Journal of Magnetism and Magnetic Materials 332 (2013) 4851

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Journal of Magnetism and Magnetic Materials

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Induction heating studies of combustion synthesized MgFe2O4 nanoparticles

for hyperthermia applications
V.M. Khot, A.B. Salunkhe, N.D. Thorat, M.R. Phadatare, S.H. Pawar n
Center for Interdisciplinary Research, D.Y. Patil University, Kolhapur 416006, India

a r t i c l e i n f o a b s t r a c t

Article history: The structural, magnetic and ac magnetically induced heating characteristics of combustion synthe-
Received 30 July 2012 sized MgFe2O4 nanoparticles have been investigated for application in magnetic particle hyperthermia.
Received in revised form As prepared nanoparticles showed ferrimagnetic behavior at room temperature with magnetization of
1 December 2012
about 33.83 emu/g at 7 15 kOe. The solid state MgFe2O4 nanoparticles exhibited specic absorption
Available online 13 December 2012
rate (SAR) of about 297 W/g at physiological safe range of frequency and amplitude. The increase in SAR
Keywords: and heating temperature in ac magnetic eld was thought to be due to enhancement in magnetic
Combustion synthesis hysteresis loss caused by dipoledipole interactions in combustion synthesized MgFe2O4 nanoparticles.
Magnetic nanoparticle & 2012 Elsevier B.V. All rights reserved.
Biomaterial
Induction heating

1. Introduction co-precipitation method is suitable for mass production of MNPs,

Magnetic particle hyperthermia (MPH) with magnetic nano-
particles (MNPs) has emerged as one of the promising cancer
modality either alone or in combination with existing cancer
modalities [1,2]. In MPH, magnetic nanoparticles are used for
heating the specic region of body via absorption of radio
frequency when subjected to an alternating current (ac) magnetic
eld [3]. In spite of enormous efforts in this eld, clinical
appliances of hyperthermia for completely treating cancer were
not effective. High heating temperatures and large specic
absorption rate (SAR) at small particle concentration are consid-
ered as most critical challenge to achieve desirable tumor
damage. Especially considering temperature reduction due to
circulation and tissue perfusion in in vivo application, bare
nanoparticles should produce sufciently high heating tempera-
ture and high SAR in physiological tolerable range of frequencies
and magnetic eld with their product en H o5  109 Am  1 s  1
[4]. Ferrimagnetic or superparamagnetic nanoparticles (especially
spinel ferrites) have been extensively studied for MPH as they
exhibit attractive biotechnical and physiological properties such
as: self heating rise due to resonance response to AC magnetic
elds excitation, easy coating with biological entities etc [5,6].
The SAR values of MNPs strongly depend on magnetic
moment, anisotropy energy, particle size and distribution which
are highly sensitive to synthesis methods [7]. Although chemical
n
Corresponding author. Tel.: 91 231 2601202, 91 231 2601235;
fax: 91 231 2601595.
E-mail addresses: wish_khot@yahoo.co.in, pawar_s_h@yahoo.com (S.H. Pawar).
it does require careful adjustment of the pH value of the solution
for particles formation. Combustion method is known for its cost
effectiveness, low reaction time, large mass production and
homogeneity among the products. Also, no further thermal
treatment is required for samples prepared by combustion
method [8]. Though, magnetic nanoparticles have been studied
intensively for MPH in recent years, no distinct report is available
for stable and saturated heat rise in physiological tolerable range
of frequencies and amplitude.
In the present investigation, ferrimagnetic MgFe2O4 nanopar-
ticles were prepared by promising combustion method having
sizes below 40 nm. The structural and magnetic properties of
nanoparticles were explored to understand their self heating
mechanism in ac magnetic eld. The effectiveness of combustion
synthesized MgFe2O4 as potential heating agents for MPH have
been investigated.
2. Materials and method
Polycrystalline MgFe2O4 nanoparticles were prepared by com-
bustion using glycine as a fuel [8]. The detailed process condition
for synthesizing MgFe2O4 nanoparticles were reported else-
where [9]. The particles were characterized by a Philips PW-
3710 automated X- ray diffractometer (XRD) and PerkinElmer
FTIR (4004000 cm  1) spectroscope for structure and phase
identication. The morphology and particle size were observed
by transmission electron microscopy (TEM, JEOL1200). Magnetic
measurements were carried out with a vibrating sample magnet-
ometer (VSM, Lakeshore model no. 7407).

0304-8853/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jmmm.2012.12.010
 V.M. Khot et al. / Journal of Magnetism and Magnetic Materials 332 (2013) 4851
Fig. 1. Typical XRD pattern (a) and FTIR spectra and (b) for as prepared MgFe2O4 powder.
Fig. 2. TEM image and SAED pattern (inset picture) of as prepared MgFe2O4
powder.
Induction heating of as synthesized MgFe2O4 nanoparticles
was performed in a plastic microcentrifuge tube (1.5 ml) using an
instrument (Easy Heat 8310, Ambrell, UK) with 6 cm diameter
coil (4 turns). Samples (25 mg/mL of distilled water) were placed
at the center of the coil and the applied frequency was 265 kHz
and eld amplitude varied [10].
3. Results and discussion
The crystal structure of combusted MgFe2O4 nanoparticles was
elucidated by XRD (Fig. 1a). Particles obtained in this case are
nanocrystallites with lattice parameter of 0.8385 nm with single
phase of spinel MgFe2O4 [11]. The formation of cubic spinel was
also supported by FTIR spectra (Fig. 1b). The observed values
illustrate that frequency bands appeared at 561 and 451 cm  1 are
responsible for the formation of spinel MgFe2O4 [9,12,13]. On the
basis of this data it can be suggested that the MgFe2O4 spinel
phase is formed with cation distribution,
Fe1x 3
Mgx 2
A Mg1x 2
Fe1 x 3
B O2
4 1
where x is inversion parameter (x 0 for inverse spinel and x1
for normal spinel) while A and B are tetrahedral and octahedral
sites in spinel structure respectively. TEM image (Fig. 2) of as
prepared powder shows the formation of quasi-spherical
49
Fig. 3. MH curve and low eld hysteresis (upper inset) for as prepared MgFe2O4
nanoparticles at different temperatures (lower inset shows magnied image for
MH at origin).
MgFe2O4 nanoparticles with sizes ranging 1040 nm ( 72 nm).
The selected area electron diffraction pattern (inset of Fig. 2) is
consistent with XRD pattern.
The MH measurements of as prepared MNPs are performed at
two different temperatures at 10 K and 300 K (Fig. 3) in order to
investigate the effect of temperature on magnetization and
coercivity. From the gure, it can be observed that magnetization
of sample is about 33.83 emu/g at 300 K and 41.60 emu/g at 10 K
respectively. This increase in magnetization at lower temperature
was attributed to frustration effects in ferrites below the blocking
temperature of the materials [14]. The combustion synthesized
MgFe2O4 nanoparticles showed typical characteristics of ferri-
magnetism at room temperature with minor hysteresis (  53 Oe).
The rise in temperature versus time for sample with varying
eld amplitude is shown in Fig. 4 a, b. Heat dissipation by
magnetic nanoparticles under ac magnetic eld is measured as
SAR (W/g) and it can be expressed as:
  
dT ms
SAR C 2
dt mm
where C is the specic heat capacity of suspension 4.186 J/(g.1C),
(dT/dt is the initial slope of temperature versus time graph, ms is
the mass of suspension and mm is the mass of the magnetic
material in suspension. This value should be as high as possible to
minimize the amount of magnetic material applied for hyperthermia.
The magnetic induction heating of ferrite materials is originated from
their power loss in alternating magnetic eld. The total power loss (P)
50 V.M. Khot et al. / Journal of Magnetism and Magnetic Materials 332 (2013) 4851

Fig. 4. Temperature versus time curves for 2 mg/mL (a) and 5 mg/mL (b) MgFe2O4 nanoparticles at applied eld, 167.6 Oe335.2 Oe (dotted line indicates the
hyperthermia temperature region).

is composed of three parts, hysteresis loss, eddy current loss and magnetic nanoparticles is forbidden by simply increasing eld
residual loss [10,14]. and frequency [14,15].
The hysteresis loss in an ac magnetic eld can be expressed From Fig. 4a and b, it is clear that the temperature increases with
as [12], increase in eld amplitude and concentration of nanoparticles. The
Z -Hmax dotted region in gure denotes the hyperthermia threshold tem-
A m0 MHdH 3 perature. It is observed that for particle concentration 2 mg/mL, the
-Hmin elds 167.6 and 209.5 Oe are not sufcient to reach hyperthermia
And thus the specic absorption rate is, threshold temperature while for concentration 5 mg/mL, hyperther-
mia temperature is reached for all values of applied elds. The
SAR Af 4
physical nature of the rapid temperature rise in the initial stage can
where e is frequency of ac magnetic eld and it is expressed as be thought to be primarily due to the magnetic hysteresis loss, Neel
e o  /2p, M is magnetization and H is applied magnetic eld. Thus rotation, Brownian and Eddy current losses of each ferrimagnetic
one has to take into account the SAR dependence on frequency and nanoparticle activated by ac magnetic eld [5,15]. However in
amplitude. The heat loss is considered to be due to Brownian present study, Brownian losses are negligible as samples are mea-
relaxation (when the particle spins to align itself with the magnetic sured in powder state in water. Since MgFe2O4 exhibit very low
moment) and Neel relaxation (when the magnetic moment spins conductivity (10  7 S/cm), contribution from eddy current losses is
within the crystal structure of the nanoparticle). Neel relaxation (tN) negligible. Therefore heat loss in case of MgFe2O4 may be due to
time can be expressed as, hysteresis and relaxation losses. The later is more prominent in
  single domain magnetic nanoparticles. The heat dissipation by
tN t0 exp KV=kb T 5
magnetic nanoparticles in AC magnetic eld is also strongly affected
and Brownian relaxations (tB) as, by size distribution [16,17].
The broad particle size distribution increases dipoledipole inter-
3ZV H
tB 6 actions which affects the induction heating properties of material.
kb T This holds true only if the particles were uniform with narrow size
where the relaxation time constant t0 is of the order of 10  9 s, VH is distribution. If the particles exhibit broad distribution, both super-
the hydrodynamic volume which is the effective volume (including paramagnetic and ferrimagnetic nanoparticle may co-exist and the
that of the nanoparticle and coating or surfactant attached to the particle size being optimal for large heating power in hyperthermia
nanoparticle), Z is the viscosity of the medium, T is the temperature may be found in this size range [14,16]. Thus broader size distribu-
and kb is the Boltzmann constant [15]. tion may be favorable to get large heat output for hyperthermia. The
The effective relaxation time is given by, reason is that in case of narrow size distribution, large particle gap
created between adjacent nanoparticles results low particle interac-
1 1
teff 7 tion energy and small coupling exchange energy. If the size distribu-
tN tB
tion is broad, this interparticle gap would possibly ll up with
The power loss corresponding to Brown or Neel relaxations is smaller particles resulting in increased particle interaction energy
approximately given by, and coupling exchange energy [18,19]. This additionally increased
coupling exchange energy results in enhancement of magnetic
P m0 pw00 f H2 8
moment as well as magnetic susceptibility. As a consequence of this,
7 there is enhanced hysteresis loss and enhanced ac magnetically
where m0 4p  10 H/m and w00 is the imaginary part of
magnetic susceptibility which can be expressed as, induced heating characteristics.
oteff Fig. 3 (upper inset) show low eld MH loops measured at the
w00 w 9 applied magnetic eld of 7600 Oe. As can be clearly conrmed,
1 oteff 2
particleparticle interaction in present system corresponding to
Though the heating power is directly proportional to square of minor hysteresis area loss was observed. This directly demon-
the amplitude (Eq. 8), the enhancement of heating power of strates that particle dipole interaction affects the magnetic hysteresis
 V.M. Khot et al. / Journal of Magnetism and Magnetic Materials 332 (2013) 4851
Fig. 5. SAR values for MgFe2O4 nanoparticles (2 mg/mL and 5 mg/mL) at applied
eld, 167.6 Oe335.2 Oe.
Fig. 6. Rise in temperature for MgFe2O4 nanoparticles (2 mg/mL and 5 mg/mL) at
applied eld, 167.6 Oe335.2 Oe.
loss, which is the main physical reason for the remarkably increased
temperature [19]. SAR values are calculated by Eq. (2) for nanopar-
ticles dispersed in distilled water (1 mL) at different elds varying
from 167.6 Oe335.2 Oe at 265 kHz (Fig. 5). The overall SAR value is
found to increase from 38 W/g to 297.5 W/g with increase in eld
from 167.6 Oe to 335.2 Oe. Thus the observed high SAR values may
be considered due to Neel relaxation of MgFe2O4 nanoparticle
induced by hysteresis losses as particle size distribution is broad.
The observed sufciently high temperature rise, around 14.98 1C and
22.25 1C (Fig. 6) of MgFe2O4 nanoparticles at 2 mg/mL and 5 mg/mL,
respectively in the physiologically tolerable range of the magnetic
eld (251.4 Oe or 20 kA m  1 and 265 kHz) are considered as
promising AC magnetically induced heating characteristics for an
in vivo hyperthermia application. Also the concentration used here to
achieve the required temperature is reasonably low (2 mg/ml and
5 mg/ml) that compared to literature values [16].
51
4. Conclusions
MgFe2O4 nanoparticles with sizes around 1040 nm and good
dispersibility were successfully prepared by combustion method.
Combustion synthesis was found more advantageous over con-
ventional methods for preparing MgFe2O4 nanoparticles as it does
not require any pH control or intermediate calcination step. The
enhancement in SAR from 38 W/g to 297.45 W/g is primarily
thought to be due to hysteresis loss as particles do exhibit low
coercivity and broad size distribution. Thus, combustion synthe-
sized MgFe2O4 nanoparticles with large enough SAR at low
particle concentration, suitable magnetic properties can be a
promising heating agent for MPH.
Acknowledgments
Author Mr. V.M. Khot acknowledges the Council of Scientic and
Industrial Research, India for the award of senior research fellowship
File No.: 09/1077/(0001)/2012/EMR-1. Authors are thankful to
Dr. D. Das, Dr. R. S. Ningthoujam and Dr. R. K. Vatsa, BARC for
availability of induction heating studies.
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