Physica B 632 (2022) 413759

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Physica B: Physics of Condensed Matter

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Structural, elastic and magnetic properties of Ca doped copper

ferrite nanoparticles
P. Raji a, K. Balachandra Kumar b, *
a
Department of Physics, Mepco Schlenk Engineering College, Sivakasi, 626005, India
b
Department of Physics, Government Arts and Science College, Sivakasi, 626124, India

A R T I C L E I N F O A B S T R A C T

Keywords: Calcium doped Copper ferrite (CaxCu1-xFe2O4, x = 0.0, 0.1, 0.2, 0.3) nanoparticles were prepared by co-
Ferrite precipitation method. The effect of calcium doping in structural, elastic and magnetic properties of copper
Co- precipitation ferrite were explored by X-ray diffraction (XRD), Scanning electron microscope (SEM), Fourier transform
XRD
infrared (FTIR), and Vibrating Sample magnetometer (VSM). X-ray diffraction verified the single phase cubic
SEM
FTIR
spinel structure and hematite phase also present in x = 0.02 with the space group Fd3m. The average crystallite
VSM size ranged in 44–58 nm and increased with increasing Ca concentration. Scanning electron microscope images
showed that the ferrite particles seem in spherical shape with agglomeration. The Fourier transform infrared
spectrum showed the two main absorption bands of spinel structure in the wavenumber scale of 476–576 cm− 1
assigned to the stretching vibration of A and B sites. The three types of moduli of elasticity, Poisson’s ratio,
velocities of elastic waves and Debye temperature estimated using FTIR. Vibrating Sample magnetometer
exhibited the room temperature ferromagnetic behavior and coercivity decreases with Ca concentration while
saturation magnetization increases.

1. Introduction doped copper nano ferrites yet. The ionic radius of the metal ions present
in Ca doped copper ferrites are Cu2+ (0.73 Å), Ca2+ (0.99 Å), and Fe3+
Over the past few decades, a very large number of works devoted to (0.64 Å). The copper ions are replaced by Ca2+ which has a large ionic
transition metal ferrites due to their multitalented and distinct struc­ radius is an important parameter to change the crystal structure of
tural, optical, and magnetic properties [1,2]. Spinel ferrites are used in a copper ferrite that alters its magnetic behavior.
diversity of applications such as inductors, isolators, circulators, trans­ Numerous methods can be adapted to synthesize copper ferrite
formers, and high frequency applications [3–8]. Among these, Copper nanoparticles such as co - precipitation [18], hydrothermal [19],
ferrite has attracted more attention because it has effective catalytic, auto-combustion [20] and sol gel method [21].
exceptional magnetic and electric properties [9]. Generally, copper Nisha Gautam et al. [22] illustrated that substitution of Zn in copper
ferrite has two crystal structures, tetragonal as well as cubic and the ferrite synthesized by coprecipitation increase the particle size and
structure depends on the occupation of ferric ions [10]. Copper ferrite magnetic properties. Naveen Kumar et al. [23] studied the magnetic
has an inverse spinel structure in which ferric ions are mutually shared properties of copper ferrite by sol-gel auto-combustion method and
in tetrahedral as well as octahedral sites while Copper ions occupy hydrothermal method. Zena Mohammed [24] reported structural,
octahedral sites [11]. The copper ferrite magnetic properties are altered electrical and magnetic properties of cobalt copper ferrite prepared by
due to the arrangement of cations on unoccupied empty spaces. This is a sol–gel method.
vital component to impress the researchers in recent years. Among these methods, coprecipitation is affordable and more suit­
Many efforts had been made to strengthen the properties of CuFe2O4 able for preparing copper ferrites nanoparticles.
by incorporating metal ions/using various methods for synthesis [12, The present paper investigated the structural, elastic and magnetic
13]. The physical properties of copper ferrite doped with nonmagnetic behavior of nonmagnetic calcium (Ca) doped copper ferrite
ions such as Ni2+ [14], Cd2+ [15], Zn2+ [16] and Al3+ [17] have been nanoparticles.
investigated. Moreover, no reports for magnetic properties of calcium

* Corresponding author.
E-mail address: [email protected] (K. Balachandra Kumar).

https://doi.org/10.1016/j.physb.2022.413759
Received 8 November 2021; Received in revised form 18 January 2022; Accepted 8 February 2022
Available online 11 February 2022
0921-4526/© 2022 Elsevier B.V. All rights reserved.
P. Raji and K. Balachandra Kumar Physica B: Physics of Condensed Matter 632 (2022) 413759

2. Experimental and characterization

2.1. Raw materials

All the chemicals were purchased from E Merck and used as received.
Copper chloride di-hydrate (CuCl2⋅2H2O), Ferric chloride hexahydrate
(FeCl3⋅6H2O), Calcium dichloride hexahydrate (CaCl2⋅2H2O) and so­
dium hydroxide (NaOH) are used as starting materials.

2.2. Synthesis of CaxCu1-xFe2O4 particles

CaxCu1-xFe2O4 nanoparticles were prepared by co-precipitation

method. The stoichiometric quantities of CaCl2⋅6H2O, FeCl3⋅6H2O,
and CuCl2⋅2H2O were dissolved in distilled water at room temperature.
Then 1 M NaOH solution was poured drop by drop into the solution
placed on the magnetic mixer till pH 13 was reached and heated at 80 ◦ C
under constant stirring. The resulting solution was turned into brown
colour and then the solution was stirred continuously for 3 h. The
resulting precipitate was collected and washed four times with de-
ionized water to remove chloride and impurities. The samples were Fig. 2. XRD Pattern of Ca doped Copper Ferrite.
dried for 8 h and the dried powders were put into a mortar and grinded
manually for 20 min to obtain a fine powder. The samples were annealed presence of hematite phase is due to the divalent element loss in the
for 4 h at 900 ◦ C to obtain the final product with better crystallinity and prepared material and the excess of Fe provided by the contamination
purity. This is shown in Fig. 1. [28].
The crystalline size of the particles have been calculated using the
0.8CaCl26H2O +0.2CuCl22H2O +2FeCl36H2O + → Ca0⋅2Cu0⋅8Fe2O4 +4Cl2
Debye-Sherrer formula [29],
+17H2O
kλ
d= (1)
β cos θ

2.2.1. Characterization techniques where d-crystallite size, k-grain shape factor (0.9), λ - wavelength of the
The structural properties of samples are studied by a Rigaku X-ray incident Cu-Kα beam,θ- Bragg’s reflection angle and β -full width at half
diffractometer using the CuKα radiation (wavelength 1.5406 Å). The maximum.
morphology of the samples are revealed using Scanning electron mi­ It was found that the value of crystallite size ranging 44.01–58.70
croscopy (EVO18 - CARL ZEISS). The functional groups are identified by nm. This is due to the replacement of smaller ions with larger ions. It
the Jasco model FT-IR 310 spectrophotometer. The room temperature indicates that Ca2+ ions successfully incorporated in CuFe2O4 ferrites
magnetic behavior was investigated using vibrating sample magne­ [30]. The particle size increases indicates the reduction in the densities
tometer (Lakeshore, 7304). of nucleation centers in the samples [31].
The lattice constant of the samples are calculated using the relation
3. Results and discussion [32]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
3.1. X ray diffraction a = d h2 + k2 + l2 (2)

The purity and the structure of the samples were analysed from XRD where a - lattice parameter, (hkl) - Miller indices and d -interplanar
and shown in Fig. 2. The peaks observed in XRD are identical with cubic distance.
copper ferrite structure (JCPDS File No. 77–0010) [25,26]. High in­ It is observed that the lattice constant increases with increasing the
tensity peaks have appeared at 31◦ (220), 35◦ (311) 38◦ (400), 45◦ (422) calcium concentration. This is by the cause of Ca2+ (0.99 Å) ions ionic
and 62◦ (440), and confirmed fd3m space group [27] in pure and doped radius related to Cu2+ (0.73 Å) and Fe3+ (0.64 Å) results in the short­
copper ferrite and two peaks present in 24.3◦ (012) and 33.2◦ (104) ening of bond length and lattice parameter [33]. The increase in unit cell
indicate the presence of Hematite (α-Fe2O3) as minor phase. The volume increases the crystallite size consecutively and proposed that the
micro-strain formed in calcium doped copper ferrite is a tensile type
strain. It also reveals that Ca2+was incorporated successfully in the
copper ferrite.
The values of X-ray density has been calculated using the formula
[34],
8M
dx = (3)
NV

where, M − molecular weight, N - Avogadro’s number and V- volume of

the unit cell. The x-ray density values decrease with the increase of
calcium doping composition.
The distance between the magnetic ions (LA and LB) in the A-site and
B-site can be determined calculated using the relation [35].
√̅̅̅
3
LA = a (4)
Fig. 1. Synthesis of Ca doped Copper Ferrite.
4

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P. Raji and K. Balachandra Kumar Physica B: Physics of Condensed Matter 632 (2022) 413759

√̅̅̅ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
2 11
LB = a (5) dBxEu = a 4u2 − 3u + (13)
4 16
[ ]
where a = lattice parameter. √̅̅̅ 1
The hopping lengths and bond lengths are directly related to the RA = a 3 δ + (14)
8
lattice constant. So, the values of hopping lengths are increases with
calcium concentration. This is due to the difference in ionic radius of [
1 δ
]12
copper and calcium ions. RB = a − + 3δ2 (15)
16 2
The theoretical lattice constant was obtained using the following
expression [36]. where a = lattice parameter, u-oxygen positional parameter and δ -
8 [ √̅̅̅ ] inversion parameter.
ath = √̅̅̅ (rA + Ro ) + 3 (rB + Ro ) (6) The ionic radius of the tetrahedral and octahedral sites increases due
3 3
to the doping of larger size Ca2+ions replace the smaller Ferric ions. As
where ath = theoretical lattice parameter, rA & rB - mean radii of the A the calcium ion was prefer to occupy the tetrahedral site (A site) by the
and B sites and R0 – radius of oxygen ion. replacement of Ferric ions in copper ferrite, therefore, the increasing
The theoretical and experimental lattice constant values are sus­ trend is considerable. The octahedral radius are larger than the tetra­
taining the same increasing tendency. As a result of Ca ions occupying hedral radius in all the samples.
the A-site by replacing Ferric ions in B-site, the small difference between The covalent bond character of the spinel ferrite is inversely pro­
these values would be expected [37]. portional to the bond lengths. The covalent bond character decreases
The calculated crystallite size of the particles, lattice constant with calcium concentration.
(theoretical and experimental), X ray density and hopping lengths, are The bond lengths between cation–cation, cation–anion and bond
reported in Table 1. angles (b,c,d,e,f,p,q,r,s,θ1, θ2, θ3, θ4, θ5) were calculated using the
The mean radii of the A and B sites (rA and rB) are calculated using following relations [41] and listed in Table 3.
the following expression [38] and reported in Table 2. √̅̅̅/
( ) b=a 2 4 (16)
√̅̅̅ 1
rA = a 3 u − − Ro (7)
4 √̅̅̅̅̅/
c = a 11 8 (17)
( )
5
r B = a − u − Ro (8) √̅̅̅/
8 d=a 3 4 (18)

where a = lattice parameter, u - oxygen positional parameter and R0 – √̅̅̅/

radius of oxygen ion. e = 3a 3 8 (19)
The values of both rA and rB increase with increasing the Ca ions
content; this is due to the replacement of Ferric ions with Ca2+ ions f = a/4 (20)
which has a large ionic radius at the A sites, and the substitution of ferric
ions with large ionic radius in the place of copper ions at the B sites. It p = a(0.5 − u) (21)
indicates that iono-covalent character of the copper ferrite decreases √̅̅̅
with Ca concentration. Similar results were reported by Lakshita et al. in q = a 3(u − 0.125) (22)
Zn – Mg [39]. √̅̅̅̅̅
The shortest distance between cation in A site/B site and oxygen ion r = a 11 (u − 0.125) (23)
(dAX&dBX), tetrahedral edge (dAXE), shared and unshared octahedral ( √̅̅̅ / )
edge (dBXE&dBXEu) can be deduced by using the following relations [40] s = a 3 3 (u − 0.5) (24)
and reported in Table 2.
( ) ( )
√̅̅̅ p2 + q2 − c2
dAX = a 3 u −
1
(9) θ1 = cos− 1
(25)
4 2pq

√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ( )
p2 + r2 − e2
dBx = a 3u2 −
11
u+
43
(10) θ2 = cos− 1
(26)
4 64 2pr

( ) ( )
√̅̅̅ 1 2p2 − b2
dAXE = a 2 2u − (11) θ3 = cos− 1
(27)
2 2p2

√̅̅̅ ( )
dBXE = a 2(1 − 2u) (12) θ4 = cos− 1 p2 + s2 − f 2
(28)
2ps
( )
r 2 + q2 − d 2
Table 1 θ5 = cos− 1
(29)
2rq
Crystallite size (D), lattice parameter (ath&aexp), and x-ray density, hopping
lengths. The bond angles θ1, θ2 and θ5 decrease represent the strengthening of
S. X D aexp dx (gm/ LA (Ǻ) LB (Ǻ) ath
A–B interactions and weakening of A–A interactions. The value of θ3 and
No (nm) (nm) cm3) (nm) θ4 increase represent the weakening of B–B interactions [42].
1 0.0 44.01 8.323 5.5 3.6038 2.9380 8.319
2 0.1 54.25 8.343 5.43 3.6125 2.9450 8.337 3.2. Microstructural studies
3 0.2 56.24 8.349 5.31 3.6151 2.9471 8.344
4 0.3 58.69 8.357 5.18 3.6185 2.9500 8.353
The Scanning electron micrographs of all the samples are shown in

3
P. Raji and K. Balachandra Kumar Physica B: Physics of Condensed Matter 632 (2022) 413759

Table 2
Ionic radius of A-site andB- site, tetrahedral and octahedral bond length, tetrahedral edge, shared and unshared octahedral edge, packing coefficients.
S.No X rA (Ǻ) rB (Ǻ) RA (Ǻ) RB (Ǻ) dAx (Ǻ) dBx (Ǻ) dAxE (Ǻ) dBxE (Ǻ) dBxEu (Ǻ) Pa Pb

1 0.0 0.568 0.710 1.880 2.031 1.887 2.014 3.180 2.796 2.929 0.302 0.349
2 0.1 0.573 0.715 1.885 2.036 1.891 2.019 3.185 2.803 2.936 0.303 0.351
3 0.2 0.574 0.717 1.886 2.037 1.893 2.020 3.187 2.805 2.938 0.304 0.351
4 0.3 0.576 0.719 1.888 2.039 1.895 2.022 3.189 2.807 2.941 0.305 0.352

energies, the nanoparticles were tend to agglomerate and grow into

Table 3
larger assemblies.
Interionic distances between the cation and anion (p, q, r and s), interionic
distance between the cations (b, c, d, e and f) and the bond angles (θ1, θ2, θ3, θ4
and θ5). 3.3. FTIR studies
Parameter X = 0.0 X = 0.1 X = 0.2 X = 0.3

p 2.08 2.085 2.087 2.089

The FTIR spectra in the range 400-4000 cm− 1 of all the samples are
q 1.80 1.802 1.803 1.805 given in Fig. 4. In FTIR, two fundamental absorption bands of spinel
r 3.445 3.454 3.456 3.459 ferrites γ1 and γ2 were noticed in the wavenumber scale of 400–600
s 3.603 3.612 3.615 3.618 cm− 1. The bands are related to the stretching vibration of the cati­
b 2.942 2.945 2.947 2.950
on–oxygen ions in A and B site [44]. The higher wavenumber band in the
c 3.450 3.454 3.456 3.459
d 3.603 3.612 3.615 3.618 range 560–576 cm− 1 observed due to the stretching vibrations of the M
e 5.401 5.414 5.418 5.423 − O at the tetrahedral site. The lower wavenumber band appeared
f 5.096 5.105 5.109 5.114 around 476-486 cm− 1 is attributed to the octahedral metal-oxygen
θ1 125.38 125.24 125.19 125.15 stretching [45]. The frequency band shifted may be due to redistribu­
154.84 154.82 154.80 154.78
tion of Cu, Ca and Fe cations on both sites. The values are tabulated in
θ2
θ3 89.82 89.83 89.85 90.01
θ4 125.07 125.10 125.13 125.32 Table 4. It is observed that the frequency of the absorption bands (γ1 and
θ5 80.17 80.16 80.14 80.12 γ2) is approaching the low frequency side. This is due to the increase of
ionic radius of the tetrahedral and octahedral sites with the addition of
Ca2+ ions. The shifting of band position may refer to the increase in the
Fig. 3. The morphology of the particles were almost spherical and reg­
bond length of cation–oxygen (A–O) and decreases the wavenumber of
ular in shape and dispersed uniformly. The reason behind the agglom­
the absorption band. The movement of Fe3+ ions from A site to B site
eration of particles was its magnetic nature (magnetic dipoles
diluted the strengthening of the metal–oxygen bonds at the A sites. The
interactions within the ferrite) and particles combined due to debilitated
observed changes in wavenumbers γ1 and γ2 and reduction in the force
surface interaction such as the van der Waals forces [43] and slow
constants can be attributed to the distribution of calcium ions with
growth of particles. The agglomeration of particles indicates the strong
simultaneous readjustments of iron ions at the A and B sites in the spinel
magnetic nature of Ca doped Copper ferrite. Due to high surface
lattice. Since calcium has a greater preference for A sites of the spinel

Fig. 3. SEM images of Ca doped Ferrite.

4
P. Raji and K. Balachandra Kumar Physica B: Physics of Condensed Matter 632 (2022) 413759

locity, transverse velocity and mean velocity of elastic waves [51],

√̅̅̅̅̅̅
c11
Vl = (33)
ρx

Vl
Vt = √̅̅̅ (34)
3
[ ]− 1
1 2 1 3
Vm = + (35)
3 Vl2 Vt2

The lattice energy is also estimated using this equation [52],

U = − 3.108MVM2 (36)

The velocities of elastic wave and energy of the lattice are given in
Table 4. The value of lattice energy decreases with Ca2+ doping. The
decrease in inter atomic spacing reduces the bond length and makes the
elastic properties of ferrite to be very strong. It is found that lattice
energy decreases with increasing Ca concentration suggests a weakening
of the strength of bonding and results in a reduction in magnitude of
elastic moduli. Lattice energy is dependent an ionic charge and ionic
Fig. 4. FTIR images of Ca doped Ferrite. radius: as the charge of the ions increase the magnitude of the lattice
energy increases and as the ionic radius decreases lattice energy in­
lattice, iron occupy both A and B sites to maintain stoichiometry of creases. The lowering of lattice energy values of polycrystalline mate­
cations at A site and at B site [46]. rials as compared to their single crystalline counterparts is due to grain
and grain boundary contribution to polycrystalline material [53].
The three modulus of elasticity and Poisson ratio (σ) have been
3.4. Elastic properties evaluated from the relations [52].

Debye temperature and three moduli of elasticity of spinel ferrites Y=

9BR
(37)
are determined from the average frequency (γav) of absorption band and 3B + R
lattice constant [38]. Debye temperature (θD) is a measure of the
1
hardness of a material and evaluated from the equation [47]. B = [C11 + 2C12 ] (38)
3
KB θD = hcγav (30)
R = ρx Vt2 (39)
− 23 2 − 2 − 1 − 34
where kB- 1.38 × 10 m kg K , h - 6.634 × 10 JS and C - 3 ×
108 m/s. σ=
Y
− 1 (40)
The addition of calcium concentration decreases the average fre­ 2R
quency of the absorption bands as well as Debye Temperature. Ac­
where Vt - transverse velocity, ρx - X-ray density.
cording to specific heat theory [48], decrease of Debye temperature
All the values are tabulated in Table 5. The modulus of elasticity
indicated the increase the electron number in conduction (n-type) and
decreases with the Ca2+ doping. It is due to the diminishing of bond
decrease the number of the holes in conduction (p-type).
lengths between the cations in the spinel ferrite.
The tetrahedral and octahedral vibrational frequencies are used to
calculate the three moduli of elasticity [49]. Apart from this, the me­
chanical characteristics like inter-atomic forces and intermolecular 3.5. Magnetic properties
attraction are estimated. The force constants were evaluated with the
given equation. The M − H curves of calcium doped copper ferrites are shown in
Fig. 5. All the samples showed the room temperature ferromagnetic
2 2 2
K = 4π c γ m (31)
behavior. The magnetic parameters such as saturation magnetization
where c, γ and m are light velocity, vibrational frequency of tetra and
octahedral sites and reduced mass of iron - Oxygen ions respectively. Table 5
The stiffness constants C11 and C12 are the same for isotropic cubic Modulus of elasticity and Poisson’s ratio.
symmetry materials [50]. S.No X B (GPa) R (GPa) Y (GPa) Σ

C11=a K (32) 1 0.0 367 104 285 0.37

exp 2 0.1 363 103 282 0.36
3 0.2 354 101 276 0.36
where K- force constant. 4 0.3 345 98 268 0.36
The following equations are used to determine the longitudinal ve­

Table 4
Wavenumbers, Debye Temperature, Force constants, Velocities of elastic waves and lattice energy.
S.No X γ1 γ2 θD Kt (dyne/cm) 105 Kl (dyne/cm) 105 Vt (cm/s) 105 Vl (cm/s) 105 Vm (cm/s) 105 U (eV)

1 0.0 576 486 765 3.06 2.18 7.543 4.354 4.829 − 173.21
2 0.1 573 482 759 3.03 2.14 7.555 4.358 4.837 − 172.77
3 0.2 567 480 753 2.96 2.12 7.566 4.368 4.849 − 170.12
4 0.3 560 476 746 2.89 2.09 7.572 4.371 4.851 − 166.75

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P. Raji and K. Balachandra Kumar Physica B: Physics of Condensed Matter 632 (2022) 413759

(Ms), coercivity (Hc), remanence (Mr) and squareness ratio (Mr/Ms) are concentration of Ca2+ ions.
estimated from M − H curves. Ferrites have three different kinds of interaction such as A-A, B–B and
The magnetic moment (nB) in (μB) per unit formula was determined A-B. Among these, A-B super-exchange interaction is effective and it
using following relation [54,55]. prevail between octa and tetrahedral sites of metal cations.
According to Néel’s theory, the nonmagnetic Ca2+ ions strongly
ηB = Mwt MS /5585 (41)

where, Mwt-molecular weight.

Table 6
Furthermore the magnetic anisotropy (K) was calculated using
Magnetization (Ms), Remanence (Mr), Coercivity (Hc), Squarenessratio (S),
following relation [56].
anisotropy constant (K), Bohr magneton (nB).
K = Hc .Ms /0.96 (42) S. Ca content Hc Ms Mr S K (erg/ nB
No (x) (G) (emu/g) (emu/g) g)
The values of saturation magnetization (Ms), coercivity (Hc), rema­
nence (Mr), squareness ratio (Mr/Ms), magnetic moment and magnetic 1 0.0 1641 0.31 0.075 0.241 529.9 0.013
2 0.1 1585 0.6233 0.12 0.192 1029 0.026
anisotropy are listed in Table 6.
3 0.2 1259 1.17 0.15 0.128 1534 0.031
From the table, it is clear that the coercivity decreases while satu­ 4 0.3 1179 1.494 0.55 0.368 1834 0.045
ration magnetization and remanence magnetization increases with the

Fig. 5. VSM images of Ca doped Ferrite.

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P. Raji and K. Balachandra Kumar Physica B: Physics of Condensed Matter 632 (2022) 413759

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