 350

ated with the increase in the effective anisotropy field Temperature (K)

(Keff), where Keff = 4pMsHirr. This can be attributed Figure 6. Variation of normalized magnetization (Mr/Ms) with
due to random freezing of nanoparticles in locally temperature.
canted states, for which the random anisotropy energy
will act as a pinning potential [24].
Figure 6 shows the variation with temperature of the
normalized magnetization (Mr/Ms). As can seen from Changes in the magnetic properties, i.e. Ms, Hc, Mr,
the figure, the magnetization of the sample decreases are due to the formation of a dead layer on the surface,
with the temperature. In the cubic system of ferrimag- the existence of random canting of particle surface spins,
netic spinels, the magnetic order is mainly due to a non-saturation effects due to random distributions of
super-exchange interaction mechanism occurring be- particle size, deviation from the normal cation distribu-
tween the metal ions in the A and B sublattices. tion, presence of adsorbed water, etc. All these factors
may reduce the magnetic properties of nanoparticles.
The deviation of cation distribution in nanoparticles
from the bulk influences the temperature dependence
of magnetization [25].
1.0 In conclusion, using cobalt nitrate, ferric nitrate and
urea as the starting materials, fine CoFe2O4 powder
has been successfully synthesized by a microwave-as-
0.5 sisted combustion process. Both X-ray diffraction and
FTIR spectroscopy confirm the formation of a spinel
phase. The considerable broadening as well as the low
M/Ms

0.0
intensity of all diffraction peaks indicate that the studied
samples consist of quite small crystallites. There are no
305 K
-0.5 200 K detectable traces of extra-crystalline phases. The materi-
120 K als prepared by this microwave-assisted combustion
60 K method are porous powders with a particle size of
-1.0 9K 66 nm and have a very large surface area.
Magnetic measurements have shown that the coerciv-
-40000 -30000 -20000 -10000 0 10000 20000 30000 40000 ity of CoFe2O4 nanoparticles increases drastically at low
Magnetic field (Oe)
temperatures. The lowest temperature coercivity of
Figure 4. Temperature dependence of hysteresis of CoFe2O4 synthe- the CoFe2O4 is much larger than that of bulk and this
sized by microwave-assisted combustion method. is attributed to the exchange anisotropy due to spin
444 N. Kasapoğlu et al. / Scripta Materialia 57 (2007) 441–444

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