Journal of Magnetism and Magnetic Materials 401 (2016) 1–8

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Exchange spring like magnetic behavior in cobalt ferrite nanoparticles

M. Chithra a, C.N. Anumol a, Baidyanath Sahu b, Subasa C. Sahoo a,n
a
Department of Physics, Central University of Kerala, Riverside Transit Campus, Nileshwar, P.O. Padnekkad, Kasaragod, Kerala 671314, India
b
Department of Physics, I.I.T. Bombay, Powai, Mumbai 400076, India

art ic l e i nf o a b s t r a c t

Article history: Cobalt ferrite nanoparticles were prepared by sol–gel technique and were annealed at 900 °C in air for
Received 7 June 2015 2 h. Structural properties were studied by X-ray diffraction, Raman spectroscopy and Fourier transformed
Received in revised form infrared spectroscopy. Scanning electron microscopy and transmission electron microscopy studies show
26 September 2015
presence of mostly two different sizes of grains in these samples. Magnetization value of 58.36 emu/g
Accepted 5 October 2015
was observed at 300 K for the as prepared sample and an enhanced magnetization close to the bulk value
Available online 9 October 2015
of 80.59 emu/g was observed for the annealed sample. At 10 K a two stepped hysteresis loop showing
Keywords: exchange spring magnetic behavior was observed accompanied by very high values of coercivity and
Cobalt ferrite remanence. Two clear peaks were observed in the derivative of demagnetization curve in the as prepared
Sol gel method
sample where as two partially overlapped peaks were observed in the annealed sample. The observed
Magnetic studies
magnetic properties can be understood on the basis of the grain size and their distribution leading to the
different types of intergranular interactions in these nanoparticles.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction increases with the decrease in grain size though it is anti-

ferromagnatic in the bulk. In Zn-ferrite thin film also, it is possible
Magnetic nanoparticles have attracted much attentions in re- to get high magnetization and a very low ferromagnetic resonance
search because of their wide range of applications in data storage line width depending on the grain size and their distribution
[1–3], magneto-optical devices [4], catalysis [5], biomedical ap- without going through high temperature processing [19,27]. Co-
plications like drug delivery [6], magnetic resonance imaging [6,7], ferrite nanoparticles also show some interesting features like su-
biosensors [8] and hyperthermia [9–12]. These nanoparticles show per-paramagnetism [28], increased/decreased saturation magne-
very interesting physical properties due to their reduced size tization [29,30], low/high coercivity [31,32], and spin glasses [29]
compared to their bulk counterpart. The physical properties of depending on the grain size. Song et al [28] observed that Co-
these nanoparticles can also be easily tailored by controlling its ferrite nanocrystals show superparamgnetic behavior at 300 K and
microstructure and enabling them for many applications [13–15]. ferrimagnetic behavior at 5 K. They have also observed coercivity
The sizes of the nanoparticles [14,16], morphology [7,13], size (HC) of 10.8 kOe at 5 K in 5 nm Co-ferrite nanocrystals. They sug-
distribution [17–19], packing density [20], intergranular exchange gested on the basis of their experimental observations that the
interaction [21–23], and cation distribution [24,25] are some of the superparamagnetic properties can be controlled through magnetic
factors which are responsible for the modified magnetic properties coupling at atomic level in spinel ferrite nanocrystals. Peddis et al.
[29] observed an enhanced saturation magnetization of 109 emu/g
in the nanomaterials. Among these, grain/particle size and their
at 5 K for ultra-small (3 nm) Co-ferrite nanoparticles compared to
distributions are most of the important factors governing the
the bulk value of 90 emu/g at 0 K [33]. Their study showed that
magnetic properties in the nanomaterials. Nlebedim et al. [17]
localized spin canting and cation distribution in the spinel struc-
observed that the particle size distribution of CoFe2O4 (Co-ferrite)
ture are responsible for such high value of magnetization. How-
is an important factor in controlling the magnetostictive proper-
ever, Lopez et al. [30] observed a reduced saturation magnetiza-
ties. Malik et al. [18] observed double peaks in the zero field cooled
tion of 27.3 emu/g and HC of 14.7 kOe at 4.2 K in Co-ferrite nano-
and field cooled magnetic measurements performed at low field
particles of average diameter of 7.2 nm. Toksha et al. [34] studied
due to bimodal particle size distribution in Ni-ferrite nano-
magnetic properties of Co-ferrite nanoparticles as a function of
particles. Chinnasamy et al. [26] found that nanostructured Zn- grain size after annealing. However, the effects of grain size and
ferrite shows ferrimagnetic behavior and the magnetization their distribution as well as the intergranular interactions on the
magnetic properties of the Co-ferrite nanoparticles need to be
n
Corresponding author. Fax: þ 91 467 2285491. studied thoroughly. In the present study we show that depending
E-mail address: [email protected] (S.C. Sahoo). on the grain size and their distribution, exchange spring magnetic

http://dx.doi.org/10.1016/j.jmmm.2015.10.007
0304-8853/& 2015 Elsevier B.V. All rights reserved.
2 M. Chithra et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 1–8

behavior, which is generally observed in bimagnetic systems [35–

39] consisting of hard and soft phases, can be observed in Co-
ferrite nanoparticles.
Different synthesis methods have been adopted to synthesize
ferrite nanoparticles keeping in mind their applications with the
modification of their specific properties suitable for those appli-
cations. A wide variety of synthesis techniques like co-precipita-
tion [40], microemulsion [41,42], hydrothermal [43], and sol–gel
technique [44] are used to synthesize Co-ferrite nanoparticles.
Among these, sol–gel method is one of the best methods due to its
advantage of low processing temperature, high purity, better
homogeneity and single phase products [44,45]. In the present
study, we prepared Co-ferrite nanoparticles by sol–gel technique
and studied their magnetic properties at different temperatures.

2. Experimental details

For the synthesis of Co-ferrite nanoparticles, stoichiometric

amounts of Fe(NO3)3  9H2O (analytical grade) and Co(NO3)2  9H2O
(analytical grade) were dissolved in 50 ml of ethylene glycol
(C2H6O2). The aqueous solution was kept at 60 °C for 15 min under
constant stirring to obtain viscous gel. The temperature was fur-
ther increased to 200 °C to evaporate the solvent. After the solvent
was evaporated, by further heating at the same temperature the
gel was self-ignited to form powder and it was cooled down to Fig. 1. XRD patterns of (a) CF-ASP and (b) CF-ANN powder samples.
room temperature. The powder was collected at room tempera-
ture and was ground well by agate mortal pestle. This powder
sample is designated as CF-ASP in this study. The as prepared
powder was annealed at 900 °C in air for two hours and was
cooled in the furnace. This annealed powder sample is designated
as CF-ANN.
The samples were characterized by a PANalytical Expert PRO
powder X-ray diffractometer with Cu Kα radiation (λ ¼1.5406 Å).
Raman spectra of the samples were recorded at room temperature
using a Horiba JobinYvonHR800 confocal micro-raman spectro-
meter equipped with argon ion (Ar þ ) laser of wave length
514.5 nm. Fourier transformed infrared (FTIR) spectra were col-
lected at room temperature for these samples in the
400–4000 cm  1 range by a Nicolet Magna-IR FTIR 550 spectro-
photometer. Microstructures of these samples were studied by a
JSM-7600F field emission gun-scanning electron microscope (FEG-
SEM) and a high resolution JEOL JEM 2100F field emission gun
transmission electron microscope (FEG-TEM) operating at 200 kV.
The grain size distributions of these nanoparticles were obtained
from the SEM and TEM images. The magnetic properties were
carried out by a vibrating sample magnetometer of Quantum De-
sign Physical Property Measurement System (PPMS) by applying
magnetic field up to 50 kOe at different temperatures varying from
300 K to 10 K.
Fig. 2. Raman spectra of (a) CF-ASP and (b) CF-ANN powder samples.

3. Results and discussion average grain size was found to be 13 nm for CF-ASP sample and
was found to be increased to 83 nm for the CF-ANN sample.
Fig. 1 shows the X-ray diffraction (XRD) patterns of the CF-ASP Fig. 2 shows the Raman spectra of the CF-ASP and CF-ANN
and CF-ANN samples. All the observed peaks were indexed to samples. Group theory predicts five Raman active phonon modes
cubic Co-ferrite spinel structure using JCPDS data (Card no.- for Co-ferrite having cubic spinel structure with symmetry
221086). It is interesting to note from Fig. 1 that the XRD peaks are O7h (Fd3¯ m) namely A1g, Eg and 3T2g [47]. It is seen in Fig. 2 that
narrower for the CF-ANN sample compared to those for the CF- Raman spectra are also narrower for the CF-ANN sample com-
ASP sample indicating grain growth after annealing. The lattice pared to that of the CF-ASP sample which corroborates our XRD
constant was found to be 0.833 nm and 0.835 nm for the CF-ASP observation about the grain growth after annealing. The observed
and CF-ANN samples respectively compared to the bulk value of spectra for the CF-ANN sample was best fitted with multiple Lor-
0.839 nm. The grain size was estimated from the peak width of the entzian curves as shown in Fig. 2(b) and seven peak positions were
most intense peak (311) using scherrer's formula [46], D ¼0.9λ/ obtained. The peak positions are found to be at 170, 208, 307, 469,
βcosθ, where D¼ grain size, λ ¼wavelength of X-rays, β ¼full 564, 621 and 691 cm  1. Cation redistribution in the tetrahedral
width of the peak at half maximum in radian, θ ¼Bragg angle. The and octahedral sites may lead to the observation of more number
 M. Chithra et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 1–8 3

shows the TEM image and grain size distribution of the CF-ASP
sample respectively. It is seen from the Fig. 4(e) that the grain size
and their distribution pattern are similar to those obtained from
SEM images of the CF-ASP powder sample shown in Fig. 4(a) and
(b) respectively. It clearly shows that in the CF-ASP sample the
grains are mostly isolated corroborating the SEM studies. The se-
lected area electron diffraction (SAED) pattern of the CF-ASP
sample is shown in Fig. 4(f). All the diffraction rings were indexed
to Co-ferrite phase.
Magnetization (M) versus applied magnetic field (H) hysteresis
(M–H) loops of the as prepared sample CF-ASP were observed at
different temperatures. Fig. 5 shows the representative M–H loops
of the CF-ASP sample. Fig. 6 shows the M–H loops at 300 K and
10 K of the annealed sample CF-ANN. Following observations were
made from the M–H loops shown in Figs. 5 and 6.

(1) A two step was observed in the M–H loops as the temperature
decreased from 300 K to low temperature of 10 K; one step
near to zero applied fields showing abrupt decrease in mag-
netization observed in both the direction of applied fields in-
dicating switching of magnetic moments of some magnetic
soft phase present in the nanoparticle samples and the other
Fig. 3. FTIR spectra of CF-ASP and CF-ANN powder samples. one at higher fields showing the presence of some magnetic
hard phase. These two step switching in the M–H loops were
clearly resolved as two peaks in the dM/dH  H plots dis-
of active vibration modes in the Raman spectrum [47]. These cussed in details below.
phonon modes were assigned with the help of literatures [47,48]. (2) M–H loops donot saturate in the highest applied fields.
The high frequency Raman modes above 600 cm  1 (peak positions Moreover, the loops of CF-ANN sample show better saturation
at 621 and 691 cm  1) corresponds to A1g due to the symmetric compared to those of the CF-ASP sample.
stretching of oxygen in tetrahedral sites. The lower frequency
Raman modes are assigned to Eg and T2g(3) corresponding to Non-saturation of M–H loop is a common phenomenon ob-
symmetric and antisymmetric bending of oxygen ion in metal- served in nanoparticles and thin films [38,50–52]. In order to get
oxygen bonds at the octahedral sites. the magnetization value, high field part of the M–H loop was ex-
Fig. 3 shows FTIR spectra recorded at room temperature for the trapolated to the zero applied fields and this value is termed as
CF-ASP and CF-ANN samples. The absorption bands observed at spontaneous magnetization (MS). The MS values, remanence (Mr),
420 and 590 cm  1 in both the samples are the characteristic peaks coercivity (HC) and Mr/MS ratio obtained from the M–H loops are
of spinel ferrites [23,49]. The higher frequency absorption band at shown in Fig. 7 for the CF-ASP sample and are listed in Table 1 for
590 cm  1 is assigned to metal-oxygen vibration at tetrahedral the CF-ANN sample at 300 K and 10 K along with those of the CF-
sites and the band at 420 cm  1 is assigned to metal-oxygen vi- ASP sample at the same temperatures.
brations at octahedral sites. The absorption bands observed at As seen in Fig. 7 and Table 1 the MS value of 58.36 emu/g was
1634 and 3434 cm  1 for the CF-ASP sample are due to O–H vi- observed at 300 K for the CF-ASP sample and was enhanced to
bration and H–O–H bending vibrations respectively and the band close to bulk value [33] of 80.59 emu/g in the CF-ANN sample. In
intensities were reduced in the annealed sample CF-ANN. The nanoparticles as the surface to volume ration increases with the
bands appeared at 2854 and 2923 cm  1 may be due to the sym- decrease in grain size, the surface contribution dominates over
metric and asymmetric stretching vibration of CH2 group, re- volume contribution leading to lower MS value in the CF-ASP
spectively [49]. These O–H, CH2 group and water (H2O) contents sample [34,45]. As the grain size is increased in the CF-ANN
are there on the surface of the nanoparticles. sample, the increase in volume contribution compared to the
Fig. 4(a) and (c) shows the SEM images of the CF-ASP and CF- surface contribution amounts to the increase in magnetization.
ANN powder samples respectively. Fig. 4(b) and (d) shows the Though some residue of O–H, H2O and CH2 groups are present on
grain size distributions of the corresponding samples. From Fig. 4 the surface of the nanoparticles as observed by FTIR, being dia-
(a) it is seen that the grains are very small in size and are mostly magnetic their contribution is negligible to the overall magneti-
isolated. Fig. 4(c) shows that grain size has been increased after zation value compared to the ferrimagnetic contribution of Co-
annealing. Even particles of  μm size are also seen in the CF-ANN ferrite.
sample. As seen in Fig. 4(b) the CF-ASP sample consists of grains It is interesting to note that the MS value does not increase
mostly of two different types; one type of grains are of size around much at 10 K compared to 300 K for both the samples. More in-
16 nm and the other type is of around  27 nm, along with some terestingly, the MS value increases from 58.36 emu/g to 61.14 emu/
smaller and bigger grains. For the CF-ANN sample also, though the g as the temperature decreases from 300 K to 200 K for the CF-ASP
grain size has been increased, the size distribution show similar sample as seen in Fig. 7(a). Further decrease in temperature results
behavior. In this case also most of the grains are of two different decrease in MS value and finally reaches 59.13 emu/g at 10 K. As
sizes;  170 nm and  270 nm with some smaller and bigger seen in Table 1 the HC value in the CF-ASP sample is higher than
grains. The grain size observed by SEM in the CF-ANN sample is that for the CF-ANN sample. There is a change in order of mag-
not of the same order as observed by XRD. It is understood that the nitude in the HC value at low temperature of 10 K. The highest HC
grains are coalesced to form bigger grains in the annealed sample value of 18.69 kOe was observed in the CF-ASP sample at 10 K. Mr
and the overall size is observed in SEM. Such bimodal distribution /MS values of 0.91 and 0.87 were observed at 10 K for the CF-ASP
of grains has also been observed in Ni-ferrite nanoparticles pre- and CF-ANN samples respectively. For the CF-ASP sample, Mr, Mr
pared by sol–gel method [18]. Fig. 4(e) and the inset in Fig. 4(e) /MS and HC increase monotonically with the decrease in
4 M. Chithra et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 1–8

Fig. 4. (a) SEM image and (b) grain size distribution of CF-ASP (200 grains), (c) SEM image and (d) grain size distribution of CF-ANN (160 grains) powder samples (grains of
 μm size were not included in grain size distribution), (e) TEM image and (f) SAED patterns of the CF-ASP powder sample. Inset in (e) shows the grain size distribution of the
CF-ASP sample obtained from TEM image (150 grains).

temperature from 300 K to 10 K as seen in Fig. 7(b)–(d). The de- increase of MS value with the decrease of temperature in the CF-
crease in HC value in the CF-ANN sample compared to the CF-ASP ASP sample is expected as the thermal energy decreases, the
sample can be understood as follows. The CF-ASP sample contains canted magnetic moments present in the sample are ordered in
grains with size  25 nm, the critical single domain size of Co- the field direction. However, the decrease of MS value at low
ferrite nanoparticles prepared by sol–gel method [34]; they are temperature is quite interesting. The as prepared sample CF-ASP
mostly single domain particles. The grain size is very large in the contains grains with different sizes as seen in Fig. 4(a) and (e). The
CF-ANN sample and contains multi-domains. Domain wall motion superparamagnetic and blocked state in the magnetic nano-
in these multi-domain grains causes HC to decrease compared to particles can be observed on the basis of their grain size [28]. It
the CF-ASP sample. The observation of higher MS and lower HC may be understood that in the blocked state (with blocking tem-
values in the CF-ANN sample compared to the CF-ASP sample is perature TB  304 K as discussed below) with the decrease in
well understood on the basis of grain growth. temperature some magnetic moments are frozen at random, as a
Generally MS value at low temperature is observed to be more result effective magnetization decreases in our sample. The mag-
than that at room temperature for any material [33,53]. The netic dipolar interaction between the superparamagnetic grains
 M. Chithra et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 1–8 5

Fig. 5. (a)–(d) M–H loops of CF-ASP sample at different temperatures as mentioned in the figure.

Fig. 6. M–H loops of CF-ANN sample at (a) 300 K and (b) 10 K.

also induces a collective behavior decreasing their magnetization some magnetic moments to align along the applied field direction.
value in the blocked state [54]. As HC is very high at low tem- We strongly believe that in addition to the intergranular interac-
perature, it is also possible that increase in anisotropy prohibits tions the anisotropy also plays an important role at low
6 M. Chithra et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 1–8

Fig. 7. (a) Magnetization value (MS), (b) Mr and (c) Mr/MS and (d) coercivity (HC) as a function of temperature for the CF-ASP powder sample. The inset in (d) shows the fitting
of the HC  T curve using Kneller's law.

Table 1 to the presence of mostly two types of grains in our samples which
Magnetic properties of CF-ASP and CF-ANN samples at 300 K and 10 K. is supported by the SEM and TEM studies shown in Fig. 4. One type
of grains can be considered as a soft magnetic phase with lower HC
Sample Temp. (K) MS (emu/g) Mr (emu/g) Mr/MS HC (kOe)
and the other type of grains can be considered as a hard phase
CF-ASP 300 58.36 16.58 0.29 0.81 with higher HC. When the field larger than HC of both the types of
10 59.13 53.59 0.91 18.69 grains is applied, magnetic moments in both the types of grains
CF-ANN 300 80.59 19.18 0.24 0.47 are parallel and are oriented along the field direction. When the
10 80.71 69.56 0.87 3.49
field is reduced and is applied in the negative direction, magne-
tization in one type of grains having lower HC switches first. As the
applied field is increased in the negative direction, the magnetic
temperature. moment in the other types of grains having higher HC also
Fig. 8 shows the derivative of magnetization with respect to the switches in that direction depending on the strength of their in-
applied magnetic field (dM/dH  H) of the demagnetization curve. tergranular interactions as discussed below.
As seen in Figs. 5 and 6 above for both the as prepared CF-ASP and It is also interesting to see in the Fig. 8 that two distinct peaks
the annealed sample CF-ANN, a two step magnetic behavior was were observed in the CF-ASP sample whereas the two partially
observed at 10 K. In Fig. 8 we see two well resolved peaks; one overlapped peaks were observed in the CF-ANN sample at 10 K.
peak near to zero applied field and the other one at higher field. This indicates that the second step of magnetization reversal was
Such type of two stepped magnetic behavior is generally observed started after the completion of the first step in the CF-ASP sample.
in bimagnetic exchange spring systems consisting of two chemi- However, this was not true in the CF-ANN sample. In this sample
cally different magnetic phases; one soft phase and the other one second step of magnetization reversal was started before the
hard phase [35–39]. It seems that both of our samples contain the completion of the first step.
magnetic nanoparticles of two different anisotropy and coercive The exchange interaction as well as magnetic dipolar interac-
fields corresponding to one soft magnetic phase and the other one tion in magnetic nanoparticles induces a collective behavior
hard magnetic phase. Such magnetic behavior may be attributed showing a single step at 300 K (as shown in Fig. 8) in the
 M. Chithra et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 1–8 7

Fig. 8. Derivative of magnetization with respect to applied magnetic field (dM/dH) of the demagnetization curves of (a) CF-ASP and (b) CF-ANN samples at 300 K and 10 K.

demagnetization curve [55]. Grains of different sizes have different enhanced from 58.36 emu/g for the as prepared sample to close to
anisotropies and HC. Due to the increase in anisotropy at low the bulk value of 80.59 emu/g for the annealed sample. A two
temperature, the intergranular interactions are weakened at 10 K, stepped M–H loop was observed in both the samples at low
i.e. anisotropy dominates over intergranular interactions. The two temperature of 10 K accompanied by very high values of coercivity
types of grains behave partially or even completely decoupled and remanence. The observed magnetic properties are attributed
from the neighboring grains depending on the strength of their to the grain size and their distribution leading to different types of
interactions. The magnetic moments reverse accordingly in the intergranular interactions in these nanoparticles.
demagnetizing field. As the field is applied in the reverse direction
the magnetic moments in the decoupled grains will orient at the
lower field and the remaining moments which are exchange Acknowledgment
coupled will orient at the higher fields leading to a two-stepped
magnetization loop. We thank Prof. Shiva Prasad, Prof. N. Venkataramani, Sophis-
The as prepared sample CF-ASP contains isolated single domain ticated Analytical Instrument Facility, and the Centre for Research
grains with smaller magnetic moments. In order to observe the in Nanotechnology and Science, Indian Institute of Technology
intergranular interactions in the CF-ASP sample, we have used a Bombay for the characterizations of the samples. One of the au-
simple model for the noninteracting single domain nanoparticles. thors, S.C. Sahoo acknowledge the financial support from UGC,
The relation connecting HC with temperature (kneller's law) for Government of India through a research grant (F.20-3(8)/2012
the non-interacting single domain magnetic nanoparticles is given (BSR)) for this work.
T
by HC = HC0 [1 − ( T )1/2], where HC0 is the coercivity at 0 K and TB is
B
the blocking temperature. This equation is best fitted to our data
Appendix A. Supplementary material
and is shown in the inset in Fig. 7(d). This clearly shows that the
intergranular interaction in the CF-ASP sample is very weak. As a
Supplementary data associated with this article can be found in
result two independent peaks were observed in the demagneti-
the online version at http://dx.doi.org/10.1016/j.jmmm.2015.10.
zation curve at 10 K (shown in Fig. 8). The blocking temperature TB
007.
was found to be 304 K by this model. The CF-ANN sample contains
bigger grains with bigger magnetic moments. The diamagnetic/
nonmagnetic residues on the surface of the nanoparticles were
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