Chapter 22

Spinel Ferrite Nanoparticles: Synthesis, Crystal

Structure, Properties, and Perspective
Applications

Tetiana Tatarchuk, Mohamed Bououdina, J. Judith Vijaya,

and L. John Kennedy

22.1 Introduction

Spinel ferrite nanomaterials (SFNs) have gained huge attention in modern days from
fundamental science point of view owing to their unique properties and promising
applications such as high-density data storage, catalysts, gas sensors, rechargeable
lithium batteries, information storage systems, magnetic bulk cores, magnetic fluids,
microwave absorbers and medical diagnostics and therapy, etc. [1–5]. The funda-
mental understanding of crystal chemistry in SF nanomaterials is very essential, and
the proper choice of synthesis route will determine its well-defined crystal lattice
structure and chemical composition, leading to enhanced/excellent physical and
chemical properties. With the general molecular formula MFe2 O4 (where M D Mn,

T. Tatarchuk ()
Department of Inorganic and Physical Chemistry, Faculty of Natural Science, Vasyl Stefanyk
Precarpathian National University, 57, Shevchenko Str., Ivano-Frankivsk, 76018, Ukraine
e-mail: [email protected]
M. Bououdina
Department of Physics, College of Science, University of Bahrain, PO Box 32038, Southern
Governorate, Bahrain
e-mail: [email protected]
J. Judith Vijaya
Catalysis and Nanomaterials Research Laboratory, Department of Chemistry, Loyola College,
Chennai, 600034, India
e-mail: [email protected]
L. John Kennedy
Materials Division, School of Advanced Sciences, Vellore Institute of Technology (VIT)
University, Chennai Campus, Chennai, 600127, India
e-mail: [email protected]

© Springer International Publishing AG 2017 305

O. Fesenko, L. Yatsenko (eds.), Nanophysics, Nanomaterials, Interface Studies,
and Applications, Springer Proceedings in Physics 195,
DOI 10.1007/978-3-319-56422-7_22
306 T. Tatarchuk et al.

Fe, Co, Ni, Cu, and Zn), the majority of SFs exhibit superparamagnetic (SPM)
properties at the nanoscale dimensions of diameter below or about 20 nm [1–7].
The metal cations in both sites are distributed based on their affinity to occupy
the positions which in turn are significantly dependent on the stabilization energy,
ionic radii of metal cations, size of interstitial site, synthesis technique, and
their synthesis reaction conditions [1–7]. In addition, the development of suitable
synthesis routes which can control the morphological properties of SFs becomes
much more important, since there is a correlation between the catalytic activity
and the morphological properties, and thus it is revealed that the catalytic activity
of SFs also depends upon the adopted synthesis method. The structural, magnetic,
electronic, and optical properties of SFs are significantly enhanced in the nanoscale
regime with the reduction in crystallite size and increase in specific surface area.
The size and shape of the SFs can modulate their physical and chemical properties,
and consequently extensive researches have been devoted to the fabrication of SFs
with controlled morphological properties.
In the past decade, various methods of synthesizing SFs have been addressed and
reported in the literature, but there is a requirement for the commercially reliable
methods, since every synthesis method has its own advantages and disadvantages.
Henceforth, the design of new synthesis method for SFs which also utilizes less
hazardous and commercially available low-cost precursor materials requires greater
attention.
The present chapter focuses on highlighting the successful synthesis methods
for SFs with few examples and pointing out their advantages and disadvantages.
Meanwhile, particular attention will be given to in-depth understanding of the
spinel crystal structure and its correlation with magnetic/optical properties. Finally,
potential applications of SFs are presented and discussed.

22.2 Synthesis Methods of Spinel Ferrites

22.2.1 Microemulsion Method

This method involves the dispersion of two relatively immiscible liquids which
is thermodynamically feasible and stabilized by added surfactant molecules [8].
The advantages of this method include changing the surfactants and co-surfactant
combination and oil-to-water ratio, and thus the particle size can be controlled [8,
9]. This reaction is known for being eco-friendly and favorable at low temperature
and reuse of surfactants for several cycles during the synthesis and possibility
of commercial production [9]. Nevertheless, the major disadvantage is the poor
crystalline nature of synthesized SFs, requirement of larger amounts of solvents
and high polydispersion due to the slower nucleation rate at low temperature. The
two major classifications of this method are reverse water-in-oil and normal oil-
in-water [8], and some SFs synthesized by this method include Fe2 Mn0.5 Zn0.5 O4 ,
Ni0.6 Fe2.4 O4 , and Fe3 O4 [8, 9].
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 307

22.2.2 Ultrasonic (Sonochemical) Method

The sonochemical route is widely employed nowadays for the synthesis of SFs
due to the facile control of reaction conditions. This method particularly targets
in achieving homogeneous mixing and controlling the particle size distribution.
Therefore, the temperature and the intensity of ultrasonic waves are major factors
which can have a direct impact on the particle size of SFs. During the synthesis,
as a resultant of the ultrasonic wave irradiation, the bubbles are formed in the
reaction medium, and SFs undergo in situ calcination due to the induced high-energy
collisions between the particles [1, 10]. By means of ultrasonication, mixing at the
atomic level can be achieved so that the formation of crystalline phase is possible by
annealing at relatively low temperatures [11]. Some SFs synthesized by this method
include CuFe2 O4 and Fe3 O4 [10, 11].

22.2.3 Non-hydrolytic Method

The synthesis of SFs via non-hydrolytic process using suitable organic solvents at
elevated temperatures is proved to be an effective method to obtain high-quality
and well-controlled sized nanoparticles [7]. Generally, the inorganic coordina-
tion complexes or organometallic compounds are used as molecular precursors
because they play a key factor in achieving well-crystalline SFs [7]. SFs are com-
monly considered as ternary metal oxides (MFe2 O4 ), and hence in non-hydrolytic
method, two different kinds of molecular precursors have been used. Some of the
reported molecular precursors are manganese(II) acetylacetonate, (Mn(acac)2 ), and
iron(III) acetylacetonate, (Fe(acac)3 ). Some SFs synthesized by this method include
CoFe2 O4 and MnFe2 O4 [12].

22.2.4 Solvothermal Method

The solvothermal method (or hydrothermal if water is solvent) is one of the most
eco-friendly and promising synthesis methods which is available and employs the
usability of aqueous or nonaqueous solvents for a better control on particle size
distribution and morphology [1]. Also, the shape, size, and morphology of SFs were
altered by adjusting the experimental reaction conditions, such as temperature, time,
solvent, precursor materials, and surfactant [1]. Due to its simplicity in procedure,
commercial production of SFs is feasible with enhanced physical and chemical
properties [1, 13–15]. A wide range of SFs have been synthesized, and some
examples are MWCNT/CoFe2 O4 , Co3 O4 , Fe3 O4 , CoFe2 O4 [1], Ni–Zn ferrite [13],
MnFe2 O4 [14], and metal-doped MgFe2 O4 [15].
308 T. Tatarchuk et al.

22.2.5 Coprecipitation Method

The synthesis of SFs by coprecipitation method is the most convenient, economic,

and less time-consuming, has high mass production, and is frequently employed
among all other methods in order to achieve uniform-sized particles [1]. This
method is also commonly used to synthesize biocompatible SFs, which have
applications in in vivo biomedical field [1]. This method employs the mixing of
aqueous solutions of divalent and trivalent transition metal salts that are uniformly
mixed together in 1:2 mole ratios with continuous and vigorous stirring in an
alkaline medium. The coprecipitation method needs careful monitoring of pH in
order to achieve high-quality SFs [4, 16]. The common disadvantage of this method
is that relatively low crystallinity of synthesized SFs and hence a subsequent
thermal treatment is necessary in order to achieve better crystallinity. This method is
preferred to be the suitable route for synthesizing water-dispersible SFs [16], and a
variety of SFs have been synthesized by coprecipitation method including CoFe2 O4
[2, 16], MnFe2 O4 [16], Fe3 O4 [4, 16], and Sn-doped MnFe2 O4 [4].

22.2.6 Sol–gel Method

The sol–gel synthesis method is widely employed for the SFs, in which the metal
alkoxide solution undergoes hydrolysis and condensation polymerization reactions
to produce gels and any volatile impurities are removed by heat treatment after
the synthesis reaction [1]. The advantages of this method include low-cost, simple,
carried out at a relatively low temperature without the need of special equipment,
and achievable of narrow particle size distribution [17–20]. However, particular
care should be taken for a better control of reaction parameters such as stirring
rate, concentration of sol, and annealing temperature [1, 6]. The major limitation of
this method is the lack of purity of the final product, and thus thermal treatment
is required after the synthesis to achieve the high purity [1]. Nevertheless, the
homogeneity, composition control, particle size, and particle distribution can be well
achieved by sol–gel method, and nanocomposites based on SFs dispersed in silica
gel matrix have been synthesized by this method, and some SFs synthesized by this
method are Ni0.4 Zn0.6x Co/Mnx Fe2 O4 [1], CoFe2 O4 [2, 17], MnFe2 O4 [6], NiFe2 O4
[17–19], Pr-substituted Mg–Zn ferrites [18], CuFe2 O4 [19], and ZnFe2 O4 [20].

22.2.7 Microwave-Assisted Method

The microwave-assisted method is a new technique which emerges rapidly for the
synthesis of SFs. The advantages of this method are generally fast, simple, lower
reaction time, high-energy efficiency, good yield, cost-effective, and appropriate
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 309

dielectric loss of the as-synthesized SFs [20]. Moreover, this method can be
employed to synthesize SFNs on a commercial scale, but a low yield can be obtained
when compared to other methods such as coprecipitation, hydrothermal, or thermal
decomposition methods [1, 20]. In this method, heating energy is internal rather
than external as in the case of conventional combustion reactions, and microwave
energy is utilized for the combustion of precursors to form SFs. Heat generation is
due to the conversion of microwave energy to thermal energy, and the temperature
usually ranges from 100 to 200 ı C for the shorter period of time. The gases produced
during the reaction were eliminated through an exhaust drain connected with Teflon
vessel [1]. Some SFs synthesized by this method are Fe3 O4 [1], Co2 Fe2 O4 [1],
Mn1x Nix Fe2 O4 [20], and ZnFe2 O4 [21].

22.2.8 Mechanical Milling Method

Mechanical milling is a top-down approach method used for the synthesis of

SFs by means of high-energy shaker, planetary ball mill, and sometimes tumbler
mills [1, 22]. Some of the advantages of this method are low-cost, short time,
simple, and large-scale production, and SFs obtained from this method have an
ordered ferromagnetic core and a random shell [1]. The major disadvantage of this
method is frequent contamination by milling tools during longtime milling, which
in turn will change the stoichiometry of the as-obtained SFs [1, 22]. Some SFs
synthesized by this method include CoFe2 O4 [1], CuFe2 O4 [1], NiFe2 O4 [1], and
Ni1x Mnx Fe2 O4 [22].

22.2.9 Other Methods

Numerous other methods frequently employed for the synthesis of SFs have been
reported in the literature, including combustion [23], reverse micelle [24], spray
pyrolysis [25], electrospinning [26], self-reactive quenching [27], double sintering
ceramics [28], powder metallurgy [29], self-propagating high temperature [30],
thermal decomposition [31], liquid exchange [32], and solid-state reaction [33].

22.3 Crystal Structure and Properties of Spinel Ferrites

Among different magnetic materials, SF nanoparticles have attracted particular

considerations. SFs are a class of compounds of general formula MFe2 O4 (where
M D Zn2C , Mg2C , Mn2C , Fe2C , Co2C , Ni2C , Cu2C , (0,5LiC C0,5Fe3C ), etc.),
which are of great interest for their remarkable magnetic, catalytic, optical, and
electrical properties [34–37].
310 T. Tatarchuk et al.

Fig. 22.1 The unit cell of

spinel structure MeFe2 O4

In the spinel structure with general formula AB2 O4 , oxygen atoms form cubic
close packing where A and B cations occupy tetrahedral and octahedral lattice sites.
The crystal structure has a space group Fd3m [38]. The cubic unit cell is formed
by 56 atoms: 32 oxygen anions distributed in a cubic close-packed structure and 24
cations occupying 8 of the 64 available tetrahedral sites (A sites) and 16 of the 32
available octahedral (B sites).
  Thus,  contains eight formula units (Z D 8)
 the2cell
corresponding to Me2C 8 A
Me 3C
16 B O 32 O . The divalent metal ions commonly
used in ferrites can be classified into those preferring B sites (Co, Fe, Ni, Cr) and
those preferring A sites (Mn, Zn) (Fig. 22.1).
 The crystal
  chemistry  of spinels is described by the general formula
Me2C1x Fe 3C
x A
Me 2C
x Fe 3C
2x B O4 , where x refers to the inversion parameter or
degree of inversion, and  depends from several factors, such as site preferences of
ions in terms of size, covalent bonding effects, and crystal field stabilization energies
(CFSE). In general, the inversion parameter of a given nanostructured ferrite is quite
different from that of the bulk counterpart and varies with the preparation method.
In the ideal normal structure (x D 0), Me2C cations are found at the A sites, and
Me3C cations are found at the B sites. Whereas in the inverse structure (x D 1),
half Me3C cations are found at the A sites with consequent migration of all the
Me2C cations to the octahedral sites. Spinels can also display a partially inversed
structure, which is described by means of the x-parameter, corresponding to the
occupancy of Me3C cations on the A sites.
In order to accommodate larger cations such as Co, Cu, Mn, Mg, Ni, and Zn,
the lattice has to be expanded. The difference in the expansion of the tetrahedral
and octahedral sites is characterized by a parameter called oxygen parameter or
anion parameter (u). The oxygen parameter (u) is a quantity which represents the
movement of O2 ion due to the substitution of cation at tetrahedral A site. As
u increases, oxygen ions move in such a way that the distance between A and O
ions (RA ) is increased while that between B and O ions (RB ) is decreased, and
when u parameter decreases, the O2 ions are displaced in such a way that RA
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 311

decreases and RB increases [39]. In all ideal spinels, the parameter u has a value
in the neighborhood of 0.375 (u D 3/8). But in the actual spinel lattice, this ideal
pattern is slightly deformed and usually corresponds to u > 0.375.
The theoretical lattice constant (ath ), radius of the ions at octahedral site (rB ), and
radius of the ions at tetrahedral site (rA ) for spinel systems have been calculated on
the basis of the cation distribution by the next relation [38]:

8 h p i
ath D p .rA C RO / C 3 .rB C RO /
3 3
5  p
rB D a 8
 u  RO rA D a 3 .u  0; 25/  RO

where RO is the radius of oxygen ion O2 (1.38 Å); rA and rB are the ionic radii of
tetrahedral (A) and octahedral (B) sites, respectively; and u is the anion (oxygen)
parameter.
For example, for Zn1x Cox Fe2 O4 system [40], the average cation radii at the
tetrahedral and octahedral sites, rA and rB , were calculated according to the
following cation distribution:
  h i  
Zn2C
1x Fe 3C
xCy Co 2C
y Co2C
xy Fe 3C
2xy O2
4 O (0  x  1, 0  y  0,21)
A B
   2C     3C     2C 
rA D C Zn2C
A  r ZnA C C Fe3C
A  r FeA C C Co2C
A  r CoA
   2C     3C 
C Co2C
B  r CoB C C Fe3C
B  r FeB
rB D
2
where
 C is the  ionic
 2Cconcentration
 at the tetrahedral and octahedral sites;
r Zn2C 3C
A ; r FeA ; r CoA are the ionic radii of Zn2C (0.60 Å), Fe3C (0.49 Å), and
   3C 
Co2C (0.58 Å) ions in the tetrahedral sites, respectively; and r Co2C B ; r FeB are
the ionic radii of Co2C (0.745 Å) and Fe3C (0.645 Å) ions in the octahedral sites,
respectively [40].
It can be seen that r(A) decreases while r(B) increases with increasing Co2C
concentration. This is due to the fact that Zn2C ions (0.60 Å) with larger ionic radius
are replaced by Co2C ions (0.58 Å) with smaller ionic radius. Some of Fe3C ions
(0.49 Å) also migrate to (A) sites as a result of the substitution process. However, in
(B) sites, Fe3C ions with smaller ionic radius are replaced by Co2C ions with larger
ionic radius, so the values of radii of octahedral sites will be increased [40].
A recent published paper [39] also reports a decrease in cationic distribution
parameters such as site radii (rA , rB ) in the Zn0.85-x Nix Mg0.05 Cu0.1 Fe2 O4 ferrites
(x D 0.00, 0.17, 0.34, 0.51, and 0.85), prepared by sol–gel auto-combustion method,
with Ni doping. The parameters obtained by cationic distribution are reported. The
cationic distribution can give a better understanding of the magnetic interaction in
spinel ferrites, because there exists a strong correlation between magnetic properties
and cation distribution of spinel ferrite [39].
312 T. Tatarchuk et al.

In addition, the substitution (doping) of rare earth metal ions (Sc3C , Dy3C , Sm3C ,
Gd3C , etc.) at Fe3C site significantly affects the structural, microstructural, optical,
electrical, and magnetic properties in the nanostructured ferrites [41]. Both magnetic
and electrical properties of SFs are found to be strongly dependent on their chemical
composition, method of preparation, grain/particle size, and distribution of cation
between two interstitial sites. The structural and the magnetic environments of these
two sites are quite different [41]. The doping of nonmagnetic ions, for example, the
transition metal/rare earth-doped ferrites, has been extensively studied. It was found
that the presence of nonmagnetic ions reduces the magnetic interactions between the
two interstitial sites and leads to a decrease in hyperfine magnetic fields and hence
changes observed in magnetic and electronic properties [41]. Table 22.1 illustrates
some characteristics of selected SFs systems reported in the literature.
It can be seen from Table 22.1 that the decrease in lattice constant in SF
systems can be explained by several mechanisms: (i) ionic radius reduction due
to the fact that the doping cation has a smaller ionic radius compared to that of
being cation; (ii) a possible redistribution of Me2C and Me3 C ions within the
tetrahedral/octahedral ionic sites, which will be followed by important changes in
the magnetic properties; (iii) a fraction of Me2C ions occupying the octahedral sites
and forcing Me3C to the tetrahedral sites against their chemical preferences [54].
Thus the cation distribution between tetrahedral (A) and octahedral (B) sites
greatly influences the structural, electrical, optical, and magnetic properties of
SFs [48]. In general, the magnetic behavior of spinel ferrites is dependent on
the physical properties of individual particles and their environments. The most
important physical characteristics include chemical composition, particle size, par-
ticle morphology, intrinsic material parameters (e.g., magnetocrystalline anisotropy,
saturation magnetization, etc.), surfaces/interfaces, and particle size distribution.
Most of these parameters are easily obtained (or are relatively non-important) for
bulk magnetic materials; however, this is not necessarily true for nanoparticles.
The magnetic properties of SFs are classified as intrinsic and extrinsic. Intrin-
sic magnetic parameters depend mainly on the crystal structure and chemical
composition of the material. Examples of intrinsic magnetic properties include
Curie temperature Tc, saturation magnetization Ms, exchange stiffness A, and
magnetocrystalline anisotropy K. On the other hand, extrinsic magnetic parameters
depend upon the microstructure of the material and are naturally affected by
the size and shape of particles. Extrinsic magnetic properties include coercivity
Hc, remanent magnetization Mr, and magnetic susceptibility ¦. The concentration
and types of cations substitution also have very dominant effect on the magnetic
properties. According to the Neel’s two-sublattice model of ferrimagnetism, the
magnetic moment per formula unit is expressed as:

M.X/ D MB.x/  MA.x/

where MB and MA are the B and A sublattice magnetic moment in B , respectively.

Actually, the net magnetic moment determines the Ms value.
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 313

Table 22.1 Composition and crystal chemical parameters for several ferrites with a cubic spinel
structure
Synthesis Lattice
Compound method constant (Å) Size, nm Strain, © Ref.
ZnFe2 O4 MCM 8.4410 5–15b 0.034 [34]
ZnFe2 O4 CCM 8.4429 30–50b 0.038 [34]
ZnFe2 O4 HEBM 8.448 9a – [42]
CoFe2 O4 MM – 85a – [43]
Co1x Znx Fe2 O4 (0  x  0.5, MCM 8.3799– 45–32a 0.035– [44]
L-arginine as a fuel) 8.3959 0.043
Zn1x Cox Fe2 O4 (x D 0; 0.1; 0.2; CM 8.4392– 37–25a – [40]
0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9; 1.0) 8.3536
Mn0.5 Zn0.5 Scy Fe2y O4 (y D 0.00, SCM 8.434–8431 20–22a – [41]
0.01, 0.03, and 0.05) 20–23c
Mn0.5 Zn0,5 Fe2 O4 SCM 8.4339 25a 0.0009 [45]
Mn1x Znx Fe2 O4 (x D 0, 0.1, 0.3, SCM 8.432–8.372 25–35 c – [46]
0.5, 0.7, 0.9, 1.0)
Mn1x Nix Fe2 O4 (x D 0.0, 0.1, 0.2, MCM 8.477–8.419 – 0.412– [20]
0.3, 0.4, 0.5) 0.200
Cox Ni0.6x Zn0.4 Fe2 O4 (x D 0.0 to PCM 8.3763– – – [47]
0.6) 8.4002
Mgx Zn1x Fe2 O4 (x D 0.5, 0.6, 0.7) CM 8.422–8.438 6.3–14.6a 0.005 [48]
Co1x Znx Fe2 O4 (0  x  0.5, urea MCM 8.284–8.356 3.07–11.3a – [49]
as a fuel)
Fe3 O4 MCM 8.393 25a 0,143 [50]
Fe3 O4 SGM 8.3639 8c – [51]
Zn1x Mgx Fe2 O4 (x D 0.0, 0.1, 0.2, MCM 8.443–8.427 41.20– 0.067– [52]
0.3 0.4, 0.5, 0.6, 0.7, and 0.8) 15.87a 0.047
Zn1x Srx Fe2 O4 (x D 0.0,0.1,0.2,0.3, MCM 8.443–8.451 42 – 25a 0.067– [53]
0.4, and 0.5) 0.077
Zn1x Cux Fe2 O4 (x D 0.0, 0.1, 0.2, MCM 8.443–8.413 43–54 a 0.067– [54]
0.3, 0.4, and 0.5) 0.056
Zn1x Nix Fe2 O4 (x D 0.0, 0.1, 0.2, MCM – 43–49a – [55]
0.3, 0.4, and 0.5)
Zn0.85x Nix Mg0.05 Cu0.1 Fe2 O4 SGM 8.412–8.352 34–42a – [39]
(x D 0.00, 0.17, 0.34, 0.51, 0.85)
Li0.5x/2 Znx Fe2.5x/2 O4 (x D 0, 0.1, SGM 8311–8.423 – – [56]
0.25, 0.3, 0.5, 0.7, 0.9, 1.0)
Mg1x Znx FeCrO4 (0.0  x  1.0) CCM 8.3610– 20.1–28.7a – [57]
8.3820
MnFe2x Mnx O4 (x D 0.0, 0.25, 0.5, RMM 8369–8379 23–28a – [58]
1.0) 4–22c
NiFe2x Gax O4 (x D 0.0, 0. 2, 0. 4, SGM 8.3491– 13.8–5.5a – [59]
0.6, 0.8, 1.0) 8.3313
Mn1x Mgx Fe2 O4 (0.0  x  1.0) HTM 8.471–8.443 20–30a – [60]
MCM microwave combustion method, CCM conventional combustion method, SCM solution com-
bustion method, PCM precursor combustion method, CM coprecipitation method, SGMsol–gel
method, MM mechanical milling, HEBM high-energy ball milling, CCM conventional ceramic
method, RMM reverse microemulsion method, HTM hydrothermal method
a, b, and c are sizes from XRD [a ], SEM [b ], and TEM [c ]
314 T. Tatarchuk et al.

Table 22.2 Magnetic properties (magnetization Ms, remanence Mr, and coercivity Hc) and
optical data (band gap) as a function of cation substitution at some SF systems
Optical
Magnetic properties properties
Band gap
Compound Ms (emu/g) Hc (Oe) Mr (emu/g) (eV) Ref.
ZnFe2 O4 -MCM 31.96 119.7 0,5247 2.08 [34]
ZnFe2 O4 - CCM 149.1 46.96 1.358 2.03 [34]
ZnFe2 O4 30 – – 2.13 [42]
CoFe2 O4 72.1 1517 37.7 – [43]
Co1x Znx Fe2 O4 – – – 1.88–2.10 [44]
(0  x  0.5)
Mn1x Nix Fe2 O4 (x D 0.0, 67.79–35.09 48.25–99.26 11.94–6.425 1.56–1.83 [20]
0.1, 0.2, 0.3, 0.4, 0.5)
Cox Ni0.6x Zn0.4 Fe2 O4 63.5–74.8 75–150 8.8–10.2 – [47]
(x D 0.0 to 0.6)
Mgx Zn1x Fe2 O4 (x D 0.5, 38.46–44.03 18.67–23.52 1.303–1.471 – [48]
0.6, 0.7)
Co1x Znx Fe2 O4 (0  x  14.26–29.61 – – 2.56–2.17 [49]
0.5, urea as a fuel)
Fe3 O4 66.12 65.89 10.2 2.12 [50]
Fe3 O4 47 0.655 – – [51]
Zn1x Cox Fe2 O4 (x D 0.0 1.638–65.20 5.027–66.36 0.0016–10.862 2.10–1.71 [52]
to 0.5)
Zn1x Mgx Fe2 O4 (x D 0.0, 1.638–64.98 5.027–65.96 0.0016–11.565 2.15–1.42 [61]
0.1, 0.2, 0.3 0.4, 0.5, 0.6,
0.7, 0.8)
Zn1x Srx Fe2 O4 (x D 0.0, 1.638–59.581 5.027–30.152 0.0016–4.6562 2.1–1.72 [53]
0.1,0.2, 0.3,0.4, 0.5)
Zn1x Cux Fe2 O4 (x D 0.0, 1.638–58.58 5.027–29.15 0.0016–4.9361 2.1–1.95 [54]
0.1, 0.2, 0.3, 0.4, 0.5)
Zn1x Nix Fe2 O4 (x D 0.0, 1.681–57.89 5.034–30.14 0.0018–4.8953 2.11–1.96 [55]
0.1, 0.2, 0.3, 0.4, 0.5)
Zn0.85x Nix Mg0.05 Cu0.1 47.63–136.93 0.97–167.5 0.27–11.87 – [39]
Fe2 O4 (x D 0.00, 0.17,
0.34, 0.51, 0.85)
MnFe2x Mnx O4 (x D 0.0, 16–30 115–223 – – [58]
0.25, 0.5, 1.0)

A few most representative examples of the magnetic SFs with their magnetic and
optical properties are given in Table 22.2.
As can be seen from Table 22.2, there is some correlation between the structural
properties of the materials (difference in the cation sharing at the A and B sites) and
their magnetic results. The magnetic properties of nanoparticles are determined by
their physical structure: the size and shape of the particles, their microstructure, the
chemical phase or phases that are present, the defects, and differences between the
crystal structure of nanoscale phases and their bulk counterparts. For example, the
magnetic properties of zinc ferrite systems are influenced by the preparation route,
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 315

cation distribution, grain size, and sintering conditions [34]. The smaller value of
saturation magnetization in ZnFe2 O4 -CCM is due to the differences in inversion
parameter, which indicates the distribution of cations between A and B sites of the
spinel lattice [34]. Moreover, the very low values of Hc and Mr indicate that the
ferrites are soft magnets. Magnetic SFs with the same chemical composition often
differ markedly from one another due to a different distribution of ions among the
sublattice (Table 22.2).
For example, zinc ferrite is a normal spinel and nonmagnetic ion Zn2C and
magnetic ion Fe3C are distributed in A and B sites, respectively [18]. But the lower
magnitudes of magnetization and occurrence of a net magnetic moment of the order
of 10.73 emu/g in zinc ferrite (for x D 1) at room temperature in the reference [46]
are indicative of the presence of Zn2C ions on the octahedral sites in nanoregime.
It can alter the cation distribution to a greater extent which is an influential factor
in determining the overall magnetic properties in the nanoregime. The small values
of coercivity indicate that the synthesized ferrites can be used for low- and high-
frequency applications [46].
In Mg–Zn ferrites [48], both Zn2C and Mg2C are diamagnetic, and therefore
the distribution of Fe3C between tetrahedral (A) and octahedral (B) sites will
determine the magnetization. In the present ferrite systems, Zn2C substantially
occupies tetrahedral (A) site, and Mg2C occupies octahedral (B) sites along with
inversion to tetrahedral (A) sites accompanied with an increase of Mg2C ion
concentration leading to the formula unit (Zn1x Mg• Fex• )[Mgx• Fe2xC• ]O4 .
Therefore the increase of Mg2C in B sites pushes the Fe3C to A sites, thereby
strengthening A–B exchange interaction and finally resulting in the increase of
saturation magnetization [48].
The preparation of ferrite nanoparticles with controlled particle sizes leading to
the appearance of a superparamagnetic behavior remains a challenging task. On the
other hand, the magnetic anisotropy of ferrite nanoparticles can be controlled by
a proper selection of divalent dopants in the spinel structure [48]. When particle
size reaches to a critical size (Dc ), in such ferrite nanoparticles, thermal fluctuations
disorganize the magnetic spins in random way like paramagnetic state, and this state
is termed as superparamagnetism. The ferrite nanoparticles with superparamagnetic
behavior are suitable for biomedical applications like targeted drug delivery, cancer
treatment by hyperthermia, etc. [48]. For example, magnetic measurements of
Zn1x Srx Fe2 O4 nanoparticles [53] revealed that, at lower Sr concentration (x < 0.2),
the system shows a superparamagnetic behavior, whereas, at higher concentration
(x > 0.2), it becomes ferromagnetic. The samples ZnFe2 O4 , Zn0.9 Mg0.1 Fe2 O4 , and
Zn0.8 Mg0.2 Fe2 O4 [61] with lesser Mg concentration (x D 0.0, 0.1 and 0.2) also
showed superparamagnetic behavior. This indicates that Zn2C ions occupied the
tetrahedral sites and Fe3C ions at the octahedral sites, whereas the dopant Mg2C
ions occupied either octahedral or tetrahedral sites, thus showing superparamagnetic
behavior.
It is known that in SFs, the saturation magnetization depends on the exchange
interaction between the A and B sites, i.e., A–B exchange interaction [39, 40]
(Fig. 22.2). The different types and amount of magnetic or nonmagnetic cationic
316 T. Tatarchuk et al.

A-B B-B A-A

B
p
p
θ1
Oxygen θ2
p d
e f q
c θ3
r
q s
θ4 θ5
p b
A r
p

θ1=125°9 θ2=154°34 θ3=90° θ4=125°2 θ5=79°38

(ideal) (ideal) (ideal) (ideal) (ideal)

Fig. 22.2 Configuration of the ion pairs in SFs with favorable distances and angles for effective
magnetic interactions

substitution on A and B sites strongly affect the exchange interactions among

them [39]. In ferrites, the exchange interaction occurs by the contribution of
oxygen “anions” which is called superexchange interaction. There are three prob-
able superexchange interactions in the ferrites as follows: A–A, B–B, and A–B
interactions. The inter-sublattice interactions (A–O–B) are much stronger than the
intra-sublattice interactions (A–O–A and B–O–B) in SFs with collinear ferrimag-
netic structure. The inter-sublattice interaction (A–O–B) is accountable for the
discrepancy of initial permeability and Curie temperature of SFs [39].
The bond distances between cations (Me–Me) (b, c, d, e, and f ) and cation–anion
(Me–O) (p, q, r, and s) are estimated using the following relations [40]:

Me–O Me–Me
  p  
p D a 58  u b D 2 a4
p   p a
q D a 3 u  14 c D 11 8
p   p  
r D a 11 u  14 d D 3 a4
p u  p  3a 
s D a 3 3 C 18 eD 3 8
p  
f D 6 a4

The overall strength of the magnetic interactions (A–B, B–B, and A–A) depends
upon the bond lengths and bond angles between the cations and cation–anion. The
strength is directly proportional to bond angle but inversely proportional to bond
length. The bond angles ( 1 ,  2 ,  3 ,  4 , and  5 ) between the cations and cation–
anion are estimated using the following relations [40]:

1 p2 C q2  c2
1 D cos
2pq

p2 C r2  e2
2 D cos1
2pr
 2
2p  b2
3 D cos1
2p2
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 317


p2 C s2  f 2
4 D cos1
2ps

1 r2 C q2  d2
5 D cos
2rq

For example, the estimated bond angles for the spinel system Zn1x Cox Fe2 O4
[40] indicate that  1 ,  2 , and  5 increase while  3 and  4 decrease with increasing
Co2C concentration. The decrease in  3 and  4 suggests a strengthening of B–B
interactions, while  1 ,  2 , and  5 increase, which is indicative of weakening A–B
and A–A interactions with decreasing Zn2C concentration. In reference [39], it is
also reported that the magnetic exchange (A–B, A–A, and B–B) strength depends
upon the bond distance and bond angles. The strength varies directly with bond
angle and varies inversely with bond length for the Zn0.85x Nix Mg0.05 Cu0.1 Fe2 O4
spinel nanoferrites for different compositions (x D 0.00, 0.17, 0.34, 0.51, 0.85).
Furthermore, ferrites are one of the most promising photocatalysts, with the
characteristic behavior of absorbing visible light, and possess band gap in the
range 1.1–2.5 eV (Table 22.2). The optical properties of ferrite nanoparticles can
be investigated by UV–visible absorption spectroscopy. The band gap energy can
be evaluated from the Eg measurements using Kubelka–Munk (K–M) model, and
the F(R) value is estimated from the following equation:

F.R/ D .1  R/2 =2R

where F(R) is the Kubelka–Munk function and R is the diffuse reflectance. A graph
is plotted between [F(R)h]2 and h; the intercept value is the band gap energy.
For example, the estimated values of the band gap of Zn1x Cux Fe2 O4 (x D 0.0,
0.1, 0.2, 0.3, 0.4, and 0.5) system are 2.1, 2.07, 2.05, 2.03, 2.0, and 1.95 eV,
respectively [54]. The band gap energy decreases with increasing Cu content, which
may be associated with various parameters including the crystallite size, structural
parameter, carrier concentrations, presence of very small amount of impurities
which are not detectable by XRD and SEM/EDX techniques, and lattice strain.
Interestingly, a possible correlation between the band gap and the lattice parameter
can be highlighted; it was noticed that both values of band gap as well as lattice
parameter decrease with increasing Cu concentration [54].

22.4 Applications

SFs offer numerous applications in wide-range fields, including biomedical, sensors

and biosensors, high-frequency components, low-temperature co-fired ceramic
(LTCC) devices, supercapacitors, microwave absorption, and photocatalytic activity.
318 T. Tatarchuk et al.

22.4.1 Biomedical

Magnetic nanoparticles possess great potential for innumerable applications like

magnetic carriers in bio-screening, magnetic resonance imaging (MRI), cell sep-
aration, contrast enhancement, tissue repair, cancer treatment and controlled drug
delivery, hyperthermia, and related biomedical areas [62]. SFs have exclusively
gained importance in magnetic hyperthermia applications. Magnetic hyperthermia
treatment is a technique whereby spherically shape-controlled ferrite nanoparticles
are targeted through the bloodstreams which can selectively kill cancer cells and
tumors by raising their temperature in the range 41–46 ı C by noninvasive manner
[63].
Spherical uniform-sized ferrite particles having an average diameter between
50 and 150 nm are used in biomedical applications to achieve high throughput.
This facilitates a uniform immobilization of bio-functional molecules on the shape-
controlled ferrite particles so as to bestow unvarying magnetic, hydrodynamic,
biocompatibility, and colloidal stability properties. Ruthradevi and co-workers [64]
attempted nickel ferrite nanoparticles in calcium phosphate nanostructure exhibiting
ferromagnetic behavior with coercivity of 0.045 T at 5 K and the superparam-
agnetic behavior with zero coercivity at 300 K giving a scope for hyperthermia
treatment. Magnetic fluid obtained by colloidal suspension of manganese/zinc
ferrite nanoparticles (15–17 nm) were stabilized through steric repulsion by coating
with biologically compatible carboxymethyl dextran (CMDx) [65]. Cell viability
measurements showed that the magnetic fluid is nontoxic to MCF-7 and CaCo-2 cell
lines at concentrations of up to 7.5 mg/mL of particle fraction for a contact time of
up to 48 h. The stability and nontoxicity, superparamagnetic behavior, and cytotoxic
effects show a possibility for biomedical applications. Calcium-doped zinc ferrite
within the range of 12–14 nm employed for hemolysis testing demonstrated that
the ferrite material was not cytotoxic when using 10 mg of ferrite/mL of solution.
Accordingly Zn0.50 Ca0.50 Fe2 O4 was found to be a potential material for cancer
treatment by magnetic hyperthermia therapy [63]. Likewise, many spherical-shaped,
uniform-sized, and colloidal stable dispersions employing ferrite particles showcase
as promising magnetic carriers for biomedical applications.

22.4.2 Sensors and Biosensors

Ferrite nanoparticles are widely used as sensor materials for detecting different
analytes at the trace levels. CoFe2 O4 plays an important role in the fabrication of gas
sensors. A simple conductometric sensor has been fabricated using samarium (Sm)-
doped cobalt ferrite for the detection of hydrogen leaks [66]. Cobalt–manganese
ferrite appears to be quite suitable for an application as CO2 gas sensors [67].
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 319

Ferrites have also proved as excellent materials for electrochemical biosensor

because of their sensing accuracy, low detection levels of the analyte, and quick
analysis time. Some of the examples include Fe3 O4 , ”-Fe2 O3 , CoFe2 O4 , MnFe2 O4 ,
and ZnFe2 O4 . Among these, gold (Au)-coated Fe3 O4 nanoparticle-based biosensors
are widely studied and used for detection of a number of biochemical moieties [8].
Nanostructured ZnFe2 O4 ionic liquid carbon paste electrode sensor exhibited low
interfacial resistance and fast electron transfer capacity, high sensitivity to trace
level, good detection limits, and excellent reproducibility for the determination of 5-
fluorourcile anticancer drug and real pharmaceutical and human urine samples even
at trace level [68].

22.4.3 High-Frequency Components

MFe2 O4 (M D Mn, Fe, Co, etc.) spinels have attracted much consideration
in the recent years in applications such as computers, communications, office
automation, remote monitoring, audio and video equipment, household appliances,
and industrial automation technology. At present, electronic industries are in need
of magnetic materials especially ferrite-based compounds. Nevertheless, with the
arrival of high-frequency applications, the regular techniques of reducing eddy
current losses, using iron cores which are in practice, become less efficient and
not cost-effective. Moreover, the existing switched mode power supplies industries
required even low energy losses in power conversion with maintenance of adequate
initial permeability. Manganese–zinc ferrite with low magnetic loss, high saturation
magnetization, high permeability, and high magnetic domain relaxation frequency
was achieved. This type of ferrite material finds use in electronic and electrical
industries especially for manufacturing deflection yoke rings, memory chips, mag-
netic recording heads, transformers, transducers, and other devices [69].

22.4.4 LTCC Devices

By the advent of miniaturization of electronic products, the low temperature co-fired

ceramic (LTCC) materials and chip devices have gained importance due to their
small volume and mass. NiCuZn ferrite and M-type barium ferrite play a dominant
role in the manufacture of components in miniature form. These ferrites led to
surface mounting devices and are used as multilayer chip inductor and wire wound
chip inductor. Specifically, NiCuZn ferrites are best suited magnetic materials
for capacitors, transformers, microwave gyromagnetic devices, and components
in electronic products like cell phones, video cameras [70], laptops, and wireless
communication systems [71, 72].
320 T. Tatarchuk et al.

22.4.5 Supercapacitors

CoFe2 O4 , SnFe2 O4 , and many other metal ferrites have been largely used for charge
storage applications. Recently, doped manganese ferrite nanoparticles chemically
anchored on graphene nanosheets exhibited an enhanced capacitive performance
as compared to individual components due to the synergistic effect of faradic
behavior and electric double layer capacitance. The ferrites in various morphologies
have influence in varying the surface area of the material leading to different
supercapacitance values. The higher the surface area, the higher the charge storage
capacity becomes. The ferrites are observed to have a specific capacitance value
around 50–400 F/g. The fascinating electrochemical activity of several ferrite
nanocomposites makes them a potential candidate for supercapacitor applications
[73–75].

22.4.6 Microwave Absorption

In the day-to-day life applications, radio broadcasting, satellite communications,

radars, GPS, cell phones, and wireless networks operate at microwave frequency
range 1–18GHz. The efficiency of these systems can be severely affected by
unwanted reflections or emissions in addition to associated health risks. In this
context, ferrites play a predominant role in reflection suppression or damping of
free space electromagnetic waves [76].
Various compounds mainly based on planar M-, W-, Y-, Z-, and U-type
hexagonal ferrite structures are extensively employed as electromagnetic (EM)
wave absorbers. Some of the widely discussed materials are lithium–zinc ferrite
doped with La and Mg, SrFe12 O19 /TiO2 nanocomposites, doped barium ferrite,
Ce-substituted barium ferrite, nickel- and zinc-substituted strontium hexaferrite,
MnFe2 O4 /wax, RGO/MnFe2 O4 /wax, and the RGO/MnFe2 O4 /PVDF; these are
some of the most excellent wave absorbing ferrites in the microwave frequency
range of 8–12 GHz (X band). All the above materials have been evaluated with
a minimum reflection loss observed at the studied frequency range. In addition,
similar substituted hexagonal ferrites are also tested for broadband absorption
between 12 and 30 GHz and thus suiting application in RADAR absorption [77–
81].

22.4.7 Photocatalytic Activity

Ferrites are one of the most promising photocatalysts, with the characteristic
behavior of absorbing visible light, and possess a band gap in the range 1.1–2.3 eV.
Besides, ferrites overcome the technical problem of separation and reuse as they
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 321

are magnetically separable. The spinel structure of metal ferrites provides extra
catalytic reaction sites resulting in enhanced photocatalytic degradation efficiency.
Ferrites possess important photocatalytic properties for many industrial processes,
including the oxidative dehydrogenation of hydrocarbons; photo-Fenton-like pro-
cess; decomposition of alcohols and hydrogen peroxide; the treatment of exhaust
gases; the oxidation of compounds such as CO, H2 , CH4 , and chlorobenzene;
the hydroxylation of phenol; alkylation reactions; the hydrodesulphurization of
crude petroleum; the catalytic combustion of methane; degradation of toxic dyes;
elimination of contaminants from water and air; odor control; bacterial inactivation;
water splitting to produce H2 ; the inactivation of cancer cells; and many others.
Numerous studies have focused on potential ferrite catalyst such as meso-CuFe2 O4 ,
meso-CoFe2 O4 , GO-NiFe2 O4 , BiFeO3 , ZnFe2 O4 , Fe3 O4 , MnFe2 O4 with activated
carbon, BaFe2 O4 , BaFeO3x , ZnFe2 O4 –graphene, mesoporous-ZnFe2 O4 , CuFe2 O4 ,
CoFe2 O4 , MnFe2 O4 , NiFe2 O4 CoFe2 O4 –graphene, SrFe12 O19 , etc. Utilizing ferrite-
based photocatalytic studies for wider applications promotes sustainable eco-
friendly and cleaner technologies [44, 82, 83].

22.5 Conclusions

In this chapter, synthesis methods, crystal structure, properties, and perspective

applications of SFs are summarized. Magnetic spinel nanoparticles gained a lot
of interest due to their ability to be manipulated upon application of an external
magnetic field and thereby can be utilized as gas sensors, catalysts, photocatalysts,
adsorbents, electronic devices, etc. The specific focus was on the methods of
preparation (microemulsion, ultrasonic, non-hydrolytic, solvothermal, coprecipita-
tion, sol–gel, microwave-assisted, mechanical milling, etc.), the crystal structure,
magnetic and optical properties, and different application of SFs. The influence of
the synthesis method on the ferrite particle size was also described. The crystal
structure, cationic distribution, and exchange interaction between the magnetic ions
are responsible for the magnetic behavior in SFs. Finally, it can be concluded that
SFs are suitable materials for many technological applications.

References

1. Yan Z, Gao J, Li Y, Zhang M et al (2015) Hydrothermal synthesis and structure evolution of

metal-doped magnesium ferrite from saprolite laterite. RSC Adv 5:92778–92787
2. Olsson RT, Salazar-Alvarez G, Hedenqvist SM et al (2005) Controlled synthesis of near-
stoichiometric cobalt ferrite nanoparticles. Chem Mater 17:5109–5118
3. Latham AH, Williams ME (2008) Controlling transport and chemical functionality of magnetic
nanoparticles. Acc Chem Res 41:411–420
4. Moussaoui HE, Mahfoud T, Habouti S et al (2016) Synthesis and magnetic properties of tin
spinel ferrites doped manganese. J Magn Magn Mater 405:181–186
5. Mathew DS, Juang R (2007) An overview of the structure and magnetism of spinel ferrite
nanoparticles and their synthesis in microemulsions. Chem Eng J 129:51–65
322 T. Tatarchuk et al.

6. Carta D, Casula MF, Falqui A et al (2009) A structural and magnetic investigation of the
inversion degree in ferrite nanocrystals MFe2 O4 (M D Mn, Co, Ni). J Phys Chem C 113:8606–
8615
7. Song Q, Ding Y, Wang ZL et al (2007) Tuning the thermal stability of molecular precursors for
the nonhydrolytic synthesis of magnetic MnFe2 O4 spinel nanocrystals. Chem Mater 19:4633–
4638
8. Kefeni KK, Msagati TAM, Mamba BB (2017) Ferrite nanoparticles: synthesis, characterisation
and applications in electronic device. Mater Sci Eng B 215:37–55
9. Pang YL, Lim S, Ong H et al (2016) Research progress on iron oxide-based magnetic materials:
synthesis techniques and photocatalytic applications. Ceram Int 42:9–34
10. Goswami PP, Choudhury HA, Chakma S et al (2013) Sonochemical synthesis and characteri-
zation of manganese ferrite nanoparticles. Ind Eng Chem Res 52:17848–17855
11. Kurikka JL, Shafi VPM, Ulman A et al (2004) Mixed ironmanganese oxide nanoparticles. J
Phys Chem B 108:14876–14883
12. Song Q, Zhang ZJ (2012) Controlled synthesis and magnetic properties of bimagnetic spinel
ferrite CoFe2 O4 and MnFe2 O4 nanocrystals with core–shell architecture. J Am Chem Soc
134:10182–10190
13. Ni D, Lin Z, Xiaoling P et al (2015) Preparation and characterization of nickel-zinc ferrites by
a solvothermal method. Rare Metal Mater Eng 44:2126–2131
14. Li Z, Gao K, Han G, Wang R et al (2015) Solvothermal synthesis of MnFe2 O4 colloidal
nanocrystal assemblies and their magnetic and electrocatalytic properties. New J Chem
39:361–368
15. Yin Y, Liu W, Huo N et al (2016) Synthesis of vesicle-like MgFe2 O4 /Graphene 3D net-
work anode material with enhanced lithium storage performance. ACS Sustain Chem Eng.
doi:10.1021/acssuschemeng.6b01949
16. Pereira C, Pereira AM, Fernandes C et al (2012) Superparamagnetic MFe2 O4 (M D Fe, Co,
Mn) nanoparticles: tuning the particle size and magnetic properties through a novel one-step
coprecipitation route. Chem Mater 24:1496–1504
17. Carta D, Loche D, Mountjoy G et al (2008) NiFe2 O4 nanoparticles dispersed in an aerogel
silica matrix: an X-ray absorption study. J Phys Chem C 112:15623–15630
18. Mukhtar MW, Irfan M, Ahmad I et al (2015) Synthesis and properties of Pr-substituted MgZn
ferrites for core materials and high frequency applications. J Magn Magn Mater 381:173–178
19. Sharma R, Bansal S, Singhal S (2015) Tailoring the photo-Fenton activity of spinel ferrites
(MFe2 O4 ) by incorporating different cations (M D Cu, Zn, Ni and Co) in the structure. RSC
Adv 5:6006–6018
20. Jesudoss SK, Vijaya JJ, Kennedy LJ et al (2016) Studies on the efficient dual performance
of Mn1–x Nix Fe2 O4 spinel nanoparticles in photodegradation and antibacterial activity. J
Photochem Photobiol B 165:121–132. doi:10.1016/j.jphotobiol.2016.10.004
21. Tadjarodi A, Imani M, Salehi M (2015) ZnFe2 O4 nanoparticles and a clay encapsulated
ZnFe2 O4 nanocomposite: synthesis strategy, structural characteristics and the adsorption of
dye pollutants in water. RSC Adv 5:56145–56156
22. Marinca TF, Chicinaş I, Isnard O et al (2016) Nanocrystalline/nanosized manganese substituted
nickel ferrites – Ni1x Mnx Fe2 O4 obtained by ceramic-mechanical milling route. Ceram Int
42(4):4754–4763. doi:10.1016/j.ceramint.2015.11.155
23. Angadi VJ, Rudraswamy B, Sadhana K et al (2016) Effect of Sm3C –Gd3C on structural,
electrical and magnetic properties of Mn–Zn ferrites synthesized via combustion route. J Alloys
Compd 656:5–12. doi:10.1016/j.jallcom.2015.09.222
24. Singh C, Jauhar S, Kumar V et al (2015) Synthesis of zinc substituted cobalt ferrites
via reverse micelle technique involving in situ template formation: a study on their
structural, magnetic, optical and catalytic properties. Mater Chem Phys 156:188–197.
doi:10.1016/j.matchemphys.2015.02.046
25. Kotsikau D, Ivanovskaya M, Pankov V et al (2015) Structure and magnetic properties
of manganese–zinc-ferrites prepared by spray pyrolysis method. Solid State Sci 39:69–73.
doi:10.1016/j.solidstatesciences.2014.11.013
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 323

26. Cortes MS, Martínez-Luevanos A, García-Cerda LA et al (2015) Nanostructured pure and sub-
stituted cobalt ferrites: fabrication by electrospinning and study of their magnetic properties. J
Alloys Compd 653:290–297. doi:10.1016/j.jallcom.2015.08.262
27. Cai X, Wang J, Li B et al (2016) Microwave absorption properties of LiZn ferrites hollow
microspheres doped with La and Mg by self-reactive quenching technology. J Alloys Compd
657:608–615. doi:10.1016/j.jallcom.2015.10.153
28. Ishaque M, Khan MA, Ali I et al (2015) Investigations on structural, electrical and
dielectric properties of yttrium substituted Mg-ferrites. Ceram Int 41(3):4028–4034.
doi:10.1016/j.ceramint.2014.11.093
29. Anjum S, Hameed S, Bashir F (2015) Microstructural, structural, magnetic and optical
properties of antimony doped cobalt spinel ferrites. Mater Today Proc 2(10):5329–5336.
doi:10.1016/j.matpr.2015.11.045
30. Cross WB, Affleck L, Kuznetsov MV et al (1999) Self-propagating high-temperature synthesis
of ferrites MFe2 O4 (M D Mg, Ba, Co, Ni, Cu, Zn); reactions in an external magnetic field. J
Mater Chem 9:2545–2552. doi:10.1039/A904431K
31. Peng E, Ding J, Xue JM (2014) Concentration-dependent magnetic hyperthermic response of
manganese ferrite-loaded ultrasmall graphene oxide nanocomposites. New J Chem 38:2312–
2319. doi:10.1039/C3NJ01555F
32. Leal MP, Rivera-Fernández S, Franco JM et al (2015) Long-circulating PEGylated man-
ganese ferrite nanoparticles for MRI-based molecular imaging. Nanoscale 7:2050–2059.
doi:10.1039/C4NR05781C
33. Kaiser M (2016) Magnetic and electric modulus properties of ln substituted Mg–Mn–Cu
ferrites. Mater Res Bull 73:452–458. doi:10.1016/j.materresbull.2015.09.015
34. Kombaiah K, Vijaya JJ, Kennedy LJ, Bououdina M (2017) Optical, magnetic and structural
properties of ZnFe2 O4 nanoparticles synthesized by conventional and microwave assisted
combustion method: a comparative investigation. Optik Int J Light Electron Optics 129:57–
68. doi:10.1016/j.ijleo.2016.10.058
35. Kurta SA, Mykytyn IM, Tatarchuk TR (2014) Structure and the catalysis mechanism of
oxidative chlorination in nanostructural layers of a surface of alumina. Nanoscale Res Lett
9:357. doi:10.1186/1556-276X-9-357
36. Tatarchuk T (2014) ´atalytic oxidation of carbon monoxide on lithium-zinc ferrites with a
spinel structure. Ekologia i Technika 32(2):70–75
37. Tatarchuk TR, Boyko EV, Yaremiy IP et al (2014) Synthesis crystal chemistry and antistructure
modelling of CoFe2 O4 nanoparticles prepared by citrate sol-gel method. Phys Chem Solid State
15(4):792–797
38. Sickafus KE, Wills JM, Grimes NW (1999) Structure of spinel. J Am Ceram Soc 82:3279–
3292. doi:10.1111/j.1151-2916.1999.tb02241.x
39. Kane SN, Satalkar M (2017) Correlation between magnetic properties and cationic distri-
bution of Zn0.85x Nix Mg0.05 Cu0.1 Fe2 O4 nanospinel ferrite: effect of Ni doping. J Mater Sci
52(6):3467–3477. doi:10.1007/s10853-016-0636-7
40. Tatarchuk TR, Bououdina M, Paliychuk ND et al (2017) Structural characterization and
antistructure modeling of cobalt-substituted zinc ferrites. J Alloys Compd 694(15):777–791.
doi:10.1016/j.jallcom.2016.10.067
41. Angadi VJ, Choudhury L, Sadhana K et al (2017) Structural, electrical and magnetic
properties of Sc3C doped Mn-Zn ferrite nanoparticles. J Magn Magn Mater 424:1–11.
doi:10.1016/j.jmmm.2016.10.050
42. Lemine OM, Bououdina M, Sajieddine M et al (2011) Synthesis, structural, mag-
netic and optical properties of nanocrystalline ZnFe2 O4 . Physica B 406(10):1989–1994.
doi:10.1016/j.physb.2011.02.072
43. Al-Saie AM, Bououdina M, Jaffar A et al (2011) The effect of annealing on the structure,
magnetic properties and AC heating of CoFe2 O4 for biomedical applications. J Alloys Compd
509:S393–S396. doi:10.1016/j.jallcom.2011.02.024
44. Sundararajan M, Sailaja V, Kennedy LJ, Vijaya JJ (2017) Photocatalytic degradation of
rhodamine B under visible light using nanostructured zinc doped cobalt ferrite: kinetics and
mechanism. Ceram Int 43(1A):540–548. doi:10.1016/j.ceramint.2016.09.191
324 T. Tatarchuk et al.

45. Angadi VJ, Anupama AV, Choudhary HK et al (2017) Mechanism of ”-irradiation induced
phase transformations in nanocrystalline Mn0.5 Zn0.5 Fe2 O4 ceramics. J Solid State Chem
246:119–124. doi:10.1016/j.jssc.2016.11.017
46. Angadi VJ, Rudraswamy B, Sadhana K et al (2016) Structural and magnetic properties of
manganese zinc ferrite nanoparticles prepared by solution combustion method using mixture
of fuels. J Magn Magn Mater 409:111–115. doi:10.1016/j.jmmm.2016.02.096
47. Gawas SG, Meena SS, Yusuf SM et al (2016) Anisotropy and domain state dependent
enhancement of single domain ferrimagnetism in cobalt substituted Ni–Zn ferrites. New J
Chem 40:9275–9284. doi:10.1039/C6NJ02121B
48. Singh SB, Srinivas C, Tirupanyam BV et al (2016) Structural, thermal and magnetic studies of
Mgx Zn1x Fe2 O4 nanoferrites: study of exchange interactions on magnetic anisotropy. Ceram
Int 42(16):19179–19186. doi:10.1016/j.ceramint.2016.09.081
49. Sundararajan M, Kennedy LJ, Vijaya JJ et al (2015) Microwave combustion synthesis
of Co1x Znx Fe2 O4 (06x60.5): structural, magnetic, optical and vibrational spectroscopic
studies. Spectrochim. Acta Part A 140:421–430. doi:10.1016/j.saa.2014.12.035
50. Manikandan A, Vijaya JJ, Mary JA et al (2014) Structural, optical and magnetic properties
of Fe3 O4 nanoparticles prepared by a facile microwave combustion method. J Ind Eng Chem
20(4):2077–2085. doi:10.1016/j.jiec.2013.09.035
51. Lemine OM, Omri K, Zhang B et al (2012) Sol–gel synthesis of 8 nm magnetite
(Fe3 O4 ) nanoparticles and their magnetic properties. Superlattice Microst 52(4):793–799.
doi:10.1016/j.spmi.2012.07.009
52. Manikandan A, Kennedy LJ, Bououdina M et al (2014) Synthesis, optical and magnetic
properties of pure and Co-doped ZnFe2 O4 nanoparticles by microwave combustion method.
J Magn Magn Mater 349:249–258. doi:10.1016/j.jmmm.2013.09.013
53. Manikandan A, Vijaya JJ, Kennedy LJ et al (2013) Microwave combustion synthesis, struc-
tural, optical and magnetic properties of Zn1x Srx Fe2 O4 nanoparticles. Ceram Int 39(5):5909–
5917. doi:10.1016/j.ceramint.2013.01.012
54. Manikandan A, Vijaya JJ, Kennedy LJ et al (2013) Structural, optical and magnetic properties
of Zn1x Cux Fe2 O4 nanoparticles prepared by microwave combustion method. J Mol Struct
1035:332–340. doi:10.1016/j.molstruc.2012.11.007
55. Manikandan A, Vijaya JJ, Kennedy LJ (2013) Comparative study of pure and Ni-doped
ZnFe2 O4 nanoparticles for structural, optical and magnetic properties. Adv Mater Res
699:524–529
56. Panchal S, Raghuvanshi S, Gehlot K et al (2016) Cationic distribution assisted tuning of
magnetic properties of Li0.5-x/2 Znx Fe2.5-x/2 O4 . AIP Adv 6(5):055930. doi:10.1063/1.4944517
57. Khalaf KAM, Al-Rawas AD, Widatallah HM et al (2016) Influence of Zn2C ions on the
structural and electrical properties of Mg1x Znx FeCrO4 spinels. J Alloys Compd 657:733–
747. doi:10.1016/j.jallcom.2015.10.157
58. Hashim M, Shirsath SE, Meena SS et al (2015) Manganese ferrite prepared using reverse
micelle process: structural and magnetic properties characterization. J Alloys Compd 642:70–
77. doi:10.1016/j.jallcom.2015.04.085
59. Heiba ZK, Mohamed MB, Ahmed MA et al (2014) Cation distribution and dielectric
properties of nanocrystalline gallium substituted nickel ferrite. J Alloys Compd 586:773–781.
doi:10.1016/j.jallcom.2013.10.137
60. Hemeda OM, Mostafa NY, Abd Elkader OH et al (2014) Solubility limits in Mn–
Mg ferrites system under hydrothermal conditions. J Magn Magn Mater 364:39–46.
doi:10.1016/j.jmmm.2014.03.061
61. Manikandan A, Vijaya JJ, Sundararajan M et al (2013) Optical and magnetic properties of Mg-
doped ZnFe2 O4 nanoparticles prepared by rapid microwave combustion method. Superlattice
Microst 64:118–131. doi:10.1016/j.spmi.2013.09.021
62. Tanaka T, Shimazu R, Nagai H et al (2009) Preparation of spherical and uniform-sized ferrite
nanoparticles with diameters between 50 and 150 nm for biomedical applications. J Magn
Magn Mater 321:1417–1420
22 Spinel Ferrite Nanoparticles: Synthesis, Crystal Structure, Properties. . . 325

63. Jasso-Terán RA, Cortés-Hernández DA, Sánchez-Fuentes HJ et al (2017) Synthesis, char-

acterization and hemolysis studies of Zn(1x) Cax Fe2 O4 ferrites synthesized by sol-gel for
hyperthermia treatment applications. J Magn Magn Mater. doi:10.1016/j.jmmm.2016.10.099
(in press)
64. Ruthradevi T, Akbar J, Kumar GS et al (2017) Investigations on nickel ferrite embedded
calcium phosphate nanoparticles for biomedical applications. J Alloys Compd 695:3211–3219.
doi:10.1016/j.jallcom.2016.11.300
65. Latorre-Esteves M, Corte’s A, Torres-Lugo M et al (2009) Synthesis and characterization of
carboxymethyl dextran-coated Mn/Zn ferrite for biomedical applications. J Magn Magn Mater
321:3061–3066
66. Falsafi F, Hashemi B, Mirzaei A et al (2017) Sm-doped cobalt ferrite nanoparticles: a
novel sensing material for conductometric hydrogen leak sensor. Ceram Int 43:1029–1037.
doi:10.1016/j.ceramint.2016.10.035
67. Sandu I, Presmanes L, Alphonse P et al (2006) Nanostructured cobalt manganese ferrite thin
films for gas sensor application. Thin Solid Films 495:130–133
68. Wen T, Zhu W, Xue C et al (2014) Novel electrochemical sensing platform based on magnetic
field-induced self-assembly of Fe3 O4 @Polyaniline nanoparticles for clinical detection of
creatinine. Biosens Bioelectron 56:180–185
69. Praveena K, Chen H-W, Liu H-L et al (2016) Enhanced magnetic domain relaxation frequency
and low power losses in Zn2C substituted manganese ferrites potential for high frequency
applications. J Magn Magn Mater 420:129–142
70. Li B, Yue Z-X, Qi X-W et al (2003) High Mn content NiCuZn ferrite for multiplayer chip
inductor application. Mater Sci Eng B 99:252–254
71. Yang Q, Zhang H, Liu Y et al (2009) Microstructure and magnetic properties of microwave
sintered M-type barium ferrite, for application in LTCC devices. Mater Lett 63:406–408
72. Reddy NR, Ramana MV, Rajitha G et al (2009) Stress insensitive NiCuZn ferrite compositions
for microinductor applications. Curr Appl Phys 9:317–323
73. Kumbhar VS, Jagadale AD, Shinde NM et al (2012) Chemical synthesis of spinel cobalt ferrite
(CoFe2 O4 ) nano-flakes for supercapacitor application. Appl Surf Sci 259:39–43
74. Bashir B, Shaheen W, Asghar M et al (2016) Copper doped manganese ferrites nanoparticles
anchored on graphene nano-sheets for high performance energy storage applications. J Alloys
Compd 695:881–887. doi:10.1016/j.jallcom.2016.10.183
75. Bindu K, Sridharan K, Ajith KM et al (2016) Microwave assisted growth of stannous ferrite
microcubes as electrodes for potentiometric nonenzymatic H2 O2 sensor and supercapacitor
applications. Electrochim Acta 217:139–149
76. Charalampos AS, Litsardakis G (2016) Y-type hexagonal ferrites for microwave absorber and
antenna applications. J Magn Magn Mater 405:54–61
77. Dadfar MR, Ebrahimi SAS, Masoudpanah SM (2015) Sol–gel synthesis and characterization
of SrFe12 O19 /TiO2 nanocomposites. J Supercond Nov Magn 28(1):89–94
78. Meng P, Xiong K, Ju K (2015) Wideband and enhanced microwave absorption performance of
doped barium ferrite. J Magn Magn Mater 385:407–411
79. Zhang X-J, Wang G-S, Cao W-Q et al (2014) Enhanced microwave absorption property of
reduced graphene oxide (RGO)-MnFe2 O4 nanocomposites and polyvinylidene fluoride. ACS
Appl Mater Interfaces 6:7471–7478
80. Chang S, Kangning S, Pengfei C (2012) Microwave absorption properties of Ce-substituted
M-type barium ferrite. J Magn Magn Mater 324(5):802–805
81. Tyagi S, Baskey HB, Agarwala RC et al (2011) Development of hard/soft ferrite nanocompos-
ite for enhanced microwave absorption. Ceram Int 37(7):2631–2641
82. Casbeer E, Sharma VK, Li X-Z (2012) Synthesis and photocatalytic activity of ferrites under
visible light: a review. Sep Purif Technol 87:1–14
83. Valero-Luna C, Palomares-Sanchéz SA, Ruíz F (2016) Catalytic activity of the barium
hexaferrite with H2 O2 /visible light irradiation for degradation of methylene blue. Catal Today
266:110–119. doi:10.1016/j.cattod.2015.08.049