Pergamon Materials Research Bulletin 36 (2001) 1369 –1377

Synthesis of nickel ferrite nanoparticles by sol-gel method

Dong-Hwang Chen*, Xin-Rong He
Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan 701, R.O.C.

(Refereed)
Received 13 November 2000; accepted 6 February 2001

Abstract
NiFe2O4 nanoparticles were prepared by the sol-gel method using polyacrylic acid (PAA) as a
chelating agent. It was shown that pure spinel NiFe2O4 nanoparticles with a diameter of 5⬃30 nm and
a specific surface area of 20.0⬃55.2 m2/g could be produced by calcining the gel precursors with
various molar ratios of PAA to total metal ions (0.5⬃2.0) in air at 300°C for 2h. As the molar ratio
of PAA to total metal ions increased, particle sizes decreased but the crystallinity increased, revealing
PAA not only worked as a chelating agent to disperse the cations homogeneously but also contributed
its combustion heat to increase the crystallinity of NiFe2O4 nanoparticles. Moreover, the magnetic
analysis showed the resultant NiFe2O4 nanoparticles might be superparamagnetic. Their saturation
magnetization (0.19 emu/mol at 298 K) was slightly lower than that for bulk materials due to small
size and increased slightly with decreasing the temperature below 360 K © 2001 Elsevier Science Ltd.
All rights reserved.

1. Introduction

Nanostructured materials exhibit unusual physical and chemical properties, significantly

different from those of conventional bulk materials, due to their extremely small size or large
specific surface area [1–3]. So, their preparation and characterization have attracted increas-
ing attention in the past decade.
Nickel ferrite (NiFe2O4) is a well-known spinel magnetic material. Its preparation by the
classical solid-state reactions requires a high calcination temperature and hence induces the
sintering and aggregation of particles [4]. To produce nanosized ferrite particles, some

* Corresponding author. Tel.: ⫹886-6-2757575 Ext.62680; fax: ⫹886-6-2344496.

E-mail address: chendh@mail.ncku.edu.tw (D.H. Chen).

0025-5408/01/$ – see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 2 5 - 5 4 0 8 ( 0 1 ) 0 0 6 2 0 - 1
1370 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377

techniques such as chemical coprecipitation [5], hydrothermal synthesis [6], hydrolysis of

metal carboxylate in organic solvent [7], and aerosolization [8] have been developed.
The sol-gel method is a useful and attractive technique for the preparation of nanosized
particles because of its advantages: good stoichiometric control and the production of
ultrafine particles with a narrow size distribution in a relatively short processing time at lower
temperatures. Recently, the use of polyacrylic acid (PAA) as a chelating agent in the sol-gel
syntheses of LiCoO2 and LiMn2O4 nanoparticles has been reported [9,10]. Compared with
citric acid, which is the conventional chelating agent, PAA has more carboxylic acid groups
to form chelates with mixed cations and results in a sol. It also greatly aids in the formation
of a cross-linked gel which may provide more homogeneous mixing of the cations and less
tendency for segregation during calcination.
In this work, NiFe2O4 nanoparticles were synthesized by the sol-gel method using PAA
as a chelating agent. The effects of PAA quantity and calcination temperature were inves-
tigated. The thermal decomposition behavior of gel precursor was examined, and the
structure, size, specific surface area, and magnetic properties of the resultant nanoparticles
were characterized.

2. Experimental

For the typical experimental procedures to prepare spinel NiFe2O4 nanoparticles, an

aqueous solution containing nickel nitrate (0.4M) and ferric nitrate (0.8M) was prepared first,
and then completely mixed with an aqueous solution of PAA. Phase separation was ob-
served. With constant stirring, an appropriate amount of nitric acid was slowly added to this
solution until a transparent green solution (pH 1⬃3) was obtained. The resulting solution was
evaporated at about 50°C until a transparent sol was formed. Then, the transparent sol was
heated at 50°C for 10 h to further remove water. The sol turned into a viscous brown gel. The
gels were prepared with different molar ratios of PAA to the total metal ions (0.5, 1.0, 1.5,
and 2). Finally, the gels were calcined in air at 300 or 400°C for 2 h with a heating rate of
5°C/min to eliminate organic content and obtain spinel NiFe2O4 nanoparticles.
The thermal decomposition behavior of the gels was examined by means of thermo-
gravimetry (TG) and differential thermal analysis (DTA) in air with a heating rate of
10°C/min on the Shimadzu TA-50WSI TGA and DTA instruments, respectively. The
crystalline phases of the calcined particles were identified by powder X-ray diffraction
(XRD) on a Rigaku D/max III. V X-ray diffractometer using Cu-K␣ radiation (␭ ⫽ 0.1542
nm). The size of NiFe2O4 nanoparticles was determined by TEM using a JEOL JEM-200CX
Transmission Electron Microscope. The sample was ultrasonically dispersed in ethanol for
several minutes prior to depositing onto a Formvar-covered copper grid. The specific surface
area of NiFe2O4 nanoparticles was determined by the BET method with nitrogen adsorption
using the Surface Area Analyzer (ASAP-2010, Micromeritics). The magnetic measurement
for NiFe2O4 nanoparticles was carried out using a SQUID magnetometer (MPMS7, Quan-
tum Design).
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Fig. 1. Thermalgravimetric and differential thermal analyses of the gel. The molar ratio of PAA to the total metal
ions was 1.0.

3. Results

A typical TGA and DTA curve for the gel with molar ratio PAA-total metal ions equal to
1.0 is shown in Fig. 1. The TGA curve exhibits three distinct weight loss steps and the DTA
curve shows one endothermic peak and two exothermic peaks. The first weight loss step in
the temperature range of 25⬃150°C, which was accompanied by an endothermic peak
around 100°C in the DTA curve, is due to the loss of residual water in the gel. The second
weight loss step in the temperature range of 150⬃230°C corresponds to the decomposition
of acetates [10,11], and the exothermic peak at 230°C in the DTA curve is presumed to be
associated with the crystallization of spinel NiFe2O4 phase. The sharp weight loss in the
narrow temperature range of 245⬃250°C and the broad exothermic peak around 300°C in the
DTA curve is considered as a result of the combustion of PAA in the gel, because the gel is
self-burning if once ignited. Almost no weight loss was observed above 250°C, implying the
presence of only NiFe2O4 in this temperature range. This pyrolysis behavior was similar to
the cases for LiCoO2 and LiMn2O4 [9,10] and was supported by the observation that the
sharp weight loss increased with the increase in the molar ratio of PAA to total metal ions.
1372 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377

Fig. 2. X-ray diffraction patterns for the particles calcined at 300°C (A) and 400°C (B). The molar ratio of PAA
to total metal ions ⫽ 0.5 (a), 1.0 (b), 1.5 (c), 2.0 (d).

Fig. 2 shows both the XRD patterns for the particles calcined at 300 and 400°C with
various molar ratios of PAA to total metal ions. Except when the molar ratio of PAA to total
metal ions was 0.5, the XRD pattern for each case showed all the characteristic peaks for a
pure crystalline phase of nickel ferrite spinel, marked by their indices. When the molar ratio
of PAA to total metal ions was 0.5, a few impurity peaks were observed. In addition, it could
be seen that the peaks became broader when the molar ratio of PAA to total metal ions
increased. This phenomenon was not resulted from lower crystallinity or amorphous struc-
ture. It implied the formation of smaller particles as usually observed for nanoparticles.
The transmission electron micrographs of the resultant NiFe2O4 nanoparticles calcined at
300°C at various molar ratios of PAA to total metal ions are indicated in Fig. 3. It was
observed that, with the increase in the molar ratios of PAA to total metal ions, the
crystallinity of particles increased but the size and agglomeration of particles were reduced.
 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377 1373

Fig. 3. Transmission electron micrographs of the NiFe2O nanoparticles calcined at 300°C. The molar ratio of
PAA to total metal ions ⫽ 0.5 (a), 1.0 (b), 1.5 (c), 2.0 (d).

When the molar ratios of PAA to total metal ions were 1.0, 1.5, and 2.0, the particle
diameters were 20⬃30 nm, 15⬃25 nm, and 7⬃10 nm, respectively. When the molar ratio of
PAA to total metal ions was 0.5, the particle diameter was not estimated due to serious
particle agglomeration. The specific surface areas for the particles were 20.0, 30.2, and 55.2
1374 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377

Fig. 4. Transmission electron micrographs of the NiFe2O4 nanoparticles calcined at 400°C. The molar ratio of
PAA to total metal ions ⫽ 0.5 (a), 1.0 (b), 1.5 (c), 2.0 (d).

m2/g when the molar ratios of PAA to total metal ions were 0.5, 1.0, and 2.0, respectively.
The increase in the specific surface area was mainly due to the reduction in particle size.
While being calcined at 400°C, the transmission electron micrographs of the resultant
NiFe2O4 nanoparticles are shown in Fig. 4. Except when the molar ratio of PAA to total
 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377 1375

Fig. 5. The plot of magnetization versus magnetic field for NiFe2O4 nanoparticles at 25°C and the temperature
dependence of magnetization at 10 kG. (The molar ratio of PAA to total metal ions for the gel precursor was 2.0
and the calcinaion temperature was 300°C).

metal ions was 0.5, the crystallinity and diameters (5⬃20 nm) of particles were similar and
there was little particle agglomeration. Compared with Fig. 3, the calcination at 400°C did
not result in the significant increases in the size and sintering of particles.
Fig. 5 shows the plot of magnetization versus magnetic field (M-H loop) at 25°C for the
typical spinel NiFe2O4 nanoparticles (calcined at 300°C and the molar ratio of PAA to total
metal ions for gel was 2.0). From the plot of M vs. H and their enlargement near the origin
as shown in the inset (a) in Fig. 5, the saturation magnetization (Ms), remanent magnetization
(Mr), coercivity (Hc), and squareness (Sr ⫽ Mr/Ms) were estimated to be 0.19 emu/mol,
0.0055 emu/mol, 31.7 Oe, and 0.029, respectively. In addition, the inset (b) in Fig. 5 shows
that the magnetization increased slightly with the decrease of temperature at 5⬃360 K at an
applied field of 10 kG.

4. Discussion

The XRD analysis revealed that the synthesis of pure spinel NiFe2O4 could be achieved
at a calcination temperature of 300°C, lower than the conventional solid-state reaction [4],
by this preparation method. It is interesting and notable that, with increasing the molar ratio
of PAA to total metal ions, the increased heat generated from the combustion of PAA did not
result in the increase in the size of NiFe2O4 particles or the reduction in their specific surface
area via the sintering of particles. This could be explained as follows.
When less PAA was used, the distance between Ni-Fe cations was shorter. This led to a
higher probability for the contact between cations and the growth of particles. Therefore,
bigger particles with a low specific surface area were produced at lower PAA quantity. When
1376 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377

PAA was increased, the cross-linked gel suppressed the mobility and contact of cations
effectively, leading to the formation of smaller particles with a large specific surface area.
Furthermore, the crystallinity of particles increased with increasing the molar ratio of PAA
to total metal ions. Also, the spinel NiFe2O4 might be formed around 230°C and the PAA
in the gel was combusted almost completely around 250°C. Therefore, the combustion heat
from PAA which corresponds to the exothermic peak around 300°C might be used to
increase the crystallinity of NiFe2O4 particles. Similar phenomenon was also observed in the
synthesis of LiMn2O4 [10]. Thus, it could be concluded that PAA not only worked as a
chelating agent to disperse homogeneously the cations but also contributed its combustion
heat to increase the crystallinity of NiFe2O4 nanoparticles.
When the calcination temperature was elevated to 400°C, no significant increases in the
size and sintering of NiFe2O4 particles were observed. This result revealed that the additional
heat supplied by the increase of calcination temperature might also be used to increase the
crystallinity of particles because PAA in the gel should be combusted completely around
250°C. The increase in the crystallinity of particles was helpful in the reduction in the
particle agglomeration, as observed in the case when the molar ratio of PAA to total metal
ions was 1.0.
The Ms value was slightly lower (0.19 emu/mol) than that for bulk materials (0.21
emu/mol [4,7]). The reduction in Ms might be due to the decrease in particle size and the
accompanied increase in surface area. It is known that the energy of a magnetic particle in
an external field is proportional to its size via the number of magnetic molecules in a single
magnetic domain. When this energy becomes comparable to thermal energy, thermal fluc-
tuations will significantly reduce the total magnetic moment at a given field [12]. As revealed
from the temperature dependence, the increase in the magnetization with the decrease in
temperature was also due to the decrease in thermal energy. In addition, it is known that a
spin-canting phenomenon can be induced near the surface by the thermal gradient between
surface and bulk [13,14]. This phenomenon is more significant for the nanoparticles due to
their large surface-to-volume ratio. Therefore, it is reasonable that the magnetization of
nanoparticles is usually smaller than that of the corresponding bulk materials. Another
possible reason for the diminution in Ms might be the incomplete crystallization of NiFe2O4
particles, which led to amorphous impurities undetectable by XRD. However, this reason
should not be the main one. Furthermore, the quite small Mr and Hc values revealed no
significant hysteresis was present. This could be explained by the fact that the particles were
so small that they might be superparamagnetic.

5. Conclusions

Spinel NiFe2O4 nanoparticles have been synthesized by the sol-gel method using PAA as
a chelating agent. Compared with the conventional method, this process showed good
stoichiometric control and allowed the production of spinel NiFe2O4 powders at a relatively
low temperature. By varying the PAA quantity and calcination temperature, the size, specific
surface area, and crystallinity of NiFe2O4 nanoparticles could be controlled. It was also
 D.H. Chen, X.R. He / Materials Research Bulletin 36 (2001) 1369 –1377 1377

shown that the resultant NiFe2O4 nanoparticles might be superparamagnetic, reflecting the
nature of nanoparticles.

Acknowledgments

This work was performed under the auspices of the National Science Council of the
Republic of China, under contract number NSC 88-2214-E006-017, to which the authors
wish to express their thanks.

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