Studies of the Magnetic Properties and

Specific Absorption of Mn0.3Zn0.7Fe2O4

Nanoparticles

Pham Thanh Phong, P.H. Nam, Do

Hung Manh, D.K. Tung, In-Ja Lee &
N.X. Phuc

Journal of Electronic Materials

ISSN 0361-5235
Volume 44
Number 1

Journal of Elec Materi (2015) 44:287-294

DOI 10.1007/s11664-014-3463-0

1 23
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 Author's personal copy
Journal of ELECTRONIC MATERIALS, Vol. 44, No. 1, 2015
DOI: 10.1007/s11664-014-3463-0
 2014 The Minerals, Metals & Materials Society

Studies of the Magnetic Properties and Specific Absorption

of Mn0.3Zn0.7Fe2O4 Nanoparticles

PHAM THANH PHONG,1,2,3 P.H. NAM,1 DO HUNG MANH,1,4 D.K. TUNG,1

IN-JA LEE,2,5 and N.X. PHUC1

1.—Institute of Materials Science, Vietnam Academy of Science and Technology, 18 Hoang Quoc
Viet Road, Cau Giay District, Hanoi, Vietnam. 2.—Department of Chemistry, Dongguk Univer-
sity-Gyeongju, 707 Suckjang-dong, Gyeongju-Si, Gyeongbuk 780-714, Korea. 3.—e-mail:
ptphong.nh@khanhhoa.edu.vn. 4.—e-mail: manhdohung@yahoo.com. 5.—e-mail: lij@dongguk.ac.kr

Nanosized mixed ferrite Mn0.3Zn0.7Fe2O4 was prepared by a hydrothermal

method at pH 11 and 180C. XRD analysis showed that the material had the
characteristic spinel structure with average particle size 14 nm. The real part
of the AC susceptibility clearly proved the ferrite had spin glass like behavior.
Magnetic inductive heating studies were performed at 236 kHz with magnetic
field amplitude 50–80 Oe. The specific absorption (SA) was investigated by use
of linear response theory. The experimental results were in good agreement
with theoretical predictions. Moreover, the intrinsic loss power (ILP) was
calculated from SA values. It is believed that Mn0.3Zn0.7Fe2O4 nanoparticles
with a high ILP will be useful for in situ hyperthermia treatment of cancer.

Key words: Mn–Zn ferrite spinel, hydrothermal, nanoparticle, superspin

glass, AC losses, hyperthermia, intrinsic loss power

INTRODUCTION the magnetic field, the properties of the magnetic

particles, and the cooling capacity of the blood flow.6
During last two decades, magnetic nanoparticles
For superparamagnetic materials with zero rema-
(NPs) have elicited much research activity because
nence, the energy transformation is mainly attrib-
of their interesting structures and expected multi-
uted to Brownian and Neel relaxation losses. In the
functional and advanced applications in magnetic
heat treatment of cancer, the best conditions, i.e.
fluid hyperthermia, imaging medical diagnosis, and
those guaranteeing the therapeutic effect of mag-
targeted drug delivery.1–4 Magnetic hyperthermia is
netic NPs hyperthermia are consistent with the
regarded as a promising therapeutic method for
lowest possible number of magnetic NPs, limited
cancer treatment. The hyperthermia technique
applied AC magnetic field (H), and frequency (f),
consists of delivering nanoparticles to the area of
and heat power generated per particle unit mass as
interest and then heating them, by use of an
high as possible within these constraints.7 High
external radiofrequency magnetic field, until the
heating temperature and large specific absorption
cell temperature reaches 42–49C, at which cancer
(SA) at low particle concentration are regarded as
tissue is destroyed without damaging surrounding
the most important challenges to achieve the effec-
normal tissue.5 The magnetic NPs have the ability
tive tumor damage desired.8
to transform magnetic energy into heat by several
A wide range of ferromagnetic nanoparticles,
mechanisms: eddy current loss, hysteresis loss, and
including metallic alloys and/or oxides with superior
relaxation loss, which include Brownian relaxation
magnetic properties, can be synthesized for use in
and Neel relaxation. Energy conversion efficiency is
magnetic fluid hyperthermia.5,9–11 Magnetite
highly dependent on the amplitude and frequency of
(Fe3O4) NPs are the most extensively studied,
because of their known optimum morphological,
crystallographic, biocompatibility, and magnetic
(Received March 8, 2014; accepted October 8, 2014; characteristics. The Curie temperature (TC) of
published online October 28, 2014) Fe3O4 is 550C, which is much higher than the

287
 Author's personal copy
288
temperature normally used for hyperthermia. When
Fe3O4 nanoparticles are used in hyperthermia
applications, therefore, a temperature of approxi-
mately 100–300C can be achieved, depending on
frequency (f), magnetic field (H), and heating time
(t). This could be harmful to normal tissue and cells.
Many research centers have sought new magnetic
materials with lower TC to replace Fe3O4. Among
magnetic nanoparticles available, nanosized Mn–Zn
ferrite materials not only have unique size-depen-
dent physical and chemical properties compared
with their bulk counterparts but have also emerged
as potential candidates for hyperthermia applica-
tion, because of their suitable TC (340 K) and high
stability of permeability with temperature and
time.12 Several methods are used to produce Mn–Zn
ferrite nanoparticles,13–19 the most common being
co-precipitation, hydrothermal precipitation, sol–gel
synthesis, and combustion synthesis.
Depending to the interaction between magnetic
moments, ferromagnetic nanoparticles are classified
as either superparamagnetic or superspin glass
(SSG). Superparamagnetic behavior occurs as a
result of non-interaction of super spins, in which
relaxation time typically obeys the Neel–Arrhenius
law.20 Superspin glass (SSG)-like behavior below
freezing temperatures occurs in highly interacting
systems in which the interaction between magnetic
moments is strong enough to create a spin frustration
effect.21 These properties of magnetic nanoparticle
systems affect their hyperthermia applications.
Recently, Verde et al.22 synthesized CoxFe3xO4
(x = 0.74 and 0.91) nanoparticles by co-precipitation
and used them in hyperthermia investigations at
500 kHz with a sinusoidal magnetic field amplitude
of up to 68 Oe. The results showed that the SA had
narrow and pronounced maxima for intermediate
anisotropy values. They also found the calculated
SA was in good agreement with theoretical predic-
tions obtained by use of linear response theory and
dynamic hysteresis simulations. In another inter-
esting report, Nikam et al.8 described investigation
of the structural and magnetic properties and
alternating current magnetic heating characteris-
tics of Co0.5Zn0.5Fe2O4 nanoparticles prepared by
chemical co-precipitation. The highest SA value was
114.98 W/g for 5 mg/mL sample concentration at a
frequency of 265 kHz and a magnetic field strength
of 335.2 Oe. This showed the particles had much
potential as heating agents for magnetic hyper-
thermia.
In the work discussed in this paper, Mn0.3Zn0.7
Fe2O4 NPs were prepared by a hydrothermal method.
The structural and magnetic properties of the NPs
were investigated to enable understanding of their
physical properties. Moreover, the SA and ILP
(intrinsic loss power) were calculated and compared
with theoretical predictions. Good quantitative
agreement between theory and experiment was
obtained and our results show that the anisotropy
and saturation magnetization are, in fact, important
Phong, Nam, Manh, Tung, Lee, and Phuc
properties in the search for materials optimized for
magnetic hyperthermia.
EXPERIMENTAL
Mn0.3Zn0.7Fe2O4 NPs were synthesized by a
hydrothermal process in a Teflon-lined stainless-
steel autoclave. FeCl3, MnCl2, ZnCl2, HCl, and
NaOH (Merck 99.9%) were used as starting mate-
rials. FeCl3, MnCl2, and ZnCl2 were dissolved in
aqueous hydrochloric acid solution, then the sodium
hydroxide was slowly added into the solution. The
reaction mixture was stirred for approximately
30 min. Finally, the solution was transferred to
Teflon-lined stainless-steel autoclave until it was
80 % full. After heating at 180C for 12 h, the
autoclave was left to cool naturally to room tem-
perature. Products were washed several times with
hot de-ionized water and acetone and finally dried
in an oven at 80C for 5 h. A x-ray D 5000 Diffrac-
tometer with Cu Ka (k = 0.1546 nm) radiation was
used to determine crystal structure and to estimate
grain sizes of the material. Commercial X’pert
Highscore Plus software (PANalytical) was used for
Rietveld refinement analysis. The composition and
microstructures of the dried powders were deter-
mined by use of x-ray diffraction and transmission
electron microscopy (TEM) (Jeol, JEM-1010). All
magnetic measurements were performed with a
Quantum Design Physical Property Measurement
System (PPMS). A homemade unit, in which an
RDO generator produced an AC magnetic field with
an amplitude in the range 50–80 Oe at a fixed fre-
quency of 236 kHz, was used to measure the mag-
netic inductive heating of Mn0.3Zn0.7Fe2O4 The
concentration of aqueous ferrofluids was 15 mg/mL.
The temperature change of the fluid was directly
monitored by dipping an optical sensor into the
fluid.
RESULTS AND DISCUSSION
Figure 1 shows an XRD pattern of Mn0.3Zn0.7
Fe2O4. The (220), (311), (400), (422), (511), and (440)
diffraction peaks are characteristic of the single
phase spinel cubic structure with the Fd/3 m space
group (JCPDF file no. 22-1012). Moreover, the broad
(311) peak indicates that the grain size of the
Mn0.3Zn0.7Fe2O4 is in the nanoscale range. The
average nanocrystalline size (D) was calculated
by the Hall–Williamson method,23 by use of the
equation:
0:89k
b cos h ¼ þ 4e sin h (1)
D
where k is the wavelength of the x-ray radiation
(k = 0.1546 nm), h is the Bragg angle, b is the full
width at half maximum of the (311) peak, and e is
the internal strain. The experimental lattice
 Author's personal copy
Studies of the Magnetic Properties and Specific Absorption of Mn0.3Zn0.7Fe2O4 Nanoparticles
constant (aexp) was determined by use of the rela-
tionship:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a ¼ dhkl h2 þ k2 þ l2 (2)
where (h k l) are the Miller indices and d is the
inter-planar spacing. The theoretical lattice con-
stant (ath) was calculated by use of the expression24:
8 h pffiffiffi i civity; the coercivity at 10 K is 130 Oe. This suggested
ath ¼ pffiffiffi ðrA þ R0 Þ þ 3ðrB þ R0 Þ (3)
3 3
where RO is the radius of the oxygen atom
(RO = 1.32 Å). The x-ray density (dx) can be deter-
mined by use of the equation25:
8M
dx ¼
Na3
where M is molecular weight and N is Avogadro’s
number.
The inter-planar spacing (d), experimental lattice
parameter (aexp), theoretical lattice parameter (ath),
x-ray density (dx), and average crystallite size (D)
are listed in Table I. As shown in Table I, the
average crystallite size, calculated from the XRD
data, is generally in agreement with Ref. 26. The
experimental lattice constant is 8.432 Å, which is in
agreement with that of bulk Mn0.3Zn0.7Fe2O4.27
However, a small deviation between ath and aexp
was observed. This may be because of the presence
at the octahedral sites of ferrous ions, Fe(II)
(rFe2þ = 0.78 Å), with larger radii than Fe(III)
(rFe3þ = 0.645 Å).28
A representative TEM image of Mn0.3Zn0.7Fe2O4
is shown in Fig. 2. The surface morphology of the
polycrystalline powders were homogeneous and the
particles were sphere-like in appearance. It is clear
that the average particle diameter is approximately
12 nm, which is not much different from that
obtained from the XRD measurements. Agglomera-
tion of the sample is because of slow particle growth
in the hydrothermal process. Grain growth did not
(311)
Intensity (a.u)
(220)
(511)
(400)
(422)
30 40 50
2θ (degree)
Fig. 1. X-ray diffraction pattern of Mn0.3Zn0.7Fe2O4 nanoparticles.
289
occur because the temperature of synthesis of the
ferrites did not exceed 200C.
To investigate the magnetic response of the parti-
cles to an external field, we measured its field-
dependent magnetization in the temperature range
10–300 K. Figure 3 shows hysteresis curves of the
material at 10 K. The room temperature magnetiza-
tion data are indicative of zero remanence and coer-
Mn0.3Zn0.7Fe2O4 was superparamagnetic (SPM) at
room temperature. A striking feature of the lower
inset of Fig. 3 is that all the results obtained at tem-
peratures>150 K fall on a single curve when plotted
as a function of H/T. This confirms the material has
SPM behavior above 150 K. The non-saturating
behavior at 10 K (upper-left inset) could be explained
(4)
by assuming the NPs have a core–shell structure.
Here, the shell may be regarded as a highly disor-
dered magnetic system, because of high surface
energy or pinning of the surface spins,29 whereas the
core is believed to be ordered. To gain further insight
into the core–shell structure of the particles we cal-
culated the thickness of the surface layer (t) of by use
of the expression:
 
6t
M s ¼ M s ð 1Þ 1  (5)
d
Table I. Inter-planar spacing (d) experimental lattice
parameter (aexp), theoretical lattice parameter (ath),
x-ray density (dx), and average crystallite size (D) of
Mn0.3Zn0.7Fe2O4
d (Å) 2.542
aexp (Å) 8.432
ath (Å) 8.446
dx (g/cm3) 5.27
D (nm) 14
(440)
60 70
Fig. 2. Transmission electron micrograph of Mn0.3Zn0.7Fe2O4 ferrite
nanoparticles.
 Author's personal copy
290 Phong, Nam, Manh, Tung, Lee, and Phuc

in which Ms(1) = 80 emu/g corresponds to the bulk
value at room temperature. By using d = 14 nm and
Ms = 27.7 emu/g in Eq. 5 we obtained a shell
thickness of approximately 0.6 nm, in good agree-
ment with the experimental data of Chen et al.,30 so
our results are in good agreement with the core–
shell model.
The temperature dependence of the field-cooled
(FC) and zero-field-cooled (ZFC) magnetization (M)
were measured from 60 K to 420 K under a field of
100 Oe; the results are shown in Fig. 4.
The magnetization in the ZFC mode reveals a
broad paramagnetic-to-ferromagnetic transition at
TC because of ferromagnetic spin ordering in the Fe
sublattice with a peak at TB. TB occurs at very close
to the onset temperature of the reversibility, indi-
cating the absence of spin clusters in our sample. As
is well known, the appearance of TB in the MZFC(T)
curve is a characteristic of both spin glass and
superparamagnetic systems, whereas the decrease
in MFC(T) with decreasing temperature is a char-
acteristic of superspin glass.31,32 TC and TB were
estimated as 340 K and 106 K, respectively. Note
that TC of our material is lower than TC of the non-
substituted (MnFe2O4) bulk ferrite (TC = 540 K).33
The observed decrease in the TC might be attributed
to the level of substitution of non-magnetic Zn2+
ions for Mn2+ ions in the lattice. Such a substitution
not only dilutes the magnetic sublattices but also
causes a reduction of the super-exchange interac-
tion between A and B sites, resulting in the decrease
in TC. Another factor which contributes to the
decrease in TC could be the paramagnetism effect of
small particles. It is evident from Fig. 4 that,
because of the reduction in the particle size, the
Fe–O–Fe paths suffer from severe degradation, with
suppression of the magnetization, and from broad-
80
ening of the PM–FM transition. To gain a better
understanding of the SPM behavior and to test the
hypothesis of the single domain particle of our sys-
tem, we estimated critical diameter for a single do-
main by use of the equation:
9wp
Dc ¼ (6)
2pMs2
where domain wall energy (wp) is defined by
wp = (2kBTCKv/a)1/2, Ms is the saturation magneti-
zation, kB is the Boltzmann constant, TC is the
Curie temperature, Kv is the magneto crystalline
anisotropy constant, and a is the lattice constant.34
Literature values of Kv, TC and Ms measured for
samples of similar composition to ours are
3.3 9 104 erg/cm3,35 340 K and 314 G. The observed
lattice constant is 8.432 Å. Thus the critical diam-
eter obtained by use of Eq. 6 is 27.8 nm, which is
larger than the grain size estimated from the TEM.
This result is indicative of the single domain nature
of the material.
From the blocking temperature TB, the effective
anisotropy constant (Keff) can be estimated by use of
Eq. 736:
25kTB
Keff ¼ (7)
V
For Mn0.3Zn0.7Fe2O4 nanoparticles, Keff calcu-
lated in this way is 1.46 9 105 erg/cm3, which is
larger than the magneto crystalline anisotropy
constant of bulk ferrite.37 We believe this is because
the surface contribution enhances the effective
anisotropy constant.
To further study the magnetic dynamic behavior
of the particles, we measured AC susceptibility as a
function of temperature and as a function of applied
field frequency. Figure 5a and b show the temper-
ature dependence of the real and imaginary parts of

53
M (emu/g) 10 K
52 7
40 51
50 6 ZFC
49 M/Ms
M (emu/g)

FC
0 48 1 150 K 5
0.5 0.75 1 0.5
4 200 K
M (emu/g)

H ( x 10 Oe) 0 250 K 4
-0.5 300 K T
-40 3 B
-1 H = 100 Oe
-60-40-20 0 20 40 60
2
H/T (Oe/K)
-80
-1 -0.5 0 0.5 1 1
4
H ( x 10 Oe)
Fig. 3. Magnetization curve at 10 K. The upper inset is a close-up of 50 100 150 200 250 300 350 400 450
the high field segment of the 10 K loop and it shows the nonsatu- T (K)
rating behavior. The lower inset is reduced magnetization versus H/T
for the temperature range 150–300 K, and is indicative of super- Fig. 4. Temperature and field-dependent dc-magnetization curves of
paramagnetic behavior. Mn0.3Zn0.7Fe2O4 ferrite nanoparticles.
 Author's personal copy
Studies of the Magnetic Properties and Specific Absorption of Mn0.3Zn0.7Fe2O4 Nanoparticles 291

(a) (b) 0.006

33 Hz
0.16 99 Hz 0.005 33 Hz
198 Hz 99 Hz
396 Hz 0.004 198 Hz
0.12
396 Hz

χ'' (emu/g)
χ' (emu/g)

0.17 594 Hz
0.16 792 Hz
0.003 594 Hz
0.08 0.15 792 Hz
χ' (emu/g)
1089 Hz 0.002
0.14 1089 Hz
0.13
0.12 0.001
0.04 0.11
0.1
40 80 120 160 200 0
T (K)
0
50 100 150 200 250 300 50 100 150 200 250 300
T (K) T (K)
Fig. 5. Temperature dependence of the AC susceptibility of Mn0.3Zn0.7Fe2O4 ferrite nanoparticles for frequencies from 33 Hz to 1089 Hz: (a)
Real part v¢(T), the peak positions are magnified in the inset; (b) imaginary part v¢¢(T).

AC susceptibility, v¢ and v¢¢, over the frequency
range 33–1089 Hz. The measurements were per-
formed at an AC field of 2 Oe. With increasing fre-
quency (f), the maxima of v¢ and v¢¢ shift toward
higher temperatures. Also, as the frequency
increases, the maximum peak height decreases for
v¢ but increases for v¢¢. This indicates that it becomes
difficult for particle magnetization to follow the field
changes as the frequency increases, as a result of
which the peak height of v¢ decrease. Furthermore,
the energy loss, and consequently the peak value of
v¢¢, increases with increasing frequency.
We used different models to obtain information
about the nature of the dynamic properties of the
nanoparticles. According to the literature, two
models, the Neel–Arrhenius model and the Vogel–
Fulcher model, are usually used to explain the
phenomenon of spin glass freezing. According to the
Neel–Arrhenius model,37 the relaxation time for a
system consisting non-interacting superparamag-
netic particles, is given by:
lnð f Þ ¼ lnðf0 Þ  Ea =kB Tf
where f0 is in the range 109–1013 Hz for super-
paramagnetic systems, and Tf is the temperature of
the peak of the real part of the AC susceptibility. By
fitting the experimental data from Fig. 5a in Eq. 8,
we obtained an unrealistically large f0 = 7.75 9
1027 Hz in comparison with 1013 Hz (the fit is not
shown here). This indicates that the nanoparticles
are not independent of each other, i.e. there is
interaction between them. We therefore used the
Vogel–Fulcher law for interacting systems to fit
these data. Using this law, the relaxation time was
calculated by use of the equation38:
 
lnð f Þ ¼ lnðf0 Þ  Ea =kB Tf  T0 (9)
where T0 is the effective temperature and Tf is the
temperature of the peak of the real part of the AC
susceptibility. The experimental data taken from
Fig. 5a can be fitted to Eq. 9 as shown in Fig. 6a.
The estimated values of f0, Ea/kB, and T0 from this
fitting are 1.8 9 105 Hz, 90 K, and 105 K, respec-
tively. As already remarked, f0 (105 Hz) is at least
three orders of magnitude smaller than the typical
value of f0  108–1011 Hz for weakly interacting
nanoparticles.38 This may be indicative of a strong
interaction between Mn0.3Zn0.7Fe2O4 nanoparticles.
A dynamic study of small interacting particles by
Dorman et al.39 showed that the Vogel–Fulcher law
is valid only if T0 > TB. Because T0 is close to TB for
our material, the Vogel–Fulcher law cannot explain
its dynamic behavior.
The criterion c, defined by c = (1/Tf)DTf/
D(log 10x), has often been used to distinguish
canonical spin glass (SG) systems from superpara-
magnetic (SPM) systems. The value of c is less than
0.06 for SGs and 0.3 for SPMs. c  for our mate-
rial is 0.04, implying it is SSG like. Figure 6b is a
plot of the relaxation time s, evaluated as s = 1/2pf,
versus Tf. The fit to data obtained by use of the
critical slowing down model40 to the solid line:
 zm
T
(8) s ¼ s0 1 (10)
Tg
yields a dynamic critical exponent zm = 9.3, a
microscopic relaxation time s0 = 3.27 9 1011 s, and
a glass transition temperature Tg = 102 K. The
values of zm and s0 are comparable with those of the
Ni0.3Zn0.7Fe2O4 ferrite nanoparticles superspin
glass reported by Rahimi et al.41: zm = 8.0 and
s0 = 2.72 9 1012 s. Recently, Parekh et al.29 also
reported the SSG-like behavior of oleic acid-coated
Mn0.5Zn0.5Fe2O4 ferrite nanoparticles. Moreover, it
should be noted that zm is also within the range of
that for the three-dimensional (3D) Ising spin
glass.42 These results indicate that our material is
an SSG.
It is well known that the magnetization behavior
of single-domain particles in thermodynamic equi-
librium can be described by the Langevin function:
     
lH lH kB T
M ¼ nlL ¼ nl coth  (11)
kB T kB T lH
 Author's personal copy
292 Phong, Nam, Manh, Tung, Lee, and Phuc

(a) 8 (b) 0.006

7 ln(f) 0.005
τ
0.004
ln(f) 6

τ (s)
0.003
5
0.002
4 0.001

3 0
114 116 118 120 122 124 114 116 118 120 122 124
T (K) T (K)
f f

Fig. 6. (a) Plot of a ln(f) versus Tf for v¢(symbols) and the fitting data (solid line) obtained by use of Eq. 9; (b) plot of s versus Tf for v¢¢(symbols)
and the fitting data (solid line) obtained by use of Eq. 10.

where n is the concentration of particles, l is the 80

magnetic moment of a single particle, and kB is the 60
Boltzmann constant. 10 K
40 300 K
Equation 11 was used to fit the M–H data recorded
at 10 K and 300 K. The results presented at Fig. 7 20

M (emu/g)
show that Eq. 11 fits the data very well at 300 K, 0
which makes it possible to calculate the magnetic
moment of a single superparamagnetic particle: -20
l  962.8 9 1019 emu (l = 10.4 9 103 lB, where lB -40
is the Bohr magneton) and the particle concentration,
-60
n  1.7 9 1018 cm3. Therefore, the volume of one
magnetic particle is 6.1 9 1019 cm3, which corre- -80
sponds to the average particle diameter d = 11 nm. -40 -20 0 20 40
This value is in good agreement with results from H (kOe)
powder XRD analysis. This correspondence also Fig. 7. Magnetization data for Mn0.3Zn0.7Fe2O4 ferrite nanoparticles
confirms that the whole volume of the particle is at 10 K and 300 K. The solid line is the fitted line using the Langevin
magnetically ordered.36 Conversely, the M(H) data at function.
10 K are not in satisfactory agreement with Eq. 11.
Therefore, the values of l  6.5 9 1019 emu and
n  4.8 9 1020 cm3 estimated from the curve fitting superparamagnetic nanoparticles at low magnetic
are not good enough to explain the experimental field. Under this assumption, the power loss for
results. This deviation may be because of the signif- superparamagnetic nanoparticles is given by:
icant contribution of the particle’s anisotropic energy
at low temperatures,43 which also corresponds with 2p2 f 2 s
Pðf ; HÞ ¼ l0 vH02 (12)
the nature of the hysteresis of the M(H) curve (Fig. 3). 1 þ ð2pf sÞ2
A better fit is obtained at 300 K, partially because the
anisotropy energy is much smaller than kT. where l0 = 4 p 9 107 T mA1 is the vacuum sus-
Magnetic heating can be effectively achieved by ceptibility, v is the magnetic susceptibility of the
delaying the relaxation of the magnetic moment in powder, H0 is the intensity of the magnetic field,
an AC magnetic field. Heating is a result of two and f is the frequency of electromagnetic field. When
different mechanisms: rotation within the particle the ensemble is of superparamagnetic particles of
(Néel losses) or rotation of the particle itself (Brown magnetic moment l, the magnetic susceptibility v
losses). Although numerous empirical data on can be calculated by use of the formula43,45:
magnetic hyperthermia—AC losses of magnetic l0 l2
nanoparticles and mechanisms of the losses—have v¼n (13)
been published, no systematic and collective inves- 3kB T
tigations have yet been performed. Recently, Carey
et al.44 proposed a theory for describing the The relaxation time is obtained by use of46:
response of an assembly of MNPs by using the pffiffiffi
Neel–Brown relaxation time. This model is based on p expðCÞ
the assumption that the magnetic system responds s¼ s0 pffiffiffiffi (14)
2 C
linearly as a function of the magnetic field
and is suitable for calculation of AC losses in where C = KeffV/kBT and s0 = 109 s.46
 Author's personal copy
Studies of the Magnetic Properties and Specific Absorption of Mn0.3Zn0.7Fe2O4 Nanoparticles 293

55
DT 1
80 Oe SA ¼ C: : (15)
50 Dt mFe
70 Oe
60 Oe in which C is the heat capacity of the material and
45 50 Oe mFe is the mass fraction of the magnetic component.
T (oC)

Reference 47 was used to obtain the value of

40 C = 670 J/kg K. The SA values obtained by use of
this method are shown in Fig. 9, which shows that
35 SA increases linearly with magnetic field, in good
agreement with data estimated by use of linearly
30 theory.
0 500 1000 1500 To directly compare values of SLP measured in
t (s) different laboratories and at different AC field
Fig. 8. Temperature versus time curves for Mn0.3Zn0.7Fe2O4 ferrite
strengths and frequencies, Kallumadil et al.48
nanoparticles, concentration 15 mg/mL, in applied fields from 50 Oe defined intrinsic loss power (ILP) as:
to 80 Oe at a fixed frequency of 236 kHz. SA
ILP ¼ 2 (16)
fH
5

4.5 The system-normalized ILP for this material is

SAexp. 0.5 nH m2/kg. Compared with the result in Ref. 48,
4 SAcalc. the ILP measured in this study is higher than that
3.5 of the best Micromode samples with the highest
SA (W/g)

3
2.5
2
1.5
1
45 50 55 60 65 70 75 80
H (Oe)
Fig. 9. Specific absorption of Mn0.3Zn0.7Fe2O4 ferrite nanoparticles
as a function of applied field: h, calculated by use of linear response
theory; o, determined experimentally.
Specific loss power (SLP) for the Mn0.3Zn0.7Fe2O4
nanopowder was calculated for magnetic fields with
f = 236 kHz and H0 = 50, 60, 70, or 80 Oe. The
values of P were 1.87, 2.70, 3.67 and 4.80 W/g,
respectively.
Figure 8 shows the variation of temperature with
heating time in different magnetic fields. From
Fig. 8 it is apparent that temperature increases
linearly with time in the initial stage of heating
then slows continuously and finally approaches
saturation. Note that the physical origin of the rapid
temperature increase in the initial stage can be
attributed to loss processes, hysteresis loss, eddy
current losses, Neel losses, and Brownian losses.
Because ferrites have very low conductivity, losses
from eddy current are negligible. So heat loss for
Mn0.3Zn0.7Fe2O4 NPs may be because of hysteresis
and relaxation losses. On the other hand, because
superparamagnetic behavior is observed for
Mn0.3Zn0.7Fe2O4 MNPs at room temperature, mea-
sured total heat generation can be attributed to
Neel losses and Brownian losses. The initial heating
rate, (dT/dt)|t=0, was obtained from these data and
used to calculate the SA by use of the equation:
ILP. Moreover, to the best our knowledge, such a
high ILP value has not previously been reported for
Mn0.3Zn0.7Fe2O4 nanoparticles.
CONCLUSION
Nanocrystalline Mn0.3Zn0.7Fe2O4 with the cubic
85 spinel structure was successfully synthesized by use
of a hydrothermal method. The spin dynamics of the
particles were analyzed on the basis of AC suscep-
tibility measurements. The SSG behavior of this
material is a result of strongly interacting super-
spins. However, the estimated negligible coercivity
and remanent magnetization at room temperature
are indicative of the superparamagnetic behavior of
these nanoparticles. The magnetic hyperthermia
properties of the powder were measured at 236 kHz
for a field range of 50–80 Oe. Specific absorption
calculated on the basis of linear response theory was
in good agreement with experimental data. The SA
can, however, be adjusted by varying the magnetic
field strength, so the material has important
potential for applications in in situ hyperthermia for
cancer therapy.
ACKNOWLEDGEMENTS
This research was funded by the Vietnam
National Foundation for Science and Technology
Development (NAFOSTED) under grant number
DT.NCCB-DHUD.2012-G/08. The authors would
like to acknowledge support from Dongguk Uni-
versity, Gyeongju.
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