Applied Physics A (2020) 126:660

https://doi.org/10.1007/s00339-020-03823-9

Surfactant based synthesis and magnetic studies of cobalt ferrite

Meenal Gupta1   · Anusree Das2   · Satyabrata Mohapatra1   · Dipankar Das2   · Anindya Datta1 

Received: 27 March 2020 / Accepted: 18 July 2020

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract 
Nanoparticles of cobalt ferrite were synthesized by two different surfactants cetyl trimethyl ammonium bromide (CTAB)
and sodium dodecyl sulphate (SDS) by the microemulsion method. Formation of cobalt ferrite was confirmed by structural
characterization techniques XRD and TEM. The magnetic properties of these systems were studied using Mössbauer spec-
troscopy and SQUID magnetometry. The study determined the impact of the synthetic procedure and surfactant composi-
tion on the nanomaterial characteristics. The overall magnetic response for the material was different compared to the bulk
with a major decrease in room temperature magnetic saturation. Magnetic properties were affected by the type of surfactant
template due to its impact on the geometry of the synthesized cobalt ferrite nanoparticles.

* Anindya Datta
anindya_datta@yahoo.com
Meenal Gupta
meenal_garg04@hotmail.com
Anusree Das
anusreedas8@gmail.com
Satyabrata Mohapatra
smiuac@gmail.com
Dipankar Das
ddas.ugcdae@gmail.com
1
BFR-206, B Block, University School of Basic and Applied
Sciences, Guru Gobind Singh Indraprastha University,
Dwarka, Delhi, India 110078
2
UGC-DAE CSR, Bidhan Nagar, Kolkata, West Bengal, India

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 660   Page 2 of 13 M. Gupta et al.

Graphic abstract

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Surfactant based synthesis and magnetic studies of cobalt ferrite Page 3 of 13  660
Keywords  Cobalt ferrite · Surfactant · Magnetic · Mössbauer spectroscopy
1 Introduction
Magnetic properties associated with materials are heavily
modified as these approach nanoscale. Large surface area
and quantum nanosize effect contribute towards superpara-
magnetism and quantum tunnelling [1]. Ferrite magnetic
nanoparticles have been found to be crucial materials for
application in magnetic resonance imaging (MRI), ferrofluid
technology, guided drug delivery, magnetocaloric refrigera-
tion among others. Among ferrites, the spinel ferrites are the
source of immense interest because of their cubic symmetry
[2–4]. Spinel structure was first observed by Bragg in natu-
ral form in ­MgAl2O4[5]. This type of lattice arrangement
was observed and further studied for magnetic nanoparticles
such as various ferric oxides or ferrites [6, 7]. The natu-
ral preference of oxides for the spinel FCC structure due to
its stability has inspired the study of the impact on various
chemical and physical properties of spinel ferrites by intro-
ducing disturbance to such an ordered system [8]. Cobalt
ferrite nanoparticle has a mixed inverse spinel structure with
divalent cobalt cations and trivalent ferric cations distributed
at tetrahedral (A) and octahedral (B) sites in its lattice [9].
Its chemical stability and magnetic hardness facilitate its
applications in magnetic refrigeration, high-density record-
ing, spintronics, ferrofluids, anti-tumour drug delivery and
many others. Cobalt ferrites exhibit large magnetocrystalline
anisotropy making them important technological materials
and they also have considerable magnetization [10, 11].
The spinel structure is of three types: normal, inverse
and mixed based on cationic distributions of the divalent
­M2+ and trivalent ­Fe3+ in octahedral and tetrahedral sites in
the cubic structure. The ferrimagnetic M ­ Fe2O4 (M = Co, Ni)
nanoparticles have spinel cubic structure with two sublat-
tices called A for tetrahedral site and B for octahedral site
and belong to the Fd3m space group. Cobalt ferrite is an
inverse spinel with general formula F ­ e3+A(Co2+ ­Fe3+)BO4
where trivalent cation is equally distributed at octahedral and
tetrahedral sites and divalent cation occupies the octahedral
site [12, 13].
Synthesis methods for ferrite nanoparticles include both
top-down and bottom-up approaches. In top-down, the fun-
damental process is the conversion of the bulk material
into smaller pieces in the presence of external energy that
may be mechanical or chemical in nature. Using atomic or
molecular precursors, bottom-up approach utilises chemical
reactions to synthesize and nanoparticles and allows the pre-
cursor particles to grow. Both methodologies can be done in
either solid, gas, liquid, supercritical fluids, or in a vacuum
with the main aim to fine-tune the properties like particle
size and distribution, shape, degree of agglomeration and
particle composition. Several methods such as sol–gel,
co-precipitation, microemulsion, etc. have been reported
for ferrite synthesis [14–19]. Aubery et al. [20] prepared
Mn − Zn ferrite using the microemulsion method using Syn-
peronic13 surfactant and isooctane oil medium. They stud-
ied reaction kinetics using small-angle neutron scattering
(SANS) and dynamic light scattering (DLS) and synthesized
nanoparticles of sizes 4 nm and 8 nm by varying reaction
conditions. Moumen and Pileni reported the formation of
nanosized cobalt ferrite by the micelle method using SDS
as surfactant with 2–5 nm as the average particle size that
could be controlled by varying the surfactant concentration
[21]. Seip et al. [22] also used the same methodology but
reverse micelles to synthesise different ferrites using AOT
instead of SDS and studied their magnetic properties. In both
cases, the particles exhibited superparamagnetic character in
2–5 nm size range. Maaz et al. [23] used oleic acid as a sur-
factant to prepare nanosized cobalt ferrite by the wet chemi-
cal route. The particle size range was 15–20 nm as deduced
from XRD and TEM. In microemulsion based chemical
synthetic technique, uniform and controlled composition
and morphology of nanoparticles are achieved because of
reagent cation confinement and particle stabilization by
surfactant molecules [24]. The surfactant molecules created
soft template matrix contains several nanoreactors enclosed
within. The surfactant molecules because of their shape,
charge distribution, head and tail groups create a different
type of micro-reactors. The nanoparticle formation occurs
inside these nanoreactors and hence the size and geometry
of these reactors influence the structural properties of the
nanoparticles. These surfactant imprints preserve even after
the surfactant is eliminated from the system [25]. The inter-
action as a result of the attractive or repulsive force between
the head and the nanoparticle due to the polarities of the
particle and the surfactant head have detrimental effect on
the nanoparticle growth [26, 27].
In the present work, we have synthesized cobalt ferrite
nanoparticles using reverse micelle nanoreactors in the
water-in-oil microemulsion system using two different sur-
factants of similar stoichiometry but different polarities.
The cationic metal ion interacts differently with the anionic
(SDS) and cationic (CTAB) surfactant causing different
kinds of nano aggregates in both cases. With equivalent
hydrophobic tails, the primary effect on the nanoparticle
formation is governed by the micellization of the head
around it. It was reported that similarly charged components
experience electrostatic repulsion while oppositely charged
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 660   Page 4 of 13
Fig. 1  XRD patterns for cobalt ferrite prepared using different SDS
concentrations
Fig. 2  XRD patterns for cobalt ferrite prepared using different CTAB
concentrations
experience attractive forces. This impacts assemblage of
surfactant micelles and thus the microreactors associated
with the microemulsion system [28].Our study is focussed
on the impact on the magnetic response of the cobalt ferrite
nanoparticles as a consequence of the two different micellar
systems used for synthesis and acting as templates and the
preservation of effects of surfactant on the lattice above the
vaporisation temperatures of the chosen surfactants.
13
M. Gupta et al.
2 Materials and methods
Wet chemical synthesis of cobalt ferrite nanoparticles by
the use of surfactants was carried out. Precursor salts of
Iron (III) and Cobalt (II) were mixed in ratio of 2:1, respec-
tively, in deionised water and gradually added to 50 mL of
Surfactant /n-Hexane/Butanol solution in stoichiometric
amounts to form a continuous phase. The reaction mixture
was continuously kept stirring for 20 h. After that, sodium
hydroxide was added dropwise to the microemulsion to
bring the pH in the range of 10. The mixture was heated at
80 °C till slurry formation was achieved with the addition
of 7 mL of triethylamine. After washing with ethanol and
water, the mixture was dried overnight in an oven at 80 °C
and then calcined at 550 °C for three hours.
The samples synthesized by SDS/n-Hexane/Butanol were
named A1, A2 and A3 and CTAB/n-Hexane/Butanol were
named B1, B2 and B3 in order of increasing surfactant con-
centrations of 0.08 M, 0.10 M and 0.14 M.
The samples were characterized using XRD, TEM,
SQUID and Mössbauer spectroscopy. The XRD patterns
were recorded by a D8 Advance diffractometer (Bruker,
Germany) using a Cu K-alpha source with 1.54 Å wave-
length. TEM images were captured on JEOL 2100 at CRNN,
University of Calcutta. SQUID measurements were per-
formed using Quantum Design, USA make MMPS XL 7
magnetometer and Mössbauer spectroscopy was studied at
room temperature using a 10 mCi Co-57 in Rh matrix as the
gamma-ray source.
3 Results and discussion
XRD and TEM techniques are utilised for structural analysis
of the samples.
Figures 1 and 2 show the XRD patterns for cobalt ferrite
synthesized using three different surfactant concentrations
of 0.08 M, 0.10 M and 0.14 M of SDS and CTAB, respec-
tively. The patterns are in agreement with JCPDS #22–1086
which corresponds to crystalline inverse spinel cobalt ferrite.
The most intense peak for (311) is observed at 35.56O. The
value of lattice constant is found to be slightly lower than the
reported value at 8.3 Å [23]. The crystallite size is calculated
from the most intense (311) peak using the Debye–Scherrer
equation [29]:
09𝜆
Cs = (1)
𝛽 cos θ
where Cs is the crystallite size and λ is the Cu wavelength
i.e. 1.54 Å, β is the full width at half maximum and θ is the
Bragg angle.
Surfactant based synthesis and magnetic studies of cobalt ferrite Page 5 of 13  660

Sch 1  Use of CTAB and SDS in Surfactant/n-Hexane/Butanol Microemulsion for Cobalt 496 Ferrite Nanoparticle Synthesis

Table 1  XRD results for samples A1-A3 and B1-B3

Sample 2Ɵ (degree) Lattice con- Crystallite X-ray density,
stant, a(Å) size (nm) ­(dx) (g ­cm−3)

A1 35.8 8.309 10.5 5.4

A2 35.8 8.310 14.1 5.4
A3 35.8 8.309 13.1 5.4
B1 35.9 8.316 13.5 5.5
B2 35.7 8.326 14.3 5.5
B3 35.7 8.336 13.6 5.4

The ferrite nanoparticles are formed by the interaction

of ferric and cobaltous salts in the nanopools that are sus-
pended in the oil phase. The interaction between the two
cations occurs in aqueous phase enclosed in these nano-
pools or nanoreactors mentioned above. The reduction of
surface tension is the main purpose of the surfactant at the
interface between oil and water layers (that are the walls of
the nanoreactors in this case) to enable the formation of the
mixed metal hydroxide compound. The type of surfactant
determines the geometry of the nanoreactor/ nanopool which
influences the morphology and size of the nanoparticles
formed as described in Scheme 1 [30]. For higher surfactant
concentration, the samples tend to be more crystalline as
evident from the XRD patterns. Increasing the surfactant
concentration introduces more nanoreactors into the system
leading to the formation of larger micellar assembly. When
the size of nanoreactor increases, the particle size is also
varied with it as seen in Table 1 [31]. The concentrations
of surfactants are above their respective critical micellar
Fig. 3  Pre-heat treatment XRD pattern for as synthesized cobalt fer-
rite
concentration (CMC) values as below CMC no micelle
formation and thus no microemulsion system is formed.
Also higher surfactant amount ensures better kinetics as the
amount of secondary and amorphous phases is observed to
be considerably lower when going from samples 1–3 for
both A (SDS) and B (CTAB) series [32]. The difference in
particle sizes among SDS and CTAB samples is because
of different nano assemblies for each. The CMC value of
CTAB is lower than that of SDS leading to early micelliza-
tion in same molarity CTAB microemulsion. The time for

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 660   Page 6 of 13
Fig. 4  a–d Pre-heat treatment TEM and SAED pattern for A3(a, b)
and B3(c, d), respectively
particle growth is more and hence B series particles have
larger sizes. The use of anionic surfactants produces smaller
sized nanoparticles compared to cationic surfactants [33].
The length of the hydrophobic chain directly affects the par-
ticle size [34, 35]. Among the various concentrations of the
same surfactant, a linear relationship between particle size
and surfactant molarity is expected. Increment in surfactant
amount leads to an increase in the size of microreactors and
hence the size of the nanocluster also increases. Excess sur-
factant causes the presence of excess hydrophobic ligands
that inhibit the particle growth [36, 37]. Leff et al. [38] has
reported an inverse relation between surfactant concentra-
tion and particle size in the presence of excess surfactant
amounts and has attributed it to positive entropy due to sur-
factant adsorption. Particle size reduces to compensate and
reduce entropy.
Consider Figs. 3 and 4 containing XRD pattern and TEM
micrographs for samples A3 and B3 before calcination.
Here,  additional phases are seen in the XRD pattern. As a
result of synthesis temperature being lower than the vapori-
sation temperature for SDS and CTAB, small quantities of
surfactant is still present in the basic morphology of the
nanostructure. Both types of nanostructures show different
nano assemblies due to different aggregation mechanism for
each type of surfactant micelle [39, 40]. Due to the presence
of surfactants in the system, the average nanoparticle size
is about 17.2 nm for SDS samples and 17.7 nm for CTAB
samples. To obtain a complete pure sample, this sample was
heated at 550 °C in the furnace. The TEM of the calcined
samples do not show surfactant impurity.
From the  TEM micrographs for cobalt ferrite speci-
mens A3 and B3 as seen in Figs. 5 and 6, it is clear that the
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M. Gupta et al.
crystalline particles are in nanoscale. The average d-spacing
for samples A3 and B3 is about 2.5 Å which is the reported
value for (311) plane that is represented by the brightest
ring in the SAED pattern. From these TEM micrographs,
the sizes of nanoparticles of the two samples are measured
and histograms plotted that are found to be best fitted with
the lognormal distribution [41]. From these histogram plots
in Fig. 7, the average nanoparticle diameters calculated for
samples A3 and B3 are 12.2 ± 3.4 nm and 13.1 ± 4.1 nm,
respectively.
With the change in the surfactant amount, the size of
nanoparticle is affected as the size of nanopool is depend-
ent on the ratios of oil/surfactant/water concentrations [42].
The type of surfactant concentrations taken for both types
of micellar systems are the same although the overall mor-
phology is distinct as the particle shapes tend to differ. This
difference arises due to two distinct mechanisms of particle
formation. SDS is an anionic surfactant. Therefore, in SDS
mediated system, the mechanism of particle formation as
described [9, 43] is due to the formation of aqueous cobalt-
iron disulphide that converts to cobalt iron oxide in basic
medium with addition of amine. On the other hand, CTA​+ is
the long-chain part of the cationic CTAB surfactant that gets
attached to the surface of the cobalt-iron hydroxide which
inhibits further particle growth to give uniform cobalt ferrite
nanoparticles [44, 45]. From the results of XRD and TEM,
the average particle sizes for both samples are below the
critical size for cobalt ferrite nanoparticles with the exist-
ence of multi domains. This leads to interesting results for
magnetic properties compared to the bulk sample and the
reported results [2, 42, 46].
Figure 8a–d show Mössbauer spectra at room temperature
for cobalt ferrite nanoparticles prepared via the microemul-
sion route using two different surfactants. The Mössbauer
effect is based on the interactions of the nuclear charge
with the electromagnetic field created by the surrounding
extranuclear electrons [47]. Being a local probe, it gives
information on the surrounding of the nucleus. The three
experimentally measurable parameters in Mössbauer spec-
troscopy are isomer shift, quadrupole splitting and hyperfine
(internal) magnetic field. The isomer shift gives information
on the valence state of Fe atoms in the sample. The quadru-
pole splitting gives information on the symmetry of charge
distribution around the probe nucleus whereas the internal
magnetic field provides a measure of magnetic ordering in
the sample [48]. The obtained Mössbauer spectra for SDS
and CTAB mediated cobalt ferrite nanoparticles are fitted
using least-squares fits of Lorentzian function to two sextets
and a doublet. It may be noted that the sextet patterns show
a signature of relaxation as the peak intensity ratio differs
from being 3:2:1: 1:2:3 expected for a powder sample with
magnetic ordering. In addition, line widths of the peaks are
very large confirming the presence of superparamagnetic
Surfactant based synthesis and magnetic studies of cobalt ferrite Page 7 of 13  660
Fig. 5  a TEM image, b–c HRTEM images and d SAED pattern for sample A3
relaxation in the samples. From Table 2, isomer shift values
are in the range of 0.31 to 0.34 mm s−1 for the sextets for
samples A2 and A3 and 0.26 to 0.37 mm s−1 and for B2 and
B3, respectively. The isomeric shift values obtained for both
are lower in comparison to the reported values at 300 K [10].
This is due to the superparamagnetic behaviour of cobalt fer-
rite nanoparticles that is verified by the absence of hysteresis
curve for these nanoparticles at the same temperature using
SQUID that will be discussed in the later section. Reduced
isomeric shift values for A2-A3 and B2-B3 with particle
sizes between 10–20 nm compared to bulk cobalt ferrite
arises due to increase in density of s-electrons of the Fe atom
because of decrease in distance between ­Fe3+–O2− ligands
at octahedral and tetrahedral sites with a decrease in size
[49, 50]. The increase in surface area with a decrease in size
leads to distortion of the crystal lattice that affects the elec-
tron density and spin orientation. The hyperfine field values
vary with particle size, decreasing with a decrease in particle
size. The presence of a central doublet confirms superpara-
magnetic behaviour. This impact of change in surfactant is
witnessed in isomeric shift and hyperfine field values due to
surface morphology as well as crystal quality as a result of
the synthetic procedure [12, 51].
From the results of magnetic measurements conducted
by SQUID magnetometry at room temperature and 5 K as
shown in Fig. 9, it is clear that prominent hysteresis curves
are obtained at 5 K while no hysteresis is seen at 300 K. The
size of cobalt ferrite nanoparticles is less than the super-
paramagnetic diameter ­(dSP) for cobalt ferrite [2, 52] which
is also seen in the room temperature hysteresis. Due to the
small size, the magnetic nanoparticles cannot accommodate
multi-domain system which reduces the corresponding mag-
netostatic energy. The magnetostatic energy or the activa-
tion energy is thus less than the thermal energy at 300 K.
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 660   Page 8 of 13
Fig. 6  a TEM image, b–c HRTEM images and d SAED pattern for sample B3
According to the theory of superparamagnetism (SPM), all
moments are aligned causing hysteresis with ideally zero
remanence and coercivity [53, 54]. From the experimental
results, some multidomain structures with the single domain
size range exist due to disordered surface spins. The main
precursor for magnetic properties is exchange interactions
between spins corresponding to different oxidation states. In
addition, the nanoparticles have a large volume to diameter
ratio value. Therefore, systems with noticeable hysteresis
but lower Ms values also exist within the d­ SP range [55]. At
low temperature, ferrimagnetic behaviour of cobalt ferrite
nanoparticles is dominant because of ordering of relaxing
magnetic moments below the blocking temperature resulting
in alignment of spins in the direction of applied magnetic
field. At room temperature, the thermal energy is sufficient
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M. Gupta et al.
to destroy such alignment [56]. A close look at Fig. 9 reveals
that saturation of magnetization fails to occur even for the
applied magnetic field as high as 50 kOe. This behaviour
along with negligible coercivity and retentivity values can
also be attributed to SPM [57]. The maximum magnetisation
at 5 K for A2 at 50 kOe is found to be 43 emu/g which is
much lower than the saturation magnetization (93.9 emu/g)
for bulk cobalt ferrite. The lower values are due to surface
effects that become prominent at nanoscale such as spin
canting and magnetically dead particle surface layer [6, 58]
and strong magnetic anisotropy [59, 60]. Structural defects
create lattice strain and influence the spin alignment. The
surface area impacts upon the electron cloud density of the
cationic nuclei (Fe for Mössbauer). The nanoparticle size,
cationic distribution and surface area are major factors that
Surfactant based synthesis and magnetic studies of cobalt ferrite Page 9 of 13  660

Fig. 7  a and b Particle size distribution from TEM results for A3 and B3, respectively

Fig. 8  a–d Mossbauer spectra for samples A2, A3, B2 and B3, respectively

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 660   Page 10 of 13 M. Gupta et al.

Table 2  Mössbauer parameters Sample Parameters I.S. (mm ­s−1) Q.S. (mm s­ −1) L.W. (mm ­s−1) Hhf (T) % Area (G)
Isomeric Shift (I.S.),
Quadrupole Splitting (Q.S.), A2 3+
Sx1Fe Tetra 0.33 0.07 1.33 441 36.7
and Hyperfine Field (Hhf)
Sx1Fe3+ Octa 0.34 0.08 0.74 481 45.8
calculated for samples A2–A3
and B2–B3 Db1 ­Fe3+Octa 0.34 0.61 0.5 – 17.5
A3 Sx1Fe3+Tetra 0.31 0.02 0.80 484 48.1
Sx1Fe3+ Octa 0.34 0.12 1.02 431 16.6
Db1 ­Fe3+Octa 0.34 0.75 0.53 – 35.3
B2 Sx1Fe3+Tetra 0.33 0.08 0.66 466 44.3
Sx1Fe3+ Octa 0.37 0.03 1.25 434 52.6
Db1 ­Fe3+Octa 0.41 0.57 0.3 – 3.1
B3 Sx1Fe3+Tetra 0.26 0.06 1.28 450 34.2
Sx1Fe3+ Octa 0.33 0.02 0.62 486 44.9
Db1 ­Fe3+Octa 0.33 0.69 0.65 – 20.9

Fig. 9  a–d M-H graph for samples A2-A3 and B2-B3 at 300 K and 5 K, respectively

influence the results from Mössbauer spectroscopy and mag- for very high values of the applied field, H. Here, Ms is the
netic measurements. saturation magnetisation and b is the fitting parameter. The
The saturation magnetisation ­(Ms) was measured by plot- intercept of the above straight line on Y-axis is the saturation
ting the function [61] magnetisation value. It is observed that the saturation mag-
netisation values increase with increasing surfactant concen-
M = Ms (1 − b∕H) (2) tration. This can be attributed to enhancement in crystalline

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Surfactant based synthesis and magnetic studies of cobalt ferrite Page 11 of 13  660
Fig. 10  FC-ZFC plots for samples A2, A3, B2 and B3 at an applied
field of 100 Oe
Fig. 11  Approach to Saturation for sample A3
structure with each sample and correlated with XRD and
Mössbauer results where the isomeric shift and quadrupole
splitting values are found to be closer to the expected range
for sample A3 [62]. From the graphs, SPM is more pro-
nounced in SDS mediated A series samples compared to
CTAB mediated B series. The particle sizes in both cases
are equivalent. However, from Mössbauer and magnetic
results, it can be concluded that the presence of spin disor-
der on the surface is greater for cobalt ferrite nanoparticles
synthesized using CTAB as surfactant because of higher
remanence and coercivity values of B series compared to
A series. The difference in ­Ms values for SDS and CTAB
systems is a combined effect of all these factors [63, 64]. The
ratio of remanence to saturation (Mr/Ms) or the squareness
ratio decreased with the increasing quantity of surfactant in
the system. The squareness ratio calculated for the samples
show a large deviation from the bulk value (0.50) which at
5 K is quite higher than the reported value and lower than
reported for room temperature measurement. Higher values
are obtained for A series at comparing Mr/Ms for samples A
and B. This is also the consequence of the superparamag-
netic nature of these nanoparticles to achieve saturation in
the given applied field.
The moment versus temperature measurements in the
presence of 100 Oe of the external magnetic field are in the
temperature range of 5 K to 300 K as shown in Fig. 10. The
upper portion of the M vs T curve refers to FC measurement
and the lower portion to ZFC, respectively. The point of
bifurcation of the FC and ZFC curves are blocking tempera-
tures that are found to be 300 K for all the samples.
The Law of Approach to Saturation (LAS) is used for
calculating the anisotropy constant ­K1. For very high values
of the applied magnetic field (H) i.e. H >  >  > Hc (coerciv-
ity), magnetization M has been plotted as a function of H
(Fig. 11). The expression for LAS is [65]:
( ))
K1 2
(
8
M(H) = MS 1 − + 𝜒n H (3)
105 Ms H
Here, K1 is the cubic anisotropy constant and ratio 8/105
holds for random polycrystalline specimens with cubic
anisotropy. The term 𝜒n H is for spontaneous magnetiza-
tion occurrence known as forced magnetization observed
at high fields and 𝜒n is the high field susceptibility. In cubic
anisotropy, three prominent axes for anisotropy are usually
the principal axis. The axis of the applied magnetic field
determines the anisotropy axis for the given system. The
anisotropy constant has been calculated using the values of
applied magnetic field greater than 1 T and corresponding
magnetization values to plot M v/s H graph that was fitted
to Eq. (3) with K1 and Ms as dependents. The values are
summarised in Table 3.
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 660   Page 12 of 13 M. Gupta et al.

Table 3  Magnetic measurement Sample Tempera- Hc (× 104 Oe) Mr (emu ­g−1) Ms (emu ­g−1) K1 × 105 ­(Jm−3) Mr/Ms
values using SQUID ture (K)

A2 5 1.5 28.4 43.0 11.6 0.66

300 0.01 2 32.7 3.52 0.06
A3 5 1.08 37.3 55.3 13.9 0.67
300 0.02 6 38.8 2.65 0.16
B2 5 1.0 38.4 60.79 6.88 0.63
300 0.11 20.6 49.34 2.38 0.42
B3 5 1.2 33.1 64.85 6.11 0.51
300 0.06 10.8 35.3 1.63 0.31

As can be seen from Table 3, anisotropy constant (K1)
values for samples of both A and B series are lower than
for bulk values because of reduced size and thus reduced
magnetostatic energy. The anisotropy constant has a larger
value at 5 K because of the absence of thermal fluctuations.
According to the Stoner-Wohlfarth theory [53], ­EA or
activation energy is a type of threshold for opposing change
in direction of magnetisation given by
EA = K1 V sin2 θ (4)
where K1 is the anisotropy constant, V is the nanoparticle
volume and θ is the angle between the easy axis and applied
field.
When the particle size is decreased to beyond the criti-
cal diameter, EA is overcome by room temperature thermal
energy. As a result, SPM state of nanoparticles is reached
and the anisotropy also decreases. The coercivity values are
higher for the samples B2 and B3 compared to A2 and A3
because of surface spin fluctuations. The magnetic response
for A series cobalt ferrite nanoparticles is superior to that
of B series. It can be said that the magnetic morphology
of the A series cobalt ferrite nanoparticles is better than
that of B series in terms of uniformity and stability in mag-
netic results. As seen in Scheme 1, the impact of cationic
and anionic surfactants is different for same nanoparticle
synthesis because micelles formed by both surfactants are
influenced by surface charges and counter ions that produce
either attractive or repulsive forces. These forces also influ-
ence the micelle self-arrangement and hence the resulting
nanoparticle assembly [40].
value is different for different surfactants. The purpose of
using ionic surfactants is to create spin distortions in the
system and study the magnetic properties in such case. The
results from Mössbauer are indicative of SPM. On com-
paring SDS and CTAB synthesized samples, SPM is more
dominant in SDS series. The CTAB synthesized particles
although within comparable sizes produce higher values of
retentivity and coercivity than the SPM limit as a conse-
quence of unresolved spin on their surface. This causes a
few spins in non-uniform alignments giving higher M ­ r and
­Hc values as well as higher M
­ s. SDS synthesized cobalt fer-
rite nanoparticles have comparably ordered surface spins
and narrow hysteresis making them susceptible to magnetic
tuning for suitable applications.
Acknowledgements  The authors acknowledge the help received from
UGC-DAE CSR, Kolkata Centre for providing the SQUID and Moss-
bauer spectroscopy facilities and Centre for Research in Nanoscience
and Technology, University of Calcutta for providing TEM facility. The
author (Meenal Gupta) is thankful to UGC for providing fellowship.
Prof. Datta is thankful to GGSIP University, New Delhi for the FRGS
grant GGSIPU/DRC/FRGS/2018/1/ (1115) and DST for FIST grant
(SR/FST/PSI-167/2011(C)).
Funding  GGSIP University, New Delhi for the FRGS grant GGSIPU/
DRC/FRGS/2018/1/ (1115) and DST for FIST grant (SR/FST/
PSI-167/2011(C)).
Compliance with ethical standard 
Conflict of interest  The authors declare that there is no conflict of in-
terest regarding the publication of this paper.

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4 Conclusions
The above work is a preliminary search for the best sur-
factant to prepare highly crystalline cobalt ferrite and to
determine the appropriate amount of the surfactant required.
The cobalt ferrite material displays good crystalline struc-
ture as seen from XRD and TEM results for a particular
amount of surfactant present in the microemulsion. This
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