Nanoscale

PAPER

Novel microwave assisted chemical synthesis of

Nd2Fe14B hard magnetic nanoparticles
Cite this: Nanoscale, 2013, 5, 2718

Viswanathan Swaminathan, Pratap Kumar Deheri, Shekhar Dnyaneswar Bhame

and Raju Vijayaraghavan Ramanujan*

Received 23rd October 2012
Accepted 25th January 2013
DOI: 10.1039/c3nr33296a
www.rsc.org/nanoscale
The high coercivity and excellent energy product of Nd2Fe14B hard magnets have led to a large number of
high value added industrial applications. Chemical synthesis of Nd2Fe14B nanoparticles is challenging due
to the large reduction potential of Nd3+ and the high tendency for Nd2Fe14B oxidation. We report the
novel synthesis of Nd2Fe14B nanoparticles by a microwave assisted combustion process. The process
consisted of Nd–Fe–B mixed oxide preparation by microwave assisted combustion, followed by the
reduction of the mixed oxide by CaH2. This combustion process is fast, energy efficient and offers facile
elemental substitution. The coercivity of the resulting powders was
8.0 kOe and the saturation
magnetization was
40 emu g1. After removal of CaO by washing, saturation magnetization increased
and an energy product of 3.57 MGOe was obtained. A range of magnetic properties was obtained by
varying the microwave power, reduction temperature and Nd to Fe ratio. A transition from soft to
exchange coupled to hard magnetic properties was obtained by varying the composition of NdxFe1xB8
(x varies from 7% to 40%). This synthesis procedure offers an inexpensive and facile platform to produce
exchange coupled hard magnets.

1 Introduction exhibited so magnetic properties; a coercivity of 200 Oe and a

Rare earth (RE)-transition metal based high energy density
magnets are of immense signicance in various engineering
applications.1 Nd2Fe14B magnets possess the highest energy
product and are widely used in electric motors, generators,
magnetic separators, magnetic levitation systems, micro
motors, MEMS and memory applications.2,3 Physical methods
such as ball milling and melt spinning are well studied and
utilized in industrial scale production. However, these methods
have several limitations including high energy consumption,
the requirement of high purity metals and inhomogenous
microstructure. Hence, there is a need to explore new methods
for synthesis of magnetic nanomaterials.
Novel chemical synthesis methods for Nd2Fe14B based
magnets have attracted considerable attention, since magnetic
properties such as energy product and coercivity can be tuned
by controlling the microstructure, crystal orientation and
annealing conditions.4,5 Dong et al.6 have reported mechano-
chemical synthesis of 1 mm size Nd–Fe–B particles sequentially
using pyrolytic decomposition, debinding, milling and reduc-
tion–diffusion (R–D) and washing of CaO. Although Nd–Fe–B
alloys with a particle size of 30–100 nm were produced by Haik
et al.7 using boro-hydride reduction, the resulting powders
School of Materials Science and Engineering, Division of Materials Science, Nanyang
Technological University, 639 798, Singapore. Fax: (+65) 6790 9081; Tel: (+65) 6790
4342. E-mail: ramanujan@ntu.edu.sg
saturation magnetization (Ms) of 24 emu g1 were reported. In
another study,8 thermal decomposition and boro-hydride
reduction were used to produce a-Fe powders and Nd2Fe14B
powders, respectively. Exchange coupled Nd2Fe14B/a-Fe nano-
composites were then prepared from these powders by self-
assembly using a surfactant. Nd2Fe14B alloys have also been
prepared by the reduction of Nd2O3, Fe and B powders with
CaH2, followed by sintering. Uncontrolled particle growth
resulted in the formation of micron size Nd2Fe14B powders.6
This size is not optimum for hard magnetic properties; extrinsic
magnetic properties such as coercivity and remanent magneti-
zation are controlled by the particle size and shape; coercivity
reaches a maximum at a particle size corresponding to single
domain formation.4,9
Moreover, the reduction potential of Nd3+ is high and Nd–Fe–
B alloys tend to oxidize very easily even in the bulk form.10,11
Hence, the synthesis of nanoparticles of these alloys is chal-
lenging. Nanoparticle synthesis can also be used to enhance
exchange coupling and to obtain high energy product nano-
composite magnets. Nd2Fe14B and a-Fe nanocomposites are
attractive because the high coercivity of the hard magnetic phase
and high saturation magnetization of the so magnetic phase
leads to high energy product permanent magnets.12–15 Lower cost
Nd-oxide or NdCl3 salts rather than pure Nd metal can be used in
chemical synthesis based on R–D methods. “Bottom-up” molec-
ular level assembly of atoms by chemical synthesis results in
uniform composition and the crystal structure appropriate for

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Paper Nanoscale

hard magnetic properties.16 Chemical methods such as electro-
deposition,17 the hydrogenation–disproportionation–desorption–
recombination (HDDR) process,18,19 the mechanochemical
process,6 boro-hydride reduction,7,8 the solid state reaction
method and the sol–gel method have been used to produce Nd–
Fe–B alloys.20,21 However, these methods have had limited
success in the production of Nd–Fe–B nanostructures.
Microwave assisted syntheses of other nanoparticles have
been reported earlier.22–27 Using microwave synthesis to obtain
the desired properties is of high research interest.23,26,28,29 We
report the facile synthesis of Nd2Fe14B nanoparticles by the
microwave assisted combustion technique. Microwave
synthesis possesses several advantages including molecular
level mixing, faster reaction compared to solid state processes,
energy efficiency and the potential for large scale production.
The process involves Nd–Fe–B oxide preparation by the micro-
wave technique, followed by the reduction of the Nd–Fe–B oxide
by Ca or CaH2.6,30,31 As compared to the sol–gel synthesis
method, no extra heating steps are required to obtain the Nd–
Fe–B oxide powder in this microwave synthesis method.31,32 In
the reduction–diffusion method, hyper-peritectic compositions
result in better magnetic properties.31,32 This process can also be
extended to produce other permanent magnet materials such as
SmCo5, FePt, Dy–Fe–B or NdxDy1xFeB/FeCo systems. To the
best of our knowledge, this work is the rst report on the
synthesis of Nd2Fe14B nanoparticles using the microwave
process.
2 Results and discussion
2.1 Reduction diffusion process
The microwave assisted combustion synthesis method is
similar to the auto-combustion method. Here, the initiation of
combustion is achieved by a microwave oven. Microwave irra-
diation of the solution caused evaporation of water. Metal
nitrates reacted spontaneously with glycine producing Nd–Fe–B
oxide powders. The reaction scheme of Nd–Fe–B oxide forma-
tion by glycine–nitrate combustion (salt to glycine molar ratio of
1 : 1) is shown in the following reaction (Reaction (1)). The Nd–
Fe–B oxide was found to be a mixture of NdFeO3, Fe3O4, FeO,
B2O3 and NdBO3 (Table 1).

Table 1 Reduction mechanism and magnetic properties of Nd–Fe–B synthesized by microwave assisted combustion synthesis

Magnetic measurement (* before washing, A aer washing)

Material identied Magnetic

from Rietveld Composition Coercivity saturation
Reduction temperature ( C) renement (weight %) (Oe) (emu g1) Remarks

Oxide powder obtained by NdFeO3 27.08 225* 35* So

microwave assisted combustion Fe3O4 33.29
synthesis FeO 15.24 103A 60A
NdBO3 11.51
Nd2O3 11.88
B2O3 1.00
400 a-Fe 5.00 325* 38* So
NdFeO3 39.51
Fe3O4 27.18
FeO 4.58 150A 75A
NdBO3 12.53
Nd2O3 11.20
500 a-Fe 42.28 265* 45* So
NdFeO3 35.82
FeO 0.34
Fe3O4 5.49 105A 81A
NdBO3 12.72
Nd2O3 3.17
600 a-Fe 88.63 290* 62* So
NdFe4B4 1.20
Nd2Fe17 10.17 158A 105A
700 a-Fe 5.17 4279* 32* Hard magnet
Nd2Fe14B 26.76
Nd2Fe14BH 41.34
CaO 16.18 2135A 71A
Nd2Fe17 10.55
800 a-Fe 5.30 5900* 31* Hard magnet
Nd2Fe14B 75.46
Nd2Fe17 10.60 3300A 105A
CaO 8.63
800 Nd–Fe–B oxide + 0.2 wt% B Fe 2.80 8000* 40* Hard magnet, magnetic
Nd2Fe14B 92.30 4000A 98A properties increased by B addition
Nd2Fe17 4.90

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Nanoscale
The Nd–Fe–B oxide powders were then reduced by CaH2 in
the temperature range of 400  C to 800  C. The phases present
were analysed by XRD and the mass percentage was calculated
from Rietveld renement (Table 1). The reduction of iron oxides
(Fe3O4 and FeO) to form a-Fe was initiated at 400  C; a larger
mass fraction of iron oxide was reduced at 500  C. At 600  C, the
ternary NdFe4B4 and Nd2Fe17 phases were identied, suggesting
that the Nd2Fe14B formation mechanism may be different from
the mechanism observed in sol–gel synthesis.31,32 The coercivity
of the starting precursor is low (225 Oe). The increase in coer-
civity of the Nd–Fe–B powder reduced at 400  C is due to a-Fe
phase formation (Table 1). The slight decrease in coercivity of
the powder reduced at 500  C is due to a-Fe grain growth. The
formation of Nd2Fe17 at 600  C resulted in a slight increase in
coercivity. At a reduction temperature of 700  C, the rate of
diffusion increased and the desired Nd2Fe14B phase formed. A
high mass percent of the desired Nd2Fe14B phase along with
Nd2Fe17, a-Fe and by-product CaO phases were formed at a
reduction temperature of 800  C (Fig. 1A). The increase in
coercivity for reduction temperatures 700  C and 800  C is due
to the formation of the high coercivity Nd2Fe14B phase. The
nonmagnetic CaO was removed by washing with water and
dilute acetic acid. The reduction reaction of Nd–Fe–B oxides at
800  C is Reaction (2):
2Nd(NO3)3 + 5Fe(NO3)3 + 3B(NO3)3 +20C2H5NO2 + 7O2 /
NdFeO3 + Fe3O4 + FeO + B2O3 +
NdBO3 + 25N2 + 40CO2 + 50H2O (1)
7NdFeO3 þ 8Fe3 O4 þ 29FeO þ NdBO3 þ B2 O3 þ 88CaH2
800  C
ƒƒƒƒƒƒ! 3Nd2 Fe14 B þ Nd2 Fe17 þ Fe þ 88CaO þ 176H2 [ (2)
However, the Nd2Fe17 mass percent is
10.6 wt% due to
boron loss during reduction as volatile boron hydride. The
Fig. 1 X-ray diffraction pattern of the Nd–Fe–B powder synthesized by micro-
wave synthesis followed by reduction–diffusion at 800  C; (A) as-synthesized, (B)
CaO removed by washing, (C) with 0.2 wt% B addition to Nd–Fe–B oxide during
reduction.
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Nd2Fe17 mass percent could be reduced to 5 wt% by 0.2 wt% of
amorphous boron addition to the Nd–Fe–B oxide and CaH2
mixture (Table 1). The magnetic properties improved as the
mass percent of Nd2Fe14B increased, the coercivity increased
from 5.9 kOe to 8 kOe and the saturation magnetization
increased from 31 emu g1 to 40 emu g1 (Fig. 2A, Table 1).
The saturation magnetization increased but the coercivity
decreased aer CaO removal by washing with water (Fig. 2B,
Table 1), as observed previously for the sol–gel synthesis
method.31 However, no Nd2Fe14BHx phases were observed by
XRD. The mass percentage of the Nd2Fe14BHx phase and the
value of x are dependent on the wt% of CaH2 used for reduc-
tion.33 Rietveld renement of CaO removed Nd–Fe–B powder,
spiked with 10 wt% of standard CeO2 showed that the Nd–Fe–B
powder consisted of
13 wt% of the amorphous phase (Fig. 3).
Hydrogenation caused amorphization of the Nd2Fe14B
phase.34,35
High resolution TEM substantiated this observation by
revealing an amorphous phase at the grain boundaries (Fig. 4).
This amorphous phase resulted in changes in the intergranular
Fig. 2 Hysteresis loops of Nd–Fe–B synthesized by microwave synthesis followed
by the reduction–diffusion method; (A) effect of boron addition, (B) effect of CaO
removal by washing with water.
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Fig. 3 Rietveld refinement of Nd–Fe–B alloy synthesized by microwave synthesis followed by reduction–diffusion. The sample was spiked with 10 wt% of standard
CeO2. The experimental X-ray data and calculated pattern fit are excellent (R Bragg values
1–2%). The amorphous content was calculated to be
13 wt%. The
normalized wt% of Nd2Fe14B and Fe phases are 85.1 wt% and 1.9 wt% respectively.
magnetic interactions, decreasing remanent magnetization and
energy product.35 The average crystallite size calculated from
Rietveld renement was
80 nm. Nd2Fe14B lattice parameters
calculated from Rietveld renement were found to be ‘a’ ¼
0.8805 nm and ‘c’ ¼ 1.2195 nm; the ‘a’ value was comparable
with earlier reports; a decrement of 0.01 Å was observed for the
‘c’ value.36 The interatomic distance between Fe to Fe nearest
neighbours can be correlated with the magnetic moment of
Nd2Fe14B; a Nd2Fe14B unit cell resembling a sandwich structure
was constructed by Diamond soware using Rietveld analysis
(Figure 5a and b).
Fig. 4 High resolution transmission electron micrograph (HRTEM) of Nd2Fe14B
synthesized by microwave synthesis method. The interplanar spacing is 2.1 Å
(close to the interplanar distance of 2.2 Å between the (400) plane of the
tetragonal Nd2Fe14B phase).
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Nanoscale
There are six types of Fe sites in the Nd2Fe14B tetragonal
phase. The shortest interatomic distances of Fe sites are Fe (k2)–
Fe (J1) (2.39 Å) and Fe (J1)–Fe (J1) (2.44 Å).37 However, in this
present study the shortest atomic distances were found to be
2.3806 Å and 2.4250 Å and were slightly less than the reported
values. This decrease in interatomic distance results in the
intrinsic magnetic moment reduction.37,38
2.2 Effect of microwave power
Microwave irradiation leads to rapid heating. Varying the
microwave power changes the heating rate,39 resulting in a
change in nucleation and growth rates of Nd–Fe–B particles. In
turn, this can alter the size and shape of the particles. The
magnetic properties depend on the particle size and shape and
thus the magnetic properties can be controlled by microwave
power. The mechanism of heat generation in the microwave by
dielectric heating is due to the microwave absorption by water
molecules. When the intensity of the microwave power
increased from 80 to 800 watts, heat generation increases
rapidly (eqn (3)). Hence there is a change in the thermal energy,
resulting in a change in nucleation and growth rates of Nd–Fe–B
oxide particles, which in turn leads to Nd–Fe–B particles of
different sizes and shapes (Fig. 6). This size and shape variation
alters the magnetic properties of the NdFeB alloys.
P ¼ s|E|2 ¼ u3o300 |E|2 (3)
Where P is the microwave power dissipation, E is the electric
eld, s is the total current, u is the frequency of the applied
eld, 3o and 300 are the dielectric constants of free space and the
imaginary part of the dielectric constant, respectively.
In this work, controlling the NdFeB nanocomposite growth
is associated with the heat produced by the input of microwave
power; this heat drives the chemical reaction. Growth of nano-
particles can be controlled by changing the microwave power
which varies the rate of temperature change and the maximum
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Fig. 5 (a) A unit cell structural design of Nd2Fe14B by Diamond and the values
are provided from Rietveld refined crystallographic parameters of Nd2Fe14B. (b) A
unit cell sandwich structural design of Nd2Fe14B using Diamond software; lattice
parameters and interatomic distances are obtained from Rietveld refinement of
the crystallographic parameters.

temperature achieved.40 In turn, these factors control the

nucleation and growth of the particles, which determines the
size and shape of the particles. Hence, microwave power
produced different shapes and sizes of nanoparticles. Since
magnetic properties are a function of shape and size, this
results in a change in the NdFeB nal energy product.
At a lower power of 80 W, the produced powder possessed an
equiaxed morphology with an average size of
20 nm (Fig. 6A).
As the power increases to 400 W, long nanorods were observed
(Fig. 6B). The selected area diffraction pattern (SADP) of the
nanorods can be indexed to Nd2Fe14B (Fig. 6B-inset). At a higher
Fig. 6 Bright field transmission electron micrograph of Nd2Fe14B synthesized by
power of 800 W, an inhomogeneous morphology consisting of
the microwave assisted combustion method, (A) equiaxed morphology (80 W),
clusters of nanorods and equiaxed morphology was observed (B) nanorod morphology, (400 W, the SADP is indexed to the Nd2Fe14B phase)
(Fig. 6C). For the rst time, the relationship between microwave and (C) inhomogeneous morphology (800 W) were observed for the identical
power and magnetic properties of Nd–Fe–B was examined reduction–diffusion (R–D) conditions.
(Fig. 7). A highest Hc of 8.0 KOe and Ms of 40 emu g1 were

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Paper Nanoscale

Fig. 7 Energy product vs. microwave power of washed Nd2Fe14B prepared by

microwave synthesis for different reduction temperatures of 700  C, 750  C
and 800  C.

obtained for materials reduced at 800  C with an intermediate

microwave irradiation power of 400 watts. The highest energy
product (BHmax) was obtained for 400 W microwave power due
to the formation of exchange coupled hard magnetic nanorods.
At low microwave power Nd2Fe14B is equiaxed. At 400 W power
Nd2Fe14B has the shape of nanorods; the coercivity is high due
to shape anisotropy, resulting in high (BHmax). However, 800 W
microwave power resulted in inhomogeneous morphology and
low (BHmax).41–43

2.3 Compositional effect

Fig. 8A and B illustrates the variation of coercivity and magnetic
moment of NdxFe92xB8 powders (where 7 < x < 40). The prop-
erties could be tuned from so to exchange coupled (hard/so) to
hard magnetic with increasing ‘x’. The coercivity of the NdFeB
powder increased as the concentration of Nd increases. The
maximum coercivity was obtained for Nd35Fe57B8, beyond
which the coercivity decreased to 6.1 kOe for a higher concen-
tration of Nd (Nd, 40 at%). This is due to the higher mass
fraction of non-magnetic phases of Nd and Nd2O3 at the grain
boundaries and smaller mass fraction of the magnetic phase of Fig. 8 Magnetic properties of different compositions of NdxFe92xB8 (where 7 <
Nd2Fe14B. Highest Hc (higher Nd concentration) and Ms (less Nd x < 40) synthesized by microwave synthesis and reduced at 800  C. (A) Coercivity
content) were obtained for as-reduced Nd35Fe57B8 and vs. Nd concentration. [Inset – hysteresis loop of hard magnet Nd35Fe57B8]. (B)
Magnetic moment vs. Nd concentration. [Inset – hysteresis loop of soft magnet
Nd7Fe85B8 powders. The highest energy density (BHmax) was
Nd11Fe81B8].
obtained for Nd15Fe77B8, but this composition does not show
the highest coercivity and magnetization. This is because the
desired mass fractions of hard and so phases were exchange 3 Experimental procedures
coupled resulting in Mr/Ms equal to 0.56. Mr/Ms is called
reduced remanence and is #0.5 for isotropic magnets. Reduced The starting materials were iron nitrate nonahydrate (Alfa
remanence greater than 0.5 indicates that the magnetic phases Aesar, 98–101%), neodymium nitrate hexahydrate (Alfa Aesar,
are exchange coupled.44 A smaller mass fraction of non- 99.9%), boron (Alfa Aesar, 99.8%), glycine (Sigma Aldrich,
magnetic phases and the appropriate size of hard and so >99%) and calcium hydride (Alfa Aesar, 92%). For example, for a
magnetic phases increased the energy product for this target composition of Nd15Fe77.5B7.5, the calculated amounts of
composition. iron nitrate nonahydrate, neodymium nitrate hexahydrate and

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Nanoscale
boron (dissolved in 4 N HNO3 solution) were dissolved in
deionized water. Glycine was added to the salt solution in a
molar ratio of 1 : 1 (salt : glycine) to obtain a stable sol. The
solution was then subjected to microwave irradiation at a low
microwave power of 400 W for 10 min and a dark-red viscous
product was obtained using a Sharp, R-899R household
microwave oven. Microwave heating of the viscous precursor
resulted in evaporation of water and other volatiles. Due to the
exothermic reaction of nitrate salts and glycine the precursor
was spontaneously converted to ultra ne Nd–Fe–B oxide
powders.
The desired Nd2Fe14B nanoparticles were then synthesized
by mixing the Nd–Fe–B oxide powder with CaH2 (Nd–Fe–B oxi-
de : CaH2 in the mass ratio of 1 : 1.1) and annealing in a
vacuum. Reduction was then carried out in the temperature
range of 400  C to 800  C for 2 h. The resulting powders were
washed with deionized water and dilute acetic acid to remove
the non-magnetic CaO by-product and later by acetone to
remove water; this was followed by vacuum drying to obtain the
dried powder.
The washed powders were characterized by X-ray powder
diffraction using a Bruker diffractometer (D8-Advance) with
CuKa radiation of wavelength 1.5414 Å. Diffraction patterns
were recorded with a step size of 0.01 , scan speed of 1 s per
step and scan angle 2q from 20 to 120 . Rietveld renement
was carried out using TOPAS-4.45 A Pseudo-Voigt function was
used to model the peak prole; crystallographic parameters
such as background, zero point shi, scale factor, unit cell
constant, and crystal size were rened. The microstructure of
washed samples was studied using a JEOL 2010 Transmission
Electron Microscope (TEM). The magnetic properties were
measured by a Lakeshore-7404 Vibrating Sample Magnetom-
eter (VSM) which was operated at a maximum magnetic eld
strength of 1.5 T due to limitations of our equipment. In
addition to the reduction diffusion process, Nd–Fe–B synthesis
by a microwave assisted hydrothermal route was studied by
varying the microwave power in the range of 100 W to 800 W,
the effect of composition on the nal product was studied by
varying the weight percentage of Nd to Fe in the range of
NdxFe92xB8 (where 7 < x < 49).
Conclusions
In summary, Nd2Fe14B nanoparticles were successfully synthe-
sized by a novel, fast and energy efficient microwave synthesis
based technique.
 The powders reduced at 800  C resulted in the desired
tetragonal Nd2Fe14B phase (a ¼ 0.8805 nm and c ¼ 1.2195 nm).
 The Nd–Fe–B powder consisted of the desired Nd2Fe14B
(85.1 wt%), a-Fe (1.9 wt%) phases as well as the amorphous
Nd2Fe14BHx (13 wt%) phase.
 Addition of 0.2 wt% of B resulted in a decrease in the mass
percentage of the Nd2Fe17 phase and improved the hard
magnetic properties.
 Nd15Fe77B8 nanoparticles exhibited an energy product of
3.57 MGOe, which is considerably lower than that of bulk
permanent magnets of the same material.
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 Formation of amorphous Nd2Fe14BHx at grain boundaries
resulted in low remanent magnetization and energy product.
 Tuning of the Nd–Fe–B particle size and magnetic prop-
erties could be readily obtained by microwave power.
 The effect of alloy composition showed that a transition
from so to exchange coupled to hard magnetic properties
could be obtained by varying the ratio of Nd to Fe from 1.3 to 12.
Acknowledgements
RVR dedicates this work to the memory of his mother, Mrs.
Susila Vijayaraghavan.
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