J Nanopart Res (2013) 15:1359
DOI 10.1007/s11051-012-1359-6
RESEARCH PAPER
Yafet–Kittel-type magnetic order in Zn-substituted cobalt
ferrite nanoparticles with uniaxial anisotropy
R. Topkaya • A. Baykal • A. Demir
Received: 8 September 2012 / Accepted: 5 December 2012 / Published online: 16 December 2012
Ó Springer Science+Business Media Dordrecht 2012
Abstract Zn-substituted cobalt ferrite (ZnxCo1-
xFe2O4 with 0.0 B x B 1.0) nanoparticles coated with
triethylene glycol (TREG) were prepared by the
hydrothermal technique. The effect of Zn substitution
on temperature-dependent magnetic properties of the
TREG-coated ZnxCo1-xFe2O4 nanoparticles has been
investigated in the temperature range of 10–400 K and
in magnetic fields up to 9 T. The structural, morpho-
logical, and magnetic properties of TREG-coated
ZnxCo1-xFe2O4 NPs were examined using X-ray
diffraction (XRD), Fourier transform infrared (FT-IR)
spectra, transmission electron microscopy (TEM),
and vibrating sample magnetometry (VSM). The
average crystallite size estimated from X-ray line profile
fitting was found to be in the range of 7.0–10 nm. The
lattice constant determined using the Nelson–Riley
extrapolation method continuously increases with the
increase in Zn2? content, obeying Vegard’s law. TEM
analysis revealed that the synthesized particles
were nearly monodisperse, roughly spherical shaped
R. Topkaya (&)
Department of Physics, Gebze Institute of Technology,
41400 Gebze, Kocaeli, Turkey
e-mail: rtopkaya@gyte.edu.tr
A. Baykal
Department of Chemistry, Fatih University, B.Çekmece,
34500 Istanbul, Turkey
A. Demir
Department of Chemistry, İstanbul Medeniyet University,
Göztepe/Kadıköy, Istanbul, Turkey
nanoparticles in the size range of 9.0–15 nm. FT-IR
spectra confirm that TREG is successfully coated on
the surface of nanoparticles (NPs). The substitution of
non-magnetic Zn2? ions for magnetic Co2? ions
substantially changes the magnetic properties of the
TREG-coated ZnxCo1-xFe2O4 NPs. The saturation
magnetization and the experimental magnetic moment
are observed to initially increase (up to x = 0.2),
which is explained by Néel’s collinear two-sublattice
model, and then continuously decrease with further
increase in Zn content x. This decrease obeys the
three-sublattice model suggested by Yafet–Kittel
(Y–K). While the Y–K angle is zero for the CoFe2O4
NPs coated with TREG, it increases gradually with
increasing Zn concentrations and extrapolates to
82.36° for ZnFe2O4 NPs coated with TREG. The
increase in spin canting angles (Y–K angles) suggests
the existence of triangular (or canted) spin arrange-
ments in all the samples (except for the samples with
x = 0.0) under consideration in this work. From the
computation of Y–K angles for the TREG-coated
ZnxCo1-xFe2O4 NPs, it can be concluded that all the
zinc-doped cobalt ferrite nanoparticles (for x [ 0.0)
have a Y–K-type magnetic order, while the pure cobalt
ferrite nanoparticles (x = 0.0) have a Néel-type
magnetic order. Zero field cooled (ZFC) and field
cooled (FC) measurement results further verify that the
samples with 0.6 B x B 1.0 have superparamag-
netic behavior at room temperature, which shows
weak interaction between magnetic particles. The
blocking temperatures obtained from ZFC–FC curves
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Page 2 of 18
decrease as a function of Zn concentration. It was
found that the effective magnetic anisotropy, the
coercivity, and remanence magnetization continu-
ously decrease with increasing Zn concentration.
Lower reduced remanent magnetization (Mr/Ms) val-
ues (\0.5) suggest that all the samples have uniaxial
anisotropy. Ferromagnetic resonance (FMR) measure-
ment shows that the FMR spectra of all the samples
have broad linewidth because of the magnetic nano-
particles with randomly distributed anisotropy axes,
and the decrease in the internal field conversely leads
to the increase in the resonance field with respect to
increasing Zn concentration.
Keywords Magnetic nanoparticles  Ferromagnetic
resonance  Yafet–Kittel angle  Magnetic anisotropy
Introduction
Magnetic nanoparticles have attracted considerable
attention over the past few decades especially because
of their promising biomedical applications such as
magnetic resonance imaging (MRI) (Yang et al.
2010), hyperthermia (Apostolov et al. 2011), and
magnetically guided drug delivery (Portet et al. 2001).
Superparamagnetic nanoparticles have been recog-
nized as the next generation magnetic probes for a
wide range of biomedical applications because of the
fast response to applied magnetic fields with negligi-
ble remanence and coercivity (Yang et al. 2010; Rana
et al. 2010). However, due to their high surface area to
volume ratio, the nanoparticles agglomerate so as to
minimize high surface energy. Also, the nanoparticles
are chemically very active and easily oxidized in air.
All of these limit the potential usage of the nanopar-
ticles in biomedical applications (Lu et al. 2007).
To prevent agglomeration and oxidation in the
magnetic nanoparticles and to make them non-toxic,
stable, and biocompatible for biomedical applications,
the surface of the magnetic nanoparticles is coated by
the materials such as silica, gold, polymer, metal or
non-metal, and metal oxide (Laurent et al. 2008). Silica
is the most common coating material to prepare silica-
coated Fe3O4 nanoparticles (Tartaj et al. 2002; Santra
et al. 2001). Silica coating not only provides chemical
stability and better protection against toxicity, but also
prevents agglomeration between nanoparticles (Wu
123
J Nanopart Res (2013) 15:1359
et al. 2008). Polyethylene glycol (PEG), a biocompat-
ible water-soluble polymer, has currently been used as
coating material (Laurent et al. 2008). Zhang and Gupta
have reported that surfaces of superparamagnetic iron
oxide nanoparticles are coated with PEG; the biocom-
patibility and the circulation time of these nanoparticles
in the blood increase (Zhang et al. 2002; Gupta and
Curtis 2004). Cai and Wan (2007) developed a facile
route to prepare high performance magnetite nanopar-
ticles using a modified polyol process. Four types of
polyols including ethylene glycol (EG), diethylene
glycol (DEG), triethylene glycol (TREG), and tetra-
ethylene glycol (TEG) were investigated to directly
react with Fe(acac)3 to magnetite at elevated temper-
ature. It was observed that only the reaction of
Fe(acac)3 in TREG produced non-agglomerated and
uniform magnetite particles with narrow size distribu-
tion. This result was confirmed with a similar study
done with Intermetallic AuCu and AuCu3 Nanocrystals
and Nanowire Networks (Sra et al. 2005). TREG
provides a biocompatible water-dispersible coating,
prevents the surface oxidation of the nanoparticles and
interparticle aggregation, reduces nanoparticle toxicity,
and avoids detection by the body’s immune system (Cai
and Wan 2007). Therefore, it is a promising candidate
for use in biomedical applications as solvent, stabiliz-
ing, and capping agent (Wan et al. 2007).
In recent years, spinel-type ferrite nanoparticles have
been extensively investigated because of their excel-
lent and convenient magnetic and electrical properties
compared to their bulk counterparts (Altincekic et al.
2010; Köseoğlu et al. 2011). Among the family of spinel
ferrites, cobalt ferrite, CoFe2O4, has been studied in
detail because of its interesting properties, such as
strong magnetocrystalline anisotropy, moderate satura-
tion magnetization, high coercivity, excellent chemical
stability, and good mechanical hardness, which make it
a promising candidate for a lot of applications (Lee et al.
1998; Berkowitz and Schuele 1959). The magnetic
properties of the CoFe2O4 are known to greatly depend
on the chemical composition, cation distribution, prep-
aration method, particle size, surface properties of the
particles and inter-particle interactions, and substitution
with different metal elements. From recent research, it
was shown that the Zn2? substituting for Co2? in
CoFe2O4 nanoparticles (Co1-xZnxFe2O4) strongly
changed magnetic and structural properties of the cobalt
ferrite nanoparticles (Hou et al. 2010; Jadhav et al. 2010;
Vaidyanathan and Sendhilnathan 2008). It is well
J Nanopart Res (2013) 15:1359
known that ZnFe2O4 (x = l) has a normal spinel
structure with Zn2? ions in tetrahedral A sites and
Fe3? ions on octahedral B sites, whereas CoFe2O4
(x = 0) has inverse spinel structure with Co2? ions in
octahedral B sites and Fe3? ions equally distributed
between tetrahedral A and octahedral B sites (Miller
1959; Hastings and Corliss 1953; Upadhyay et al. 2004;
Navrotsky and Kleppa 1968).
Many authors have investigated the dependence of
saturation magnetization and magnetic moment values
on Zn concentration in Zn-substituted cobalt ferrites
(Jadhav et al. 2010; Vaidyanathan and Sendhilnathan
2008; Rani et al. 2012; Birajdar et al. 2005). Jadhav et al.
(2010) reported that the saturation magnetization and
magnetic moment values increase up to x = 0.2 in Co1-
xZnxFe2O4 nanoparticles. Vaidyanathan and Sendhilna-
than (2008) observed that the variation of the saturation
magnetization as a function of Zn content showed an
increase for small substitutions and went through a
maximum for x = 0.1 in Co1-xZnxFe2O4 nanoparticles
prepared by the chemical co-precipitation method. A
similar increase to some extent has been reported by
some authors (Rani et al. 2012; Birajdar et al. 2005;
Islam et al. 1998). The reason for this increase has been
explained with Néel’s (1950) collinear two-sublattice
model of ferrimagnetism. However, it was observed in
these studies that saturation magnetization and magnetic
moment then decrease with a further increase in Zn
content x. This decreasing is explained on the basis of
the three-sublattice model suggested by Yafet and Kittel
(1952).
However, to our knowledge, the influence of the
zinc substitution on magnetic properties of TREG-
coated ZnxCo1-xFe2O4 nanoparticles (0.0 B x B 1.0)
has not been extensively reported so far in the
literature. In this work, the magnetic properties of the
zinc-substituted cobalt ferrite nanoparticles (ZnxCo1-
xFe2O4) coated with TREG prepared by a hydrothermal
technique have been investigated in detail in the
temperature range of 10–400 K and in magnetic fields
up to 9 T.
Experimental details
In this work, we have focused on the Zn substitution
dependence of the magnetic properties of TREG-coated
ZnxCo1-xFe2O4 NPs (0.0 B x B 1.0) synthesized by
the hydrothermal method. CoCl24H2O, FeCl32H2O,
Page 3 of 18
ZnCl26H2O, NaOH, and TREG were purchased from
Merck and used without further purification. A stoichi-
ometric amount of metal chlorides was entirely dis-
solved in 20 ml distilled water under magnetic stirring.
Then, 2 ml TREG was added to the above mixture,
followed by the addition of a certain amount of sodium
hydroxide solution until the mixture had a pH value of
11. After the mixture was continuously stirred for 1 h, a
homogeneous solution was obtained. The mixed solu-
tion was poured into a Teflon-lined stainless-steel
autoclave of 60-ml capacity with a filling degree of
60 %. The autoclave was heated and maintained at
150 °C for 12 h, and then cooled down to room
temperature by removing the heat source. The products
were filtered and washed with distilled water and
absolute ethanol for several times, and then finally dried
in a vacuum oven at 70 °C for 6 h (Scheme 1).
X-ray powder diffraction (XRD) analysis was
conducted on a Rigaku Smart Lab Diffractometer
operated at 40 kV and 35 mA using Cu Ka radiation
(k = 1.54059Å). Fourier transform infrared (FT-IR)
spectra of the samples were recorded in the transmis-
sion mode with a Perkin Elmer BX FT-IR infrared
spectrometer in the range of 4000–400 cm-1. The
powder samples were ground with KBr and com-
pressed into a pellet. Transmission electron micros-
copy (TEM) analysis was performed using a FEI
Tecnai G2 Sphera microscope. A drop of diluted
sample in alcohol was dripped onto a TEM grid. The
magnetization measurements were performed using a
vibrating sample magnetometer (VSM, Quantum
Design, PPMS 9 T) in an external field up to 90 kOe
in the temperature range of 10–400 K. The ferromag-
netic resonance (FMR) measurements were carried out
using a Bruker EMX model X-band electron spin
resonance spectrometer at a microwave frequency of
9.8 GHz.
OH
HO OH OH
OO
ZnCl 2 HO O O OH
O O
+ O OH HO
HO O O ZnxCo1-x Fe2O4 O OH
CoCl2 O
O
+ triethylene glycol HO
OH
O
HO O O O
FeCl 3 OO OH
HO HO
OH
HO
Scheme 1 Schematical representation of synthesis of TREG-
coated ZnxCo1-xFe2O4
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Page 4 of 18 J Nanopart Res (2013) 15:1359

Results and discussion Fig. 2 TEM images of TREG-coated ZnxCo1-xFe2O4 NPs with c
a x = 0.0, b x = 0.2, c x = 0.4, d x = 0.6, e x = 0.8, and
f x = 1.0
XRD analysis
r, are tabulated in Table 1 as a result of this line profile
X-ray powder diffraction patterns of TREG-coated fitting.
ZnxCo1-xFe2O4 NPs (0.0 B x B 1.0) synthesized by The exact lattice parameter of each sample was
the hydrothermal method are shown in Fig. 1. All determined from the XRD data using the Nelson–
XRD peaks in the pattern match well with the standard Riley extrapolation method (Köseoğlu et al. 2009;
data of ZnFe2O4 (JCPDS card no. 89-1012) and Gözüak et al. 2009) and is listed in Table 1. It was
CoFe2O4 (JCPDS card no. 22-1086). The average observed that the lattice constant of TREG-coated
crystallite size was estimated from the powder ZnxCo1-xFe2O4 NPs increases linearly with increas-
diffraction patterns by the line profile fitting method ing Zn concentration obeying Vegard’s law (Denton
using Eq. (1) given in the study of Wejrzanowski et al. and Ashcroft 1991). This increase can be attributed to
(2006). The line profile, shown in Fig. 1, was fitted for the variation of ionic sizes of the Zn2? and Co2?
observed six peaks with the following miller indices, cations because the ionic size of Co2? (0.72 Å) is
(220), (311), (400), (422), (511), and (440), and the lower than that of Zn2? (0.74 Å) (Akther Hossain et al.
average crystallite size, DXRD, and standard deviation, 2008). Thus, the values of the determined lattice
constants for all the samples were found between the
values of the lattice constants of ZnFe2O4 and
CoFe2O4. A similar behavior was also reported by
311

Akther Hossain et al. (2008) and Patil et al. (2009).

440
511
220

400

422
Intensity (arb.units.)

a)
TEM analysis
b)

c) Figure 2 shows TEM images of TREG-coated ZnxCo1-

d) xFe2O4 NPs (0.0 B x B 1.0). Their particle size distri-
bution histograms determined from the TEM images
e)
are also presented in Fig. 3. Through TEM images, the
f) size and morphology of these as-prepared ferrite
samples were further investigated. It is easily seen
20 30 40 50 60 70 from th TEM images in Fig. 2 that the particles are well
2 Theta (degree) separated from each other to count the particles, but
somehow little agglomeration is observed between the
Fig. 1 XRD powder patterns and line profile fitting of TREG-
particles in all the samples under consideration. It is
coated ZnxCo1-xFe2O4 NPs: (a) x = 0.0, (b) x = 0.2,
(c) x = 0.4, (d) x = 0.6, (e) x = 0.8, and (f) x = 1.0 known that magnetic nanoparticles attract each other

Table 1 Crystallite size (DXRD) with standard deviation (r), particle size (DTEM), lattice constant (ao), saturation magnetization (Ms)
for RT and 10 K, blocking temperature (TB) and Y–K angle (aYK) for ZnxCo1-xFe2O4 NPs coated with TREG (0.0 B x B 1.0)
x Av. size ao (Å) Ms (emu g-1) (RT) Ms (emu g-1) (10 K) TB (K) aYK (°)
DXRD (nm) DTEM (nm)

0.0 9±5 14.8 ± 0.2 8.381 (0.002) 74.5 88.8 – 0

0.2 8±3 8.9 ± 0.3 8.405 (0.003) 76.6 103.06 – 30.6
0.4 7±3 9.4 ± 0.1 8.415 (0.001) 64.1 102.3 308 49.46
0.6 8±3 9.2 ± 0.2 8.421 (0.002) 57.1 105.4 230 62.52
0.8 10 ± 3 11.6 ± 0.2 8.431 (0.003) 33.3 79.5 94 75.4
1.0 7±3 9.3 ± 0.2 8.435 (0.001) 30.8 78.7 51 82.36

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123
Page 6 of 18 J Nanopart Res (2013) 15:1359

60
(a) (b)
30
Relative Frequency %

Relative Frequency %
40

20

20
10

0 0
12 14 16 18 20 8 12 16 20
Diameter (nm) Diameter (nm)

40
(c) 40
(d)

30
30
Relative Frequency %

Relative Frequency %

20
20

10
10

0 0
6 8 10 12 14 6 8 10 12 14
Diameter (nm) Diameter (nm)

30
(e) (f)
30
Relative Frequency %

Relative Frequency %

20

20

10
10

0 0
6 8 10 12 14 6 8 10 12 14

Fig. 3 The particle size distribution histograms derived from TEM images and log-normal fits for TREG-coated ZnxCo1-xFe2O4 NPs
with a x = 0.0, b x = 0.2, c x = 0.4, d x = 0.6, e x = 0.8, and f x = 1.0

123
J Nanopart Res (2013) 15:1359
by van der Waals forces and magnetic dipolar interac-
tions. The reason for why there is almost no agglomer-
ation in any of the as-prepared samples is the presence of
steric barrier originating from the strong hydrophilic
TREG ligands coated on the nanoparticles as surfactant
during the synthesis. Also, the presence of TREG coating
on the surface of the nanoparticles was confirmed by FT-
IR analysis. It can be seen that the nanoparticles have a
roughly spherical shape. The particle size distribution
histograms were obtained by counting a total of 150
particles in the TEM images for each sample. It is found
that the average particle sizes are in the range of
9.0–15 nm. It should be noted that these values are in
good agreement with the crystallite sizes estimated from
the X-ray line profile fitting from XRD patterns for all the
samples used in this study. In this study, it is concluded
from the TEM images of these monodisperse nanopar-
ticles that the magnetic nanoparticles are coated with
TREG, which is suitable for the biomedical applications.
FT-IR analysis
FT-IR spectra of TREG-coated ZnxCo1-xFe2O4 NPs
are presented in Fig. 4. In the FT-IR spectra presented
in Fig. 4, two characteristic bands at 2925–2810 cm-1
of C–H stretching and 1116–1050 cm-1 of C–O
stretching in spectra confirm the attachment of TREG
on the ZnxCo1-xFe2O4 NP’s surfaces, Fig. 4. No
evidence of other organic species is found in the
spectra. The broad band (3600–2500 cm-1) centered
at 3430 cm-1 can be assigned to hydrogen-bonded O–
H stretching vibration arising from surface hydroxyl
groups on nanoparticles and adsorbed TREG and
water (Duong et al. 2007; Kumar et al. 2008; Yang
et al. 2010; Cai and Wan 2007). The bands at 2923 and
2845 cm-1 are assigned to the stretching of C–H
group and the bands at 1120–1060 cm-1 to the C–O
stretching. The broad band centered at 3430 cm-1 can
be assigned to hydrogen-bonded O–H stretching
vibration arising from surface hydroxyl groups on
nanoparticles and adsorbed TREG and water (Fiorani
and Viticoli 1985).
Two main broad metal–oxygen bands are seen in the
FT-IR spectra of all spinels, and ferrites in particular.
The band observed at round 561 cm-1 for TREG-
stabilized ZnFe2O4 NPs (x = 0.0) can be assigned to
tetrahedral Zn2? stretching, m1, and the band observed
at 453 cm-1 involves the Fe3? vibration at the
octahedral site, m2. As the mole content of Zn is
Page 7 of 18
a
Transmittance % (arb.units)
f
Transmittance % (a.u.)
550
532
700 650 600 550 500
-1
450
Wavenumber (cm )
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
Fig. 4 FT-IR spectra of TREG-coated ZnxCo1-xFe2O4 NPs
with (a) x = 0.0, (b) x = 0.2, (c) x = 0.4, (d) x = 0.6,
(e) x = 0.8, and (f) x = 1.0
increasing, m1 stretching is also decreasing linearly.
Stretching wave number is inversely proportional to
the atomic weight. Due to the low atomic weight of Co,
as Co mole content increases, m1 is increasing from
561 cm-1 for ZnFe2O4 to 582 cm-1 for CoFe2O4
(Baykal et al. 2008, 2009). It seems that the m1 band
shifts slightly toward the lower wave numbers with
increase in x over the composition range (inset in
Fig. 4) and indicating weakening of the metal–oxygen
bonds in the tetrahedral sites due to the transition
between the extent of normal spinel and inverse
structures (Sertkol et al. 2009).
Magnetic measurements
Figure 5 shows the M–H curves for TREG-coated
ZnxCo1-xFe2O4 NPs with different Zn concentrations
taken at room temperature (a) and 10 K (b). The
magnetization curves of all the samples were recorded
at different temperatures in the range of 10–300 K up
to a maximum magnetic field strength of 90 kOe. The
inset in Fig. 5a shows the low field part of the RT
hysteresis loops (between ±2 kOe). It is observed from
the inset in Fig. 5a that at the low Zn concentrations
(0.0 B x B 0.4), TREG-coated ZnxCo1-xFe2O4 NPs
show a typical magnetic hysteresis loop at room
temperature (300 K). This indicates that TREG-coated
ZnxCo1-xFe2O4 NPs with Zn concentration for x B 0.4
have ferromagnetic behavior at room temperature
(RT). However, at the higher Zn concentrations
(0.6 B x B 1.0), the coercive fields and remanences
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Page 8 of 18 J Nanopart Res (2013) 15:1359

90 120
20

Magnetization (emu/g) 10
Magnetization (emu/g)

Magnetization (emu/g)
0
45 60
-10

-20

-2 -1 0 1 2
Magnetic Field (kOe)
0 0
x=0.0 x=0.0
x=0.2 x=0.2
x=0.4 x=0.4
-45 x=0.6 -60
x=0.6
x=0.8 x=0.8
x=1.0 (b) x=1.0
(a)
-90 -120
-90 -60 -30 0 30 60 90 -90 -60 -30 0 30 60 90
Magnetic Field (kOe) Magnetic Field (kOe)

Fig. 5 The magnetic hysteresis loops of TREG-coated ZnxCo1-xFe2O4 NPs with different Zn concentrations at a RT and b 10 K

of TREG-coated ZnxCo1-xFe2O4 NPs are almost literature by several authors (Pankhurst and Pollard
negligible, indicating that TREG-coated ZnxCo1- 1991; Li et al. 2010; Montoya and Rinaldi 2010). The
xFe2O4 NPs with Zn concentration for x C 0.6 have spinel ferrites with cubic crystal structure have two
superparamagnetic behavior at RT. At room temper- different crystallographic sublattices for magnetic ions,
ature, these superparamagnetic samples in this study tetrahedral (A) and octahedral (B) sublattices. The
can be used for biomedical applications such as magnetic order of the spinel ferrites mainly results from
hyperthermia treatment (Apostolov et al. 2011) and super-exchange interaction between the magnetic ions
MRI (Yang et al. 2010). Low temperature hysteresis in the A and B sublattices mediated by oxygen ions.
loops were measured after zero field cooling. Also, it According to the Néel’s two-sublattice model of
can be easily seen from Fig. 5b that all the samples ferrimagnetism, the magnetic moments of ions on the
have ferromagnetic behavior with an opened hysteresis A and B sublattices are aligned antiparallel to each other
loop at 10 K. The saturation magnetization value at and their spins have a collinear structure. Therefore,
10 K compared to room temperature saturation mag- total magnetization is Moct - Mtet (Moct and Mtet are the
netization increases because of a decrease in thermal sum of the magnetic moments on B sublattice and A
fluctuations’ effects on magnetic ions. sublattice, respectively) (Néel 1950; Chikazumi 1997).
The room temperature saturation magnetization (Ms)
was estimated from the interception of the magnetiza- 100
tion axis with 1/H axis as 1/H approaches zero. The
variation of saturation magnetization (Ms) as a function
of Zn concentration is shown in Fig. 6 and Table 1 75
shows the value of saturation magnetization of the
M S (emu/g)

samples used in this study for room temperature (300 K)

50
and 10 K. It can be seen that the Ms of TREG-coated
ZnxCo1-xFe2O4 NPs is strongly dependent on the Zn
concentration. Ms values of all samples at RT are lower 25
than that of the bulk cobalt ferrite (80 emu g-1) (Cullity
and Graham 2009) due to surface spin disorder or spin
canting effects (Coey 1971; Kodama et al. 1996; 0
0.0 0.2 0.4 0.6 0.8 1.0
Martinez et al. 1998). The spin orientation at the surface
Zn concentration (x)
cannot be the same as that of the magnetic core and
hence reduces the saturation magnetization. Similar Fig. 6 Variation of the saturation magnetization (Ms) of
reduced magnetization values have been reported in the TREG-coated ZnxCo1-xFe2O4 NPs with Zn concentration at RT

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J Nanopart Res (2013) 15:1359
In the present study, with increasing Zn concentration
from 0 to 0.2, Ms increases from 74.5 to 76.5 emu g-1.
These magnetization values are very high and close to
that of the bulk cobalt ferrite despite the coating with
TREG. These higher Ms values of the CoFe2O4 and
Zn0.2Co0.8Fe2O4 NPs coated with TREG can be suitable
for biomedical applications like hyperthermia.
The variation of saturation magnetization with
concentration of ferrite nanoparticles can be explained
on the basis of cation distribution and of strength of the
exchange interaction between the ions at the tetrahe-
dral (A) and octahedral (B) sites. Site-preference
calculations (Miller 1959), neutron-diffraction studies
(Hastings and Corliss 1953), and Mössbauer spectros-
copy studies (Upadhyay et al. 2004) showed that Zn2?
ions with zero magnetic moment have a strong
preference to occupy the tetrahedral A sites, and also
Fe3? ions have a stronger preference to occupy the
tetrahedral A sites as compared to the octahedral B
sites (Navrotsky and Kleppa 1968).
As zinc is introduced in the system, it pushes Fe3?
ions from tetrahedral A sites to octahedral B sites
(Upadhyay et al. 2004). This causes the increase in
magnetization of TREG-coated ZnxCo1-xFe2O4 fer-
rites. That is, while the magnetic moment of the A site
decreases due to increase of non-magnetic Zn ions in
the A site, the magnetic moment of the B site increases
due to increase of Fe3? ions in B site. Therefore, in
present study, when the Zn concentration x increases
from 0 to 0.2, total magnetization (Moct - Mtet) of
TREG-coated ZnxCo1-xFe2O4 NPs increases due to
the increase of inter-sublattice A–B super-exchange
interaction between the magnetic ions of the sublat-
tices A and B. This increase in saturation magnetiza-
tion with Zn concentration from x = 0.0 to x = 0.2 is
a good agreement with Néel’s collinear two-sublattice
model (Néel 1950). A similar result for Zn-substituted
cobalt ferrites has been reported by several authors
(Jadhav et al. 2010; Rani et al. 2012; Vaidyanathan
and Sendhilnathan 2008; Birajdar et al. 2005). After-
ward, with further increase in the Zn concentration
from x = 0.2 to x = 1.0, the saturation magnetization
gradually decreases from 76.5 to 30.8 emu g-1. In
order to explain the variation of the saturation
magnetization with respect to Zn concentration, the
magnetic moment values were calculated as a function
of Zn concentration.
According to Néel’s two-sublattice model of ferrimag-
netism, the magnetic moments of ions on the tetrahedral
Page 9 of 18
(A) and octahedral (B) sites are aligned antiparallel to
each other and their spins have a collinear structure (Néel
1950; Chikazumi 1997). Therefore, the theoretic mag-
netic moment per formula unit in lB, ntB , is described as
n tB ðxÞ ¼ MB ðxÞ  MA ðxÞ; ð1Þ
where MB(x) and MA(x) are the B and A sublattice
magnetic moments in lB, respectively. The cation
distribution of the ZnxCo1-xFe2O4 NPs coated with
TREG can be written as

 
Znx 2þ Feð1xÞ 3þ A Coð1xÞ 2þ Feð1þxÞ 3þ B O4 2 :
ð2Þ
As a function of Zn concentration, the theoretic
magnetic moment values, ntB , of the ZnxCo1-xFe2O4
NPs coated with TREG were calculated using the
cation distribution given in Eq. 2 and the ionic
magnetic moments of Fe3?, Co2?, and Zn2? as 5 lB,
3 lB, and 0 lB, respectively. The experimental values
of the magnetic moments, neB , per unit formula in Bohr
magnetron (lB) were calculated according to the
relation (Smit and Wijn 1959)
MW  Ms
neB ¼ ; ð3Þ
5585
where Mw is the molecular weight, Ms is the saturation
magnetization, and 5585 is the magnetic factor. The
variation of the theoretic magnetic moment and
experimental magnetic moment (ntB andneB ; respec-
tively) with respect to Zn composition in the ZnxCo1-
xFe2O4 NPs coated with TREG is represented in
Fig. 7. It can be seen from Fig. 7 that the theoretic
magnetic moment, ntB , increases linearly as a function
of Zn concentration, and also the experimental mag-
netic moment, neB , increases with Zn concentration of
up to x = 0.2 and then gradually decreases with
further increase in Zn concentration. This increase in
neB with Zn concentration of up to x = 0.2 can be
attributed to the Néel’s collinear two-sublattice model.
However, this model is unable to explain the decrease
of neB (and hence Ms) with Zn concentration for
x [ 0.2. The decrease in neB (and hence Ms) for
x [ 0.2, which results from the existence of non-
collinear spin arrangement in the system, can be
explained on the basis of the three-sublattice model
suggested by Yafet and Kittel (1952). When higher
Co2? ions are substituted by Zn2? ions in the ZnxCo1-
xFe2O4 NPs coated with TREG, the magnetic ions of
123
Page 10 of 18
10
e
nB (experimental)
nB
t
(theoretical)
Magnetic Moment, nB ( µB )
8
6 Yafet and Kittle (Y–K) angle have been calculated
4
2
0.0 0.2 0.4 0.6
Zn concentration (x)
Fig. 7 Variation of magnetic moment, nB of TREG-coated
ZnxCo1-xFe2O4 NPs with Zn concentration at RT
tetrahedral A site are so much decreased that the
dominant inter-sublattice A–B super-exchange inter-
action becomes weaker and hence the intra-sublattice
B–B super-exchange interaction strengthens, which in
turn results in occurrence of random spin canting on
the B site with respect to the direction of spins of the A
site. Therefore, it can be reasonably concluded that the
canted (non-collinear) spins lead to a decrease in the
values of the experimental magnetic moment (and thus
the magnetization) with Zn concentration for x [ 0.2.
Mazen and Abu-Elsaad (2012), from their study on the
magnetic properties of manganese-substituted lithium
ferrite system with high content of Mn, have observed
the occurrence of triangular spin arrangements on B
sites resulting in a decrease of experimental magnetic
moment and also magnetization, which is a good
agreement with our experimental results. The signif-
icant difference between the experimental and theo-
retic magnetic moment values suggests that the
magnetic order in the present ferrite system is not
governed by the Néel-type magnetic order, but by the
Yafet–Kittel (Y–K)-type magnetic order (Akther
Hossain and Rahman 2011; Birajdar et al. 2005).
According to the Y–K model, the B lattice can be
divided into two sublattices, B1 and B2, each having
magnetic moments equal in magnitude and each
oppositely canted at the same angle, aYK , relative to
123
J Nanopart Res (2013) 15:1359
the net magnetization at 0 K. In this way, the two
sublattices B1 and B2 have the triangular spin
arrangement which becomes more significant with
the changing concentration. The existence of canted
spin and the behavior of the magnetic moment with
increasing Zn concentration can be observed by
determining the Y–K angle (aYK ). The values of the
using the formula
neB ¼ MB cos aYK  MA ; ð4Þ
where neB
is the experimental magnetic moment
expressed in the units of Bohr magneton and MA and
MB are the Bohr magneton on the A site and B sites,
respectively. The variation of the calculated Y–K
angles for different concentrations of the TREG-
0.8 1.0 coated ZnxCo1-xFe2O4 NPs is shown in Fig. 8 and the
values of the Y–K angles for each sample are listed in
Table 1. The Y–K angle is zero for the TREG-coated
ZnxCo1-xFe2O4 NPs for x = 0.0, indicating that the
magnetization can be explained on the basis of the
Néel’s two-sublattice theory for only the sample with
x = 0.0 in the present study. That is, the sample
CoFe2O4 NPs coated with TREG show a Néel-type of
magnetic ordering. It is clear from Fig. 7 that the
calculated value of the Y–K angles gradually increases
with the increase of Zn concentration and finally
extrapolates 82.36° for the ZnFe2O4 NPs (x = 1.0).
The non-zero Y–K angles suggest that for all the
samples (for x [ 0.0), the magnetization behavior
cannot be explained on the Néel two-sublattice model
due to the presence of non-collinear spin structure on
100
75
Y-K angle ( )
o
50
25
0
0.0 0.2 0.4 0.6 0.8 1.0
Zn concentration (x)
Fig. 8 The variation of Y–K angle with Zn concentration for
TREG-coated ZnxCo1-xFe2O4 NPs
J Nanopart Res (2013) 15:1359
B sites, which strengthens the B–B interaction and
thus decreases the A–B interaction. The increase in
spin canting angles (Y–K angles) for the samples with
x [ 0.0 with the increase in Zn content suggests the
increased favor for triangular spin arrangements on B
sites resulting in the decreasing in the A–B exchange
interaction and the existence of canted spin arrange-
ments in all the samples (for x [ 0.0) under consid-
eration in this study. Therefore, it also leads to a
reduction in saturation magnetization after Zn con-
centration with x [ 0.2. This indicates that in the
present system of TREG-coated ZnxCo1-xFe2O4 NPs
with the increasing of Zn concentration, randomness
and frustration increase and show significant departure
from the Néel-type collinear magnetic order (Ajmal
and Maqsood 2008). Similar results have been also
reported for Cu–Mn ferrites (Rana et al. 2003) and
Mn–Li ferrites (Mazen and Abu-Elsaad 2012). It can
be concluded from the evaluation of Y–K angles for
the TREG-coated ZnxCo1-xFe2O4 NPs
(0.0 B x B 1.0) that the TREG-coated ZnxCo1-
xFe2O4 NPs with x [ 0.0 have a Y–K-type magnetic
order, while the TREG-coated CoFe2O4 NPs (x = 0.0)
have a Néel-type magnetic order. In other words, in
this study, all the Zn-doped cobalt ferrite nanoparticles
(except for the pure cobalt ferrite NPs) show a Y–K-
type of magnetic ordering.
Figure 9 shows zero field cooled (ZFC) and field
cooled (FC) curves of the TREG-coated ZnxCo1-
xFe2O4 NPs (0.0 B x B 1.0) measured in the temper-
ature range of 10–400 K under an applied field of
50 Oe. Firstly, the NPs were cooled down without any
external magnetic field and then the magnetization
(MZFC) of NPs was recorded during heating up to
400 K under an applied field of 50 Oe. Later, the NPs
were cooled down again in an applied field of 50 Oe
and then the magnetization (MFC) of NPs was recorded
during heating up to 400 K under an applied field of
50 Oe. As the temperature increases in ZFC measure-
ment, firstly, the MZFC increases and then achieves a
maximum value at specific critical temperature, which
is called the blocking temperature, TB. Above TB, in
the unblocked region, the MZFC monotonically
decreases with increasing temperature. This is the
characteristic behavior of superparamagnetic materi-
als. As can be seen from Fig. 9, in the present study,
only the TREG-coated ZnxCo1-xFe2O4 NPs with Zn
concentration of 0.6 B x B 1.0 show superparamag-
netic behavior at RT, indicating that for these samples,
Page 11 of 18
magnetic interactions between their particles are weak
and that these samples can be regarded as good
candidates for the biomedical applications. The ZFC
and FC measurements of all the ZnxCo1-xFe2O4 NPs
coated with TREG except for the samples with Zn
concentration (x = 0.0 and 0.2) show an irreversible
magnetic behavior below the temperature, called
irreversibility (Tirr) temperature. Tirr is defined as the
temperature at which the ZFC and FC curves split
from each other and corresponds to the blocking
temperature of the largest nanoparticles in the super-
paramagnetic systems (Hansen and Mørup 1999).
Figure 10 shows the variation of the coercive field,
Hc, as a function of temperature for the TREG-coated
ZnxCo1-xFe2O4 NPs (0.0 B x B 1.0). It can be easily
seen that the Hc strongly depends on both Zn
concentration, x, and temperature. Also, Hc substan-
tially increases with decreasing temperature. This is
due to the increasing of the effective magnetic
anisotropy with decreasing temperature because the
content of the Co2? ions on the octahedral (B) sites
increases with decreasing temperature (Franco and
Silva 2010). In this study, the coercive field value of
pure cobalt ferrite coated with TREG is 11353 Oe at
10 K, which is much larger than that of bulk CoFe2O4
(about 5 kOe at 5 K). At low temperatures, the frozen
surface spins resulting from coating material are
strongly pinned with ordered core spins by exchange
interactions, and thus extra energy is needed to switch
the ordered core spins. This interaction in the ZnxCo1-
xFe2O4 NPs coated with TREG can be the reason for
the observed increase in coercive field at low temper-
atures (Martinez et al. 1998). Similar results have been
reported in metal-substituted ferrite particles
(Köseoğlu et al. 2012; Melikhov et al. 2006).
The variation of remanence magnetization, Mr, with
Zn concentration in the TREG-coated ZnxCo1-xFe2O4
NPs (0.0 B x B 1.0) at room temperature is depicted
in Fig. 11. The inset in Fig. 11 shows the change in the
reduced remanent magnetization (Mr/Ms) with the Zn
concentration. As shown, the Mr of only the TREG-
coated ZnxCo1-xFe2O4 NPs (0.6 B x B 1.0), and thus
Mr/Ms is zero, which proves that these samples are
superparamagnetic at room temperature. As shown in
the inset in Fig. 11, the Mr/Ms gradually decreases with
increasing Zn concentration and all Mr/Ms values are
lower than the theoretic value of 0.5. This can be
explained with decreasing magnetic anisotropy depend-
ing on the increasing Zn concentration (Fendler 1998).
123
Page 12 of 18 J Nanopart Res (2013) 15:1359

15 CoFe 2O 4 Zn 0.2 Co 0 .8Fe 2O 4

Magnetization (emu/g) 5

Magnetization (emu/g)
14 4

13 3 ZFC
FC
ZFC 2
12
FC

0 100 200 300 400 0 100 200 300 400

Temperature (K) Temperature (K)

3 5
Zn 0 .4C o 0.6 Fe2O 4 Zn 0 .6C o 0.4 Fe2O 4
Magnetization (emu/g)

Magnetization (emu/g)
4
2

3
1

2
0
ZFC 1 ZFC
-1 FC FC
0
0 100 200 300 400 0 100 200 300 400

Temperature (K) Temperature (K)

4
Zn 0 .8C o 0.2 Fe 2O 4 ZnFe2 O 4
Magnetization (emu/g)

Magnetization (emu/g)

3
3

2
2

1
1 ZFC ZFC
FC FC
0
0 100 200 300 0 100 200 300
Temperature (K) Temperature (K)

Fig. 9 Zero field cooled (ZFC) and field cooled (FC) curves of the ZnxCo1-xFe2O4 nanoparticles coated with TREG under an applied
magnetic field of 50 Oe

According to the Stoner–Wohlfarth model, Mr/Ms for
an assembly of non-interacting 3D random particles is
given by Mr/Ms = 0.5 for uniaxial anisotropy and Mr/
Ms = 0.832 for cubic anisotropy (Stoner and Wohlf-
arth 1948).
As seen from the inset in Fig. 11, the Mr/Ms values of
all the samples are lower than 0.5 in this study. These
reduced remanent magnetization values observed in the
inset in Fig. 11 are more in agreement with uniaxial
anisotropy rather than the expected cubic anisotropy
according to the Stoner–Wohlfarth model. Therefore,
it can be concluded that all the samples used in this
study have uniaxial anisotropy because their reduced
remanent magnetization values are lower than 0.5.
Cobalt-substituted ferrite nanoparticles with uniaxial
anisotropy have been reported by some authors

123
J Nanopart Res (2013) 15:1359 Page 13 of 18

12 particles is given by Hc = 0.985 Keff/Ms for uniaxial

x=0.0 anisotropy and Hc = 0.64 Keff/Ms for cubic anisotropy
x=0.2 (Stoner and Wohlfarth 1948). It was found from the
9 x=0.4 Mr/Ms results that all the samples in this study have
x=0.6
uniaxial anisotropy. Therefore, to calculate the Keff,
H C (kOe)

6 x=1.0
3
0 samples. The coercive field is associated to the
0 100
Temperature (K)
Fig. 10 Temperature dependence of the coercive field, Hc, for
the TREG-coated ZnxCo1-xFe2O4 NPs (0.0 B x B 1.0)
(Victoria et al. 2007; Ammar et al. 2001). The uniaxial
anisotropy in magnetic nanoparticles can arise from
surface effects (Kodama 1999). The lower Mr/Ms values
than 0.3 found for the samples with x = 0.2 and 0.4 in this
study suggest that the interactions between the nanopar-
ticles are not negligible (Hadjipanayis et al. 1981).
Figure 12 shows the variation of the coercive field,
Hc, and effective magnetic anisotropy constant, Keff,
with respect to Zn concentration x at room tempera-
ture. It can be easily seen from Fig. 12 that the
coercive field, Hc, and effective magnetic anisotropy
constant, Keff, decrease with increasing Zn concentra-
tion x. According to the Stoner–Wohlfarth model, Hc
for an assembly of non-interacting 3D random
30
x=0.8
the relation Hc = 0.985 Keff/Ms was used. As shown as
from Fig. 5, 10, and 12, the Hc is almost negligible at
room temperature for only the TREG-coated ZnxCo1-
xFe2O4 NPs with 0.6 B x B 1.0, indicating the exis-
tence of superparamagnetic behavior for only these
200 300 strength of the magnetic field that is required to
overcome the anisotropy barrier. According to the
Stoner–Wohlfarth theory, magnetic anisotropy energy
(EA) for non-interacting single-domain particles is
given by
EA ¼ KV sin2 h; ð5Þ
where K, V, and h are magnetic anisotropy energy
constant, volume of the particles, and the angle
between magnetization direction and the easy axis of
a nanoparticles, respectively (Stoner and Wohlfarth
1948). With reducing of magnetic anisotropy, the
magnetic anisotropy energy barrier (EA) decreases,
which causes lower external magnetic field for spin
reversal. The strong magnetocrystalline anisotropy of
cobalt ferrite is mainly due to the presence of Co2?
ions in the octahedral (B) sites of the spinel structure
(Tachiki 1960). When the Zn concentration increases
in cobalt ferrite, the concentration of the Co2? ions in
the octahedral (B) sites decreases, which leads to

Anisotropy Constant, K eff (x10 erg/cm )

0.4 0.8
Mr / Ms
1200
0.3 Hc
Mr / Ms

Coercive Field, Hc (Oe)

20 0.2 0.6
Keff
Mr (emu/g)

800
0.1

0.0 0.4
10 0.0 0.2 0.4 0.6 0.8 1.0 400
Zn concentration (x)
0.2
0
5

Mr
0
0.0
0.0 0.2 0.4 0.6 0.8 1.0
3

0.0 0.2 0.4 0.6 0.8 1.0

Zn concentration (x)
Zn concentration (x)
Fig. 11 The remanence magnetization, Mr, versus Zn concen-
tration taken at room temperature for the TREG-coated ZnxCo1- Fig. 12 Composition dependence of coercive field, Hc, and
xFe2O4 NPs (0.0 B x B 1.0). Inset presents the change in
effective magnetic anisotropy constant, Keff, of the TREG-coated
reduced remanent magnetization (Mr/Ms) with Zn content ZnxCo1-xFe2O4 NPs (0.0 B x B 1.0) at room temperature

123
Page 14 of 18
decreasing the effective magnetic anisotropy. There-
fore, in this study, the effective magnetic anisotropy,
Keff, and accordingly coercive field, Hc, of the TREG-
coated ZnxCo1-xFe2O4 NPs decrease with increasing
Zn concentration. The decreasing of the effective
magnetic anisotropy, Keff, and thus coercive field, Hc,
with increasing Zn concentration is generally the
expected behavior in the metal-substituted ferrite
particles (Jadhav et al. 2010; Köseoğlu et al. 2012).
At blocking temperature TB, the magnetic anisot-
ropy energy barrier of the single-domain nanoparticles
Keff V is overcome by thermal energy kTB, where Keff
and V are magnetic anisotropy energy constant and
volume of the particles, respectively, k is the
Boltzmann constant, and TB is the blocking tempera-
ture, and then the spins fluctuate randomly above TB.
The TB values of all the ZnxCo1-xFe2O4 NPs coated
with TREG are listed in Table 1 (0.0 B x B 1.0). It is
observed from the ZFC and FC measurements in Fig. 9
that the TB of only the TREG-coated ZnxCo1-xFe2O4
NPs with 0.0 B x B 0.2 is higher than 400 K because
of higher effective magnetic anisotropy, and the TB of
the TREG-coated ZnxCo1-xFe2O4 NPs with
0.4 B x B 0.6 gradually decreases with increasing
Zn concentration x. It is known that the blocking
temperature depends on the effective magnetic anisot-
ropy. As easily seen from Fig. 12, the anisotropy
constant continuously decreases as s function of Zn
concentration. Therefore, the blocking temperature
decreases with increasing Zn concentration, x. It has
been widely reported that the magnetic interactions
such as dipole–dipole interactions between the parti-
cles and exchange interactions between surface spins
and core spins of the nanoparticles play an important
role in determining the magnetic properties of the
particles (Gao et al. 2008; Pal et al. 2009). The stronger
dipolar interactions also result in the increase in the
blocking temperature (Pal et al. 2009). As well as
decreasing magnetic anisotropy, a weakening of dipo-
lar interactions at high Zn concentrations is another
reason for the reducing blocking temperature.
In order to further determine the magnetic proper-
ties of the TREG-coated ZnxCo1-xFe2O4 NPs, we used
the FMR method. It is known that FMR spectroscopy is
a very efficient tool to investigate magnetic materials
and to determine magnetic properties, such as mag-
netic anisotropy, effective magnetization, magnetic
damping, etc. (Topkaya et al. 2010; Erkovan et al.
2011; Altincekic et al. 2010; Dursun et al. 2012;
123
J Nanopart Res (2013) 15:1359
Kartopu et al. 2011). Figure 13 shows FMR spectra
(first derivative of the absorption curves) of the TREG-
coated ZnxCo1-xFe2O4 NPs as function of Zn concen-
tration x at the room temperature. It can easily be seen
that all FMR curves have an asymmetrical and intense
broad line, especially above the resonance field region.
The asymmetric behavior of FMR curves of all the
samples studied in this work is caused by non-uniform
modes in addition to the main resonance mode, and a
random orientation of the magnetic nanoparticles leads
to asymmetrical FMR absorption curve. Moreover, the
broad FMR signal of the samples under consideration
originates from the magnetic nanoparticles with ran-
domly distributed anisotropy axes (Sukhov et al.
2008). The FMR condition for the magnetic materials
is written as
x ¼ cHeff ; ð6Þ
where x, c, and Heff are the angular frequency,
gyromagnetic ratio, and effective magnetic field,
respectively. The observed resonance field of the
samples is different from the resonance field value
(3400 Oe) at g = 2.0023 for isolated free electron,
which indicates the presence of the interaction
between the magnetic nanoparticles. Therefore, the
effective magnetic field can be described by the sum of
two terms:
Heff ¼ Hext þ Hint ; ð7Þ
where the first term in the right side of the Eq. 7
represents the external applied magnetic field, that is
the resonance field read from ESR spectrometer, Hext
(=Hr), and the second term represents the internal
magnetic field, defined as follows:
0
Hint ¼ Hdem þ Hdip þ Hdip ; ð8Þ
where Hdem is the internal magnetic field due to
demagnetization, Hdip is the internal field due to the
dipole–dipole interaction between the neighboring
magnetic nanoparticles, and H0 dip is the internal field
arising from dipole–dipole interaction between
agglomerates. In this work, the internal fields shift
the resonance field toward lower magnetic field.
Table 2 shows the values of the resonance field Hr
(=Hext), peak-to-peak linewidth DHpp, g-factor, and the
internal field Hint obtained from FMR data. It is seen
from Fig. 13 and Table 2 that the magnetic parameters
obtained from FMR measurements strongly depend on
J Nanopart Res (2013) 15:1359 Page 15 of 18

Zn concentration for the TREG-coated ZnxCo1-
xFe2O4 NPs. The change in magnetic parameters such
as Hr and DHpp is due to the influence of the cationic
stoichiometry and occupancy in the lattice sites. As
seen from Fig. 13 and Table 2, the resonance field of
the samples initially decreases (up to x = 0.2) and then
continuously increases as Zn content x increases, and
the internal field also persistently decreases with
increasing Zn concentration except for the sample
with x = 0.2. Sparks suggested that one of the factors
affecting resonance field is the internal field (Sparks
1965). The reduction in the internal field shifts the
resonance field in the opposite directions. That is,
the increase in the resonance field is due to the fact that
the internal field decreases with increasing Zn concen-
tration. FMR linewidth, DHpp, is broadened by the
Intensity (arb. units)
anisotropy field and narrowed by the exchange field and
can be described by the equation (Castner and Seehra
1971; Anderson and Weiss 1953; Dutta et al. 2008)
Ha2
DH  ; ð9Þ
Hex
where Ha and Hex are the anisotropy and exchange
field, respectively. The anisotropy field, Ha, is calcu-
lated by the relationship Ha = Keff/Ms using the
saturation magnetization, Ms, and anisotropy constant,
Keff. It can be seen easily Fig. 12 that the Keff
continuously decreases with increasing Zn concentra-
tion. Therefore, the anisotropy field, Ha, correspond-
ingly decreases with Zn concentration with respect to
the relation Ha = Keff/Ms. According to Eq. 9, the
corresponding decrease in Ha continuously causes a
reduction in FMR linewidth as a function Zn concen-
tration for TREG-coated ZnxCo1-xFe2O4 NPs. The
similar reduction was reported recently by Hemeda in
Co0.6Zn0.4MnxFe2-xO4 ferrite system (Hemeda 2002).
As shown as from Fig. 13, only the TREG-coated
ZnxCo1-xFe2O4 NPs with x = 0.0 and 0.2 absorb

microwave in a broad field range of about ten thousand

Oe. Therefore, these samples may be a good candidate
for radar absorbing materials used in microwave
applications.

x=0.0
x=0.2 Conclusion
x=0.4
x=0.6 In this paper, we reported a detailed study on magnetic
x=0.8
x=1.0 properties of TREG-coated ZnxCo1-xFe2O4 nanopar-
ticles (0.0 B x B 1.0) prepared by the hydrothermal
0 4 8 12 16 method in the temperature range of 10–400 K and
Magnetic Field (kOe) under magnetic fields up to 9 T. The magnetic
properties of the zinc-substituted cobalt ferrites nano-
Fig. 13 FMR spectra of the ZnxCo1-xFe2O4 NPs coated TREG particles with average crystallite size of approximately
as a function of Zn concentration x at RT
7–10 nm strictly depend on the coating, Zn concen-
tration, temperature, and applied magnetic field. The
Table 2 g-Value, resonance field Hr, internal field Hint, and FT-IR analysis confirmed the presence of TREG
linewidth DH of MnxCo1-xFe2O4 NPs
coating on the surface of the nanoparticles. The initial
x g Hr (Oe) Hint (Oe) DH (Oe) increase in Ms (up to x = 0.2) was explained by the
0.0 3.45 1972 1428 4053
Néel’s collinear two-sublattice model and then with
0.2 4.30 1623 1777 2960
further increase in Zn content x, the continuous
decrease in Ms and/or magnetic moment was attributed
0.4 3.53 2015 1385 3178
to the three-sublattice model of Yafet and Kittel. It was
0.6 2.59 2712 688 2634
observed from M–H curves that the Keff, Hc, Mr, and
0.8 2.11 3259 141 1044
Mr/Ms ratio continuously decreased with increasing Zn
1.0 2.00 3400 0 213
concentration. The Y–K angle is zero for the CoFe2O4

123
Page 16 of 18
NPs coated with TREG and then increases gradually
with increasing Zn concentrations and extrapolates to
82.36° for ZnFe2O4 NPs coated with TREG. It can be
concluded from computation of the Y–K angles for the
TREG-coated ZnxCo1-xFe2O4 NPs that the TREG-
coated ZnxCo1-xFe2O4 NPs with x [ 0.0 have a Y–K-
type magnetic order, while the TREG-coated CoFe2O4
NPs (with x = 0.0) have a Néel-type magnetic order.
ZFC–FC curves and hysteresis loops at RT indicate
that the samples with 0.6 B x B 1.0 have superpara-
magnetic behavior at RT. The TB obtained from ZFC–
FC curves decreases as a function of Zn concentration.
From lower Mr/Ms values, it was concluded that all the
samples have uniaxial anisotropy. FMR measure-
ments revealed that all the TREG-coated ZnxCo1-
xFe2O4 NPs have a large internal magnetic field and
broad FMR linewidth resulting from the random
distribution of anisotropy axis. The decreasing internal
field causes the increase in resonance field of the
samples with increasing Zn concentration.
Acknowledgments The authors are thankful to the Fatih
University, Research Project Foundation (Contract No. P5002
1104-B), the State Planning Organization of Turkey (DPT-
Project No. 2009K120730), and TUBITAK (Contract No.
110T487) for financial support of this study.
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