Ceramics International 45 (2019) 17243–17251

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Structural changes of cerium doped copper ferrites during sintering process T

and magneto-electrical properties assessment
Tiberiu Romana,b, Aurel Puib,∗, Alexandru V. Lukacsc, Nicanor Cimpoesua, Stefan Lupescud,
Adrian Iulian Borhanb, Konstantinos Kordatose, Afroditi Ntziounie, Petronel Postolachec,
Marius Zahariaf, Sergiu Stanciua, Liliana Mitoșeriuc
a
„Gheorghe Asachi” Technical University of Iasi, Faculty of Materials Science and Engineering, D. Mangeron, Nr. 61A Blvd., Iasi, 700050, Romania
b
„Alexandru Ioan Cuza” University of Iasi, Faculty of Chemistry, Carol I Nr. 11 Blvd., Iasi, 700506, Romania
c
„Alexandru Ioan Cuza” University of Iasi, Faculty of Physics, Carol I Nr. 11 Blvd., Iasi, 700506, Romania
d
„Gheorghe Asachi” Technical University of Iasi, Faculty of Mechanics, D. Mangeron, Nr. 61A Blvd., Iasi, 700050, Romania
e
National Technical University of Athens, School of Chemical Engineering, Iroon Polytechneiou Nr. 9 Str., Zografou Athens, 15780, Greece
f
Petru Poni Institute of Macromolecular Chemistry, 41A Gr. Ghica Voda Alley, 700487, Iasi, Romania

A R T I C LE I N FO A B S T R A C T

Keywords: Crystalline CuCexFe2-xO4 nanoparticles with different rare earth metal content (x = 0.00, 0.03, 0.05, 0.08 and
Doped ferrites 0.10) were synthesized using a co-precipitation technique that involves a 600 °C calcination treatment. The
Sintering process newly obtained powders were pressed into pellets and heated up to 950 °C in order to form a compact and less
Spinel's structure modification porous material, ideal for dielectric measurements. X-ray investigations revealed a structural modification from
Magnetic properties
typical cubic system to a tetrahedral spinel form, accompanied by Ce3+ cations exclusion and formation of
Dielectric properties
secondary phases. The amount of phases and cations distribution were determined by Rietveld refinement
method. A degradation process of cerium doped copper ferrite was proposed based on X-ray analysis and
Rietveld refinement. Furthermore, the magnetic behavior of both 600 °C and 950 °C samples was investigated
from the hysteresis loops recorded from a vibrating sample magnetometer (VSM) in a ± 10 kOe range. Room
temperature dielectric values for the 950 °C samples were determined using the parallel-plate capacitor con-
figuration in a frequency range of 10 Hz – 1 MHz.

1. Introduction
Spinel ferrites are currently used for a wide area of applications due
to their specific properties. They have a great potential in medicine
being used as biosensors, carriers in controlled drug delivery systems
and hyperthermia treatments [1–3], in electronics as inductors, as gas,
humidity or magnetic sensors [4,5] and also in wastewater manage-
ment as adsorbent or photocatalytic materials for removal and de-
gradation of unwanted pollutants [6–8]. Numerous techniques have
been developed to produce ferrites with controlled morphology in na-
noparticle form [9], nanotubes and nanorods [10] or thin and thick
films [11,12].
Simple or mixed nanoferrites can be obtained using sol-gel [13],
hydrothermal [14] co-precipitation [15,16] and laser ablation for layer
formations [17] methods. Co-precipitation is a well-known tunable
synthesis route that offers a good control over composition, homo-
geneity, size and morphology of particles by choosing the right range of
temperature, stirring speed and surfactant agent in the synthesis pro-
cess [18,19]. In order to improve structural, morphological, magnetic
and electrical properties of ferrites [20–23], scientists manifested a
great interest to synthesize various type of ferrites by adding in the
structure rare earth (RE) metal ions. Previous studies reported that
Ce3+ cations presence in spinel oxides can produce good magnetic and
electrical properties, ideal for different types of applications [24,25].
Akhtar et al. studied the magnetic properties of copper ferrites doped
with Ce3+ cations prepared through sol-gel method. The study in-
dicates that Bohr magneton and magnetocrystalline anisotropy in-
creased after the doping of copper ferrite with Ce3+ cations [26].
Ferrites with general formula AB2O4 usually prefer a cubic spinel
structure where B3+ cations are occupying the octahedral position and
A2+ cations (Co2+, Fe2+, Mg2+, Mn2+, Ni2+, Cu2+, Zn2+ etc.) the
tetrahedral positions. It is known that ferrites can also present a dif-
ferent structure where the positions of the metallic cations are inversed
or partially inversed [27].

∗
Corresponding author.
E-mail address: aurel@uaic.ro (A. Pui).

https://doi.org/10.1016/j.ceramint.2019.05.280
Received 18 January 2019; Received in revised form 17 May 2019; Accepted 24 May 2019
Available online 25 May 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
T. Roman, et al.
Rare earths (RE) ferrites such as cerium doped copper ferrites prefer
a cubic crystallization system with Ce3+ occupying the octahedral sites
due to ionic radius. The insertion of Ce3+ may cause structural mod-
ification over the structure of ferrites as some studies report that sub-
stituted copper ferrite has a dual crystallization structure, one with Fd-
3m symmetric group specific for cubic structure and the other one with
I41/amd space group specific for tetragonal structure. This structural
change may be caused also by cation substitution and heating treatment
of copper ferrites [26,28,29]. Furthermore, the exchange of electrons
that occurs in the ferrite structure between the Fe–Fe, Fe–Cu, Fe–Ce and
Cu–Ce cations produces changes over the properties of nanostructured
material.
The goal of this study is to obtain CuCexFe2-xO4 ferrites (where
x = 0.00, 0.03, 0.05, 0.08 and 0.10) and to determine how structural
modifications influence the magnetic behavior of cerium doped copper
ferrites and bring a conclusive dielectric measurement of a less porous
ferrite material.
2. Materials and methods
2.1. Sample preparation
The investigated cerium doped copper ferrites have a nominal
composition of CuCexFe2-xO4 (where x = 0.00, 0.03, 0.05, 0.08 and
0.10). The samples are obtained through a wet chemical route by co-
precipitation of metallic chlorides (FeCl3, CuCl2, and CeCl3).
Carboxymethyl cellulose (CMC) was added over the mixture of metal
chlorides in order to act as surfactant agent and prevent the agglom-
eration of the newly formed particles. Throughout the synthesis pro-
cess, a temperature of 80 °C and continuous vigorous stirring was
maintained. A 3 M solution of NaOH was added over the mixture until a
pH value of 12 was reached, indicating the absence of metal chlorides
in the system. The particles were washed several times with distilled
water to remove the impurities formed in the synthesis process, fol-
lowed by a heating treatment at 600 °C for 6 h.
Furthermore, all samples were pressed into cylindrical pellets with a
diameter of 13 mm at 140 MPa and thermally treated 6 h at 950 °C in
order to obtain a compact and less porous material for dielectric mea-
surements. Fig. 1 illustrates the sample pellets before and after the
950 °C sintering process. Changes in diameter and color indicates
structural and density modifications after heat treatment occurs.
2.2. Samples characterization
Phase identification was made by means of X-ray diffraction using a
Xpert Panalytical Pro MPD diffractometer equipped with a copper
source radiation (CuK1 radiation, λ = 1.5406 Å). Background subtrac-
tion, smoothing and Rietveld refinement of XRD data were made using
X'Pert HighScore Plus and MAUD (Materials Analysis Using Diffraction)
software [30]. Infrared spectra of powders were recorded in the 4000-
400 cm−1 region using a Jasco 660 Plus and KBr pelletizing technique.
The morphology and elemental composition of the samples were ana-
lysed by a scanning electron microscope Vega Tescan LMH II equipped
with a Bruker EDAX XFlash detector. A Malvern Nano ZS equipment
was used to determine the powders formations size range by DLS
Fig. 1. CuCexFe2-xO4 samples before and after the 950° thermal treatment.
17244
Ceramics International 45 (2019) 17243–17251
(Dynamic Light Scattering) means. Furthermore, an EasyScan 2 from
Nanosurf noncontact AFM was used to scan the surface of the 950 °C
sintered samples and CMC-ferrite film. Specific magnetic values were
determined from the hysteresis loops provided by a MicroMag 3900
(Princeton Measurements Co.) Vibrating Sample Magnetometer (VSM)
in a field range of ± 10 kOe. The electrical characterization was per-
formed using the parallel-plate capacitor configuration, with applied
silver electrodes onto the polished surfaces of 950 °C CuCexFe2-xO4
ceramic samples. The measurements were carried out on Solartron
1260 A Impedance Analyzer, coupled with 1296 Dielectric Interface, in
the frequency range of 10 Hz – 1 MHz, at room temperature.
3. Results and discussions
3.1. XRD analysis
Room temperature X-ray analysis of CuCexFe2-xO4 nanoferrites
(x = 0.00, 0.03, 0.05, 0.08 and 0.10) indicates the formation of crys-
talline phases in the samples. Using MAUD software and Rietveld re-
finement technique, all XRD patterns were analysed and illustrated in
Fig. 2. The results indicate the formation of cubic spinel structure with
Fd-3m space group and tetragonal spinel structure with characteristic
I41/amd space group. Also, secondary phases can be observed in the
diffractograms corresponding to CuO and CeO2. For the 600 °C thermal
treated samples, CeO2 phase is observed at higher RE metal con-
centration which is explained by rare earth metal ions limited solubility
and a higher temperature requirement for RE ferrite spinel phase to
form [31]. The presence of CuO phase is due to ionic radius of Cu2+
cations and formation of tetragonal ferrite when the structural changes
occur.
The XRD pattern of 950 °C sintered samples indicates the formation
of tetragonal copper spinel. This structural change occurs with the ex-
pulsion of Ce3+ metal cations out of the structure of ferrite and the
formation of CeO2 phase with a specific Bragg reflection appearing
around 28.5°. Rietveld refinement indicates the formation of both
spinel structures at 600 °C, with a majority of cubic phase. A similar
pattern was observed for the 950 °C sintered samples with a preferential
tetragonal phase.
In Table 1 the weight percentage of phases identified in the samples
are presented. The estimated quantities of impurities were found in a
range of 0.50–3.3% for CeO2 phase and 2.5–11.0% for CuO phase. For
the 600 °C samples, CeO2 phase is absent at lower concentration of RE
metal cations and its presence occurs at 0.08 cerium content and above.
For the sintered samples, CeO2 presence is found at 0.03 content of RE
metal and keeps a constant rising. This indicates that at 950 °C the
formation of cerium doped copper ferrite in tetragonal and also cubic
form is not favorable. Therefore, due to the structural changes and
tensions that occur in the material at 950 °C, the Ce3+ cations with a
1.01 Å [32] ionic radius are not able to remain in the spinel structure.
Cation distribution and structural parameters for the 600 °C samples
were refined and showed in Table 2. The results indicated the pre-
ference of Cu2+ and Ce3+ cations to occupy the octahedral sites and
Fe3+ cations to relocate and fully occupy the tetrahedral sites of the
spinel's structure. For the samples with 0.00, 0.03, and 0.05 cerium
content the chemical formula is representative and fits the refined va-
lues. Instead, for the samples with 0.08 and 0.10 Ce content is more
likely that chemical formula is CuFe1.94Ce0.06O4 and CuFe1.92Ce0.8O4,
due to the cerium oxide formation. Also, the Cu content in octahedral
sites is smaller than normal, which can be explained by the presence of
CuO in the samples.
The 950 °C sintered samples can be described as composite mate-
rials with a mixture of metal oxides mostly formed by tetragonal copper
ferrite, with some amount of cubic Cu ferrite, copper oxide and cerium
oxide. Structural changes and simulated structures occurred during the
950 °C sintering process are illustrated in Fig. 3.
The x-ray densities (ρx) were calculated using two expressions, one
T. Roman, et al. Ceramics International 45 (2019) 17243–17251

Fig. 2. Rietveld refined XRD patterns of 600 °C and 950 °C thermal treated CuCexFe2-xO4 samples.

for cubic ferrite (eq. (1)) and the second one for tetragonal ferrite (eq. the presence of CMC organic groups. The remaining CMC can act as a
(2)). The values are dependent on molecular weight (MW), number of coating agent and influence the properties of the material [33,34]. The
unit cells (8 for cubic and 4 for tetragonal), cell volume (V), and Avo- infrared spectra of CuCexFe2-xO4 ferrites (Fig. 4), indicate the presence
gadro's number (N – 6.0225·1023). of a small amount of organic residue even after the 600 °C thermal
treatment. Characteristic vibrational bands of MTd-O and MOh-O bonds
8·MW
ρx = are observed around 585 cm−1 and 400 cm−1 [5,28]. Bending vibra-
N ·V (1)
tion of C–H bonds is noticeable around 960 cm−1 and also for the COO-
4·MW asymmetric and symmetric stretching vibration at 1620 and
ρx = 1520 cm−1. The 2850 cm−1 and 2930 cm−1 peaks correspond to me-
N ·V (2)
thylene's symmetrical and asymmetrical stretching vibrations. H–OH
stretching vibration is present at 3430 cm−1.
3.2. FTIR analysis High temperature treatment and low intensities absorption bands
specific to organic compounds in IR spectra indicates a small amount of
Infrared spectroscopy was used to investigate the 600 °C samples for CMC remains, which is very unlikely to affect particles morphology and

17245
T. Roman, et al. Ceramics International 45 (2019) 17243–17251

Table 1
Phases amount identified through Rietveld refinement.
Temperature (°C) Samples Phases (%)

Cubic ferrite Tetragonal ferrite CuO CeO2

600 x = 0.00 85.39 10.85 3.76 –

x = 0.03 82.49 12.11 5.40 –
x = 0.05 91.50 4.35 4.15 –
x = 0.08 83.97 4.71 10.82 0.52
x = 0.10 79.23 14.82 5.18 0.77
950 x = 0.00 1.74 90.65 7.61 –
x = 0.03 6.70 82.89 9.35 1.06 Fig. 3. Structural changes of cubic cerium doped copper ferrite and phase
x = 0.05 10.16 81.63 6.92 1.28 formation during sintering process.
x = 0.08 15.84 71.22 10.30 2.62
x = 0.10 4.96 88.85 2.50 3.29

magnetic measurements.

3.3. SEM and EDX analysis

Calcination and sintering process of a powder material leads to

morphological changes by increasing the particles size and favoring the
formation of bulks [35]. SEM results (Fig. 5b and d) show an agglom-
erated form of nanoparticles. Beside bulks, the presence of nano-
particles into the 600 °C sample is indicated by the porous formations
shown in Fig. 5b. The agglomeration degree and porosity of the nano-
particles represent key factors for sensor device development. In order
to have a specific sensor response it is important to have a uniform
metal cation distribution, which for the samples with the highest
cerium amount (x = 0.10) does not apply.
Fig. 5a and c illustrate CeO2 phase formation for both 600 °C and
950 °C samples with 0.10 cerium content. The EDX element distribution
images reveals a total displacement of iron cations around the cerium
oxide phase. For the 950 °C sample (Fig. 5c) copper agglomerations are
observed, most likely in an oxide form (CuO), without displacing the
iron. Beside those aspects, the cation distribution in the samples with
highest cerium content is uniform distributed. For the other samples, Fig. 4. FTIR spectra of 600 °C calcined CuCexFe2-xO4 samples.
the EDX distribution maps indicate a uniform distribution of elements
without the CeO2 phase agglomerations revealed. of cerium doped copper ferrites. Before measuring, the samples were
In addition to X-ray diffraction, EDX analysis is essential to confirm sonicated for 15 min in a 20% aqueous ethanol solution but large bulks
the chemical composition, especially for phases' formation. The results were still observed. This effect is due to magnetic interactions between
are similar with those identified by X-ray means techniques and minor the particles that constantly tend to agglomerate in larger and larger
differences can be attributed to the desired composition of the samples bulks [36]. The technique cannot discriminate the particles and the
due to the intrinsic error of the method. Theoretical and EDX results formed bulks of the sample and thus, it measures the overall suspension
composition for the 600 °C and 950 °C samples are presented in Fig. 6. size. Therefore, the hydrodynamic size distributions are larger than
those that are observed by other particles size measurement techniques.
3.4. DLS powder analysis Fig. 7 illustrates the hydrodynamic size distribution of 600 °C
samples. The average particles' size of CuCexFe2-xO4 is 205.9 nm for a
DLS measurements were made to determine the particles' size range cerium content of x = 0.00; 203.7 nm for x = 0.03; 203 nm for

Table 2
Cation distribution of the 600 °C samples for cubic and tetragonal spinel structures, calculated XRD density and their refined formula - ( ): tetrahedral site, [ ]:
octahedral site.
Samples Atom occupancy site Space group a(Å) c(Å) V (Å3) Refined formula ρXRD (g/cm3)

Cu (Td) Fe (Td) Ce (Td) Cu (Oh) Fe (Oh) Ce (Oh)

Cubic x = 0.00 0.000 1.000 0.000 0.498 0.501 0.000 Fd-3m 8.381 8.381 589 (Fe) [Cu0.99Fe]O4 5.397
x = 0.03 0.000 0.999 0.000 0.490 0.494 0.015 Fd-3m 8.385 8.385 590 (Fe) [Cu0.98Fe0.98Ce0.03]O4 5.441
x = 0.05 0.000 1.000 0.000 0.487 0.488 0.024 Fd-3m 8.398 8.398 592 (Fe) [Cu0.97Fe0.98Ce0.05]O4 5.449
x = 0.08 0.000 0.999 0.000 0.480 0.488 0.031 Fd-3m 8.386 8.386 590 (Fe) [Cu0.96Fe0.98Ce0.06]O4 5.495
x = 0.10 0.000 1.000 0.000 0.475 0.483 0.041 Fd-3m 8.411 8.411 595 (Fe) [Cu0.95Fe0.97Ce0.08]O4 5.483
Tetragonal x = 0.00 0.000 1.001 0.000 0.497 0.501 0.000 I41/amd 5.793 8.729 293 (Fe) [Cu0.99Fe]O4 5.421
x = 0.03 0.000 1.000 0.000 0.495 0.502 0.003 I41/amd 5.800 8.695 292 (Fe) [Cu0.99FeCe0.01]O4 5.486
x = 0.05 0.000 0.999 0.000 0.486 0.499 0.005 I41/amd 5.827 8.682 295 (Fe) [Cu0.97FeCe0.01]O4 5.475
x = 0.08 0.000 0.999 0.000 0.490 0.499 0.011 I41/amd 5.867 8.668 298 (Fe) [Cu0.98FeCe0.02]O4 5.430
x = 0.10 0.000 1.000 0.000 0.482 0.498 0.020 I41/amd 5.881 8.671 300 (Fe) [Cu0.97FeCe0.04]O4 5.443

17246
T. Roman, et al.
Fig. 5. EDX elemental distribution map (a) and SEM micrograph (b) for 600 °C
sample with 0.10 cerium content. EDX elemental distribution map (c) and SEM
micrograph (d) for 950 °C sample with 0.10 Ce content.
Fig. 6. Theoretical and EDX composition.
x = 0.05; 181.7 nm for x = 0.08 and 196.8 nm for x = 0.10, respec-
tively. Due to the magnetic interaction between the particles and bulk
formation, the results indicate a uniform wide distribution range,
starting from around 100 nm and up to 450 nm.
3.5. AFM analysis
Non-contact AFM technique was used to measure the particles' size
for 600 °C and 950 °C ferrite samples. The 600 °C powder samples
needed a pre-measuring preparation step to prevent the particle inter-
action with the AFM scanning tip by including them into a CMC film.
The CMC-powders films were obtained by mixing dry CMC and ferrites
17247
Ceramics International 45 (2019) 17243–17251
Fig. 7. Particles distribution range of 600 °C thermal treated samples.
powder (3:1 mass ratio) in ethanol. Furthermore, the mixture was so-
nicated for 15 min and water was added to dissolve the CMC. Finally,
the viscous mixture was poured onto glass slides and dried out.
AFM topography results for CMC film (Fig. 8a) indicate a porous
surface with spherical pores' sizes ranging from ⁓ 60 nm up to 300 nm
CMC-powder film images (Fig. 8b–f) illustrate both bulk and spherical
particle forms present in the sample. A higher density of particles is
noticeable around and on the surface bulks, indicating that ferrites still
tend to agglomerate after sonication, due to their magnetic nature. The
average sizes of the CuCexFe2-xO4 particles are 126.5 nm for x = 0.00;
104.2 nm for x = 0.03; 92.8 nm for x = 0.05; 118.2 nm for x = 0.08
and 154 nm for the sample with x = 0.10.
Powders' sintering process generates a growth in particles size as M.
Rozman et al. demonstrated for nonsized ferrites [37]. The AFM results
(Fig. 8g–k) show different formations of compact bulks with irregular
shapes and sizes ranging from 0.5 μm up to several μm. By comparing
the AFM images of 950 °C sample with those of CMC-ferrite films there
can be noticed the absence of nanoscale particles onto bulks surface.
3.6. Magnetic behavior of CuCexFe2-xO4
A standard technique was used for the analysis of bulk magnetic
properties of ferrites by magnetic hysteresis loops as shown in Fig. 9.
Room temperature VSM measurements describe the ferrites under
consideration as a magnetically soft ferrimagnetic material with low
coercivity.
Considering the different content of cerium, synthesis and sintering
process used in this study, a clear comparison with other research
groups cannot be made, but the specific magnetization values are
comparable with other reported data [21,26,38].
The magnetic values like saturation magnetization (Ms), remanent
magnetization (Mr) and coercivity (Hc) were recorded from the M − H
loops. Squareness ratio (R), magnetic moment per formula unit (μB/f.u.)
and anisotropy constant (K) were calculated using the following rela-
tions [26]:
Mr
R=
Ms (3)
Hc ·Ms
K=
0.96 (4)
MW ·Ms
μB =
5585 (5)
Magnetization values do not present a certain monotonous depen-
dence with the amount of cerium present in the samples. The shape and
width of loops resulted from several factors that influence the samples'
magnetization behavior, such as cerium contribution over magnetic
T. Roman, et al.
Fig. 8. AFM topography images of CMC film (a); CMC-CuCexFe2-xO4 powder films with x = 0.00 (b), x = 0.03 (c), x = 0.05 (d), x = 0.08 (e), x = 0.10 (f) cerium
content; Sintered sample with x = 0.00 (g), x = 0.03 (h), x = 0.05 (i), x = 0.08 (j) and x = 0.10 (k) cerium content.
moment, limited intercalation of RE elements in the spinel structure
and decreasing magnetic interaction between cerium and iron cations,
grain size, porosity and density.
The coercivity of 600 °C ferrites samples (Fig. 9a and b) rises with
the amount of cerium due to existence of more pinning sites and surface
spin disorder. Also, a slight increase of magnetization values is noticed
in 0.00 and 0.08 cerium content range. This exception is explained by
large formations of cerium oxide present in the CuFe1.9Ce0.10O4 sample
as suggested by EDX analysis, which minimalizes the interactions of
Fe–Ce cations.
The 950 °C treated samples have increased saturation and remanent
magnetization compared with the ones at 600 °C, possibly attributed to
grain size growth and porosity modification. Dependent on the amount
of cerium content, a clear dependency cannot be established, even if
saturation magnetization tends to decrease according with it.
Observed (ρobs) and calculated (ρcalc) densities of the samples were
determined and correlated with the magnetic parameters in Table 3 ρcalc
is dependent on the amount of phases identified in the samples. Using
equation (6) the porosity values of both 600 °C and 950 °C samples were
calculated.
ρcalc − ρobs
P= ∗ 100
ρcalc (6)
In addition, the samples' M − H lops' shape is uniform, without any
uneven variation of magnetization over the applied magnetic field,
indicating that the secondary phases present in the sample do not in-
teract separately, acting as a single material.
3.7. Dielectric properties
Room temperature dielectric properties of CuCexFe2-xO4 ceramic
composites with x = 0.00, 0.03, 0.05, 0.08 and 0.10, determined by
17248
Ceramics International 45 (2019) 17243–17251
impedance spectroscopy, are shown in Fig. 10(a–c) for the 950 °C
samples. The differences of the real part of permittivity (ε’) in low
frequency regime are attributed to the extrinsic phenomena represented
by dipolar, interfacial or surface polarization, that play a leading role in
determining the dielectric properties of ferrite materials [39]. These
extrinsic contributions, represented by slow charged species (space
charge effects), that cause Maxwell-Wagner relaxations and DC-con-
ductivity, are activated at low frequencies. Since these relaxations are
related to inhomogeneities and interfaces (more evident in composites
than in single-phase structures), they are responsible for the much
higher values of permittivity in the case of the samples with x = 0.03,
0.05 and 0.08, at low frequencies. These samples are showing a higher
total percentage of secondary phases (CuO and CeO2) in comparison
with that of x = 0.00 and x = 0.10, according to Rietveld refinement
analysis. In addition, the presence of secondary phases indicates a
higher probability of Fe2+ ions and oxygen vacancies formation that
accompany the Cu2+ and Ce3+ diffusion from the ferrite lattice during
the thermal treatment at 950 °C. For copper ferrites, the charge carrier
hopping between the Fe2+ ↔ Fe3+ and Cu2+ ↔ Cu1+ sites is re-
sponsible for polarization [40], thus, polarization and permittivity are
expected to vary according to the concentration of these ions.
With the increasing frequency, the permittivity decreases, reaching
constant intrinsic values towards 1 MHz, due to the fact that beyond a
certain frequency, the electron hopping cannot follow the alternating
field.
The dielectric loss dependence presented in Fig. 10 (b) reveals a
resonant behavior exhibited by x = 0.03, 0.05, 0.08 samples empha-
sized in the inset of the figure. The loss peaks are usually attributed to
the electron jump between the Fe2+ and Fe3+ sites. When the fre-
quency of the applied electric field matches the hopping frequency of
the charge carrier, the resonance condition is achieved and the elec-
trical energy presents a maximum in transfer to the oscillating carriers.
T. Roman, et al. Ceramics International 45 (2019) 17243–17251

Fig. 9. 600 °C (a and b) and 950 °C (c and d) thermal treated CuCexFe2-xO4 hysteresis loops.

Similar behavior was also observed in case of earlier reported sub-
stituted ferrite materials [39].
The conduction mechanism evolution with frequency is shown in
Fig. 10 (c), where the AC conductivity was evaluated from the ima-
ginary part of permittivity, being represented by the relation:
σAC = 2πfε0 ε"
where σAC represents the AC conductivity, f is the alternating frequency,
ε0 is the vacuum permittivity (permittivity of free space) and ε" is the
imaginary part of permittivity.
At low frequencies (< 100 Hz), a plateau is observed in the case of
CuFe2O4 and CuFe1.9Ce0.10O4 samples indicating the contribution from
the DC conductivity (σDC ), for which σDC assumes saturated values of
10−3S/m and 6 × 10−3S/m, respectively. For all the other composi-
tions, room temperature conductivity still decreases with reducing
frequency towards 10−4 S/m. The non-monotonous variation of
conductivity in relation to “x” composition of CuCexFe2-xO4 and the
differences between the low frequency dielectric trends in such complex
materials arise mainly from extrinsic contributions (interfaces, porosity,
grain sizes, local oxygen vacancies distribution etc.). These contribu-
tions cannot be controlled in a series of ceramic samples, even sintered
in the same conditions [41]. The overall dielectric behavior arises from
(7)
an interplay between the ratio of Fe3+/Fe2+, Cu2+/Cu1+ cations in the
ferrite lattice and the concentration/distribution of inhomogeneities
given by the presence of secondary phases in the material.
4. Conclusions
Several cerium doped copper ferrites with the general formula
CuCexFe2-xO4 (where x = 0.00, 0.03, 0.05, 0.08 and 0.10) were syn-
thesized using co-precipitation method and calcined at 600 °C.
Furthermore, a compact form of the samples was obtained by a

Table 3
Magnetization data from M − H loops, calculated (ρcalc) and observed (ρcalc) densities, porosity (P) and mean AFM grain size.
Samples Magnetic values Material characteristics

Mr (emu/g) Ms (emu/g) Hc (Oe) Mr/Ms K·103 Magnetic moment (μB/f.u.) ρcalc (g/cm3) ρobs (g/cm3) Porosity % (P) AFM mean grain size (nm)

600°C x = 0.00 2.27 18.5 61.26 0.123 1.181 0.792 5.432 3.173 41.597 126.5
x = 0.03 4.91 19.07 159.7 0.257 3.172 0.825 5.492 3.207 41.610 104.2
x = 0.05 5.90 18.21 236.66 0.324 4.489 0.792 5.484 3.205 41.562 92.8
x = 0.08 6.47 19.44 246.27 0.333 4.987 0.849 5.589 3.229 42.231 118.2
x = 0.10 5.38 16.39 257.08 0.328 4.389 0.721 5.532 3.350 39.452 154
950°C x = 0.00 8 37.79 97.78 0.212 3.849 1.618 5.489 4.996 8.983 2779
x = 0.03 10.08 35.57 158.82 0.283 5.885 1.539 5.579 4.937 11.514 2293
x = 0.05 8.8 35.23 116.61 0.250 4.279 1.533 5.553 4.805 13.471 718
x = 0.08 9.5 34.45 150.42 0.276 5.398 1.505 5.577 4.966 10.969 745
x = 0.10 7.66 34.62 113.67 0.221 4.099 1.524 5.504 5.017 8.855 1276

17249
T. Roman, et al.
Fig. 10. Frequency dependence of the: real part of permittivity (a), dielectric loss (b) and conductivity (c) for 950 °C sintered CuCexFe2-xO4 samples.
pelletizing powders technique followed by a sintering process at 950 °C.
The structural properties investigated by X-ray means, suggested an
obvious different spinel structure between the 600 °C and 950 °C
thermal treated ferrites samples. Also, Rietveld refinement enabled us
to determine the type of preferential spinel structure and the amount of
secondary phases present in the prepared samples before and after the
sintering process at 950 °C. Furthermore, a decomposition mechanism
of cubic cerium doped copper ferrite was proposed regarding the oc-
curred structural changes during sintering process and cerium exclu-
sion, which led to secondary phases formation.
Using microscopy and scattering techniques, significant morphology
and dimensional differences were observed between the samples, ac-
companied by the growth of nano-sized particles and formation of ir-
regular bulks within micro-domain range. All samples present a ferri-
magnetic behavior with an improbably monotonous dependence of
magnetic values regarding cerium content due to phase formation,
different sizes and cation interactions. Noticeable differences were ob-
served between the forms of the samples where remanent and satura-
tion magnetization increased after sintering process. The dielectric
measurements show a typical frequency variation for spinel ferrites
based on Fe2+–Fe3+ transition, with extrinsic contributions char-
acteristic to multiphase materials.
Considering all the aspects mentioned before, the sintering process
of cerium doped copper ferrites destabilizes them leading to significant
structural changes which affect their morphology and properties.
Acknowledgements
Adrian Iulian Borhan gratefully acknowledges for the grant of
Ministry of Research and Innovation, CNCS - UEFISCDI, project number
PN-III-P1-1.1-PD-2016-1510, within PNCDI III.
17250
Ceramics International 45 (2019) 17243–17251
References
[1] L. Stanciu, Y.-H. Won, M. Ganesana, S. Andreescu, Magnetic particle-based hybrid
platforms for bioanalytical sensors, Sensors 9 (2009) 2976–2999, https://doi.org/
10.3390/s90402976.
[2] B. Sahoo, K.S.P. Devi, S. Dutta, T.K. Maiti, P. Pramanik, D. Dhara, Biocompatible
mesoporous silica-coated superparamagnetic manganese ferrite nanoparticles for
targeted drug delivery and MR imaging applications, J. Colloid Interface Sci. 431
(2014) 31–41, https://doi.org/10.1016/j.jcis.2014.06.003.
[3] E. Myrovali, N. Maniotis, A. Makridis, A. Terzopoulou, V. Ntomprougkidis,
K. Simeonidis, D. Sakellari, O. Kalogirou, T. Samaras, R. Salikhov, M. Spasova,
M. Farle, U. Wiedwald, M. Angelakeris, Arrangement at the nanoscale: effect on
magnetic particle hyperthermia, Sci. Rep. 6 (2016) 1–11, https://doi.org/10.1038/
srep37934.
[4] R. Valenzuela, Novel applications of ferrites, Physiother. Res. Int. 2012 (2012),
https://doi.org/10.1155/2012/591839.
[5] V. Constantin, T. Florin, P. Aurel, Increased sensibility of mixed ferrite humidity
sensors by subsequent heat treatment, Int. J. Appl. Ceram. Technol. 14 (2017)
1174–1182, https://doi.org/10.1111/ijac.12706.
[6] A.I. Borhan, P. Samoila, V. Hulea, A.R. Iordan, M.N. Palamaru, Photocatalytic ac-
tivity of spinel ZnFe2-xCrxO4 nanoparticles on removal Orange I azo dye from
aqueous solution, J. Taiwan Inst. Chem. Eng. 45 (2014) 1655–1660, https://doi.
org/10.1016/j.jtice.2013.12.002.
[7] C. Vîrlan, R.G. Ciocârlan, T. Roman, D. Gherca, N. Cornei, A. Pui, Studies on ad-
sorption capacity of cationic dyes on several magnetic nanoparticles, Acta Chem.
Iasi 21 (2013) 19–30, https://doi.org/10.2478/achi-2013-0003.
[8] T. Roman, R.L. Asavei, N.E. Karkalos, C. Roman, C. Virlan, N. Cimpoesu, B. Istrate,
M. Zaharia, A.P. Markopoulos, K. Kordatos, S. Stanciu, A. Pui, Synthesis and ad-
sorption properties of nanocrystalline ferrites for kinetic modeling development,
Int. J. Appl. Ceram. Technol. 16 (2019) 693–705, https://doi.org/10.1111/ijac.
13091.
[9] D. Gherca, A. Pui, V. Nica, O. Caltun, N. Cornei, Eco-environmental synthesis and
characterization of nanophase powders of Co, Mg, Mn and Ni ferrites, Ceram. Int.
40 (2014) 9599–9607, https://doi.org/10.1016/j.ceramint.2014.02.036.
[10] S. Lalwani, R.B. Marichi, M. Mishra, G. Gupta, G. Singh, R.K. Sharma, Edge enriched
cobalt ferrite nanorods for symmetric/asymmetric supercapacitive charge storage,
Electrochim. Acta 283 (2018) 708–717, https://doi.org/10.1016/j.electacta.2018.
07.008.
[11] N. Sangeneni, K.M. Taddei, N. Bhat, S.A. Shivashankar, Magnetic properties of
superparamagnetic, nanocrystalline cobalt ferrite thin films deposited at low tem-
perature, J. Magn. Magn. Mater. 465 (2018) 590–597, https://doi.org/10.1016/j.
T. Roman, et al.
jmmm.2018.06.038.
[12] A.I. Popov, Z.V. Gareeva, F.A. Mazhitova, R.A. Doroshenko, Magnetoelectric
properties of epitaxial ferrite garnet films, J. Magn. Magn. Mater. 461 (2018)
128–131, https://doi.org/10.1016/j.jmmm.2018.04.042.
[13] P. Samoila, L. Sacarescu, A.I. Borhan, D. Timpu, M. Grigoras, N. Lupu, M. Zaltariov,
V. Harabagiu, Magnetic properties of nanosized Gd doped Ni-Mn-Cr ferrites pre-
pared using the sol-gel autocombustion technique, J. Magn. Magn. Mater. 378
(2015) 92–97, https://doi.org/10.1016/j.jmmm.2014.10.174.
[14] G. Rekha, R. Tholkappiyan, K. Vishista, F. Hamed, Systematic study on surface and
magnetostructural changes in Mn-substituted dysprosium ferrite by hydrothermal
method, Appl. Surf. Sci. 385 (2016) 171–181, https://doi.org/10.1016/j.apsusc.
2016.05.092.
[15] R.G. Ciocarlan, A. Pui, D. Gherca, C. Virlan, M. Dobromir, V. Nica, M.L. Craus,
I.N. Gostin, O. Caltun, R. Hempelman, P. Cool, Quaternary M0.25Cu0.25Mg0.5Fe2O4
(M = Ni, Zn, Co, Mn) ferrite oxides: synthesis, characterization and magnetic
properties, Mater. Res. Bull. 81 (2016) 63–70, https://doi.org/10.1016/j.
materresbull.2016.05.001.
[16] D. Gherca, A. Pui, N. Cornei, A. Cojocariu, V. Nica, O. Caltun, Synthesis, char-
acterization and magnetic properties of MFe2O4 (M=Co, Mg, Mn, Ni) nanoparticles
using ricin oil as capping agent, J. Magn. Magn. Mater. 324 (2012) 3906–3911,
https://doi.org/10.1016/j.jmmm.2012.06.027.
[17] M. Oujja, L. Martín-García, E. Rebollar, A. Quesada, M.A. García, J.F. Fernández,
J.F. Marco, J. de la Figuera, M. Castillejo, Effect of wavelength, deposition tem-
perature and substrate type on cobalt ferrite thin films grown by pulsed laser de-
position, Appl. Surf. Sci. 452 (2018) 19–31, https://doi.org/10.1016/j.apsusc.2018.
05.012.
[18] S. Dabagh, K. Chaudhary, Z. Haider, J. Ali, Study of structural phase transformation
and hysteresis behavior of inverse-spinel α-ferrite nanoparticles synthesized by co-
precipitation method, Results Phys. 8 (2018) 93–98, https://doi.org/10.1016/j.
rinp.2017.11.033.
[19] T. Boobalan, S. Pavithradevi, N. Suriyanarayanan, M. Manivel Raja, E. Ranjith
Kumar, Preparation and characterization of polyol assisted ultrafine Cu–Ni–Mg–Ca
mixed ferrite via co-precipitation method, J. Magn. Magn. Mater. 428 (2017)
382–389, https://doi.org/10.1016/j.jmmm.2016.12.124.
[20] Z. Liu, Z. Peng, X. Fu, Structural and electromagnetic properties of Ni0.5Zn0.5HoxFe2-
xO4ferrites, Ceram. Int. 43 (2017) 14938–14944, https://doi.org/10.1016/j.
ceramint.2017.08.011.
[21] H. zhen Duan, F. ling Zhou, X. Cheng, G. hong Chen, Q. ling Li, Preparation of
hollow microspheres of Ce3+ doped NiCo ferrite with high microwave absorbing
performance, J. Magn. Magn. Mater. 424 (2017) 467–471, https://doi.org/10.
1016/j.jmmm.2016.10.069.
[22] M. Hashim, M. Raghasudha, S.S. Meena, J. Shah, S.E. Shirsath, S. Kumar,
D. Ravinder, P. Bhatt, Alimuddin, R. Kumar, R.K. Kotnala, Influence of rare earth
ion doping (Ce and Dy) on electrical and magnetic properties of cobalt ferrites, J.
Magn. Magn. Mater. 449 (2018) 319–327, https://doi.org/10.1016/j.jmmm.2017.
10.023.
[23] C. Virlan, G. Bulai, O.F. Caltun, R. Hempelmann, A. Pui, Rare earth metals' influ-
ence on the heat generating capability of cobalt ferrite nanoparticles, Ceram. Int. 42
(2016) 11958–11965, https://doi.org/10.1016/j.ceramint.2016.04.121.
[24] Z. Mosleh, P. Kameli, A. Poorbaferani, M. Ranjbar, H. Salamati, Structural , mag-
netic and microwave absorption properties of Ce-doped barium hexaferrite, J.
Magn. Magn. Mater. 397 (2016) 101–107, https://doi.org/10.1016/j.jmmm.2015.
08.078.
[25] M. Rahimi-nasrabadi, M.B.A. Sobhani-nasab, Nanocrystalline Ce-doped copper
ferrite : synthesis , characterization , and its photocatalyst application, J. Mater. Sci.
Mater. Electron. 27 (2016) 11691–11697, https://doi.org/10.1007/s10854-016-
17251
Ceramics International 45 (2019) 17243–17251
5305-8.
[26] M.N. Akhtar, A.B. Sulong, M.N. Akhtar, M.A. Khan, Systematic study of Ce 3+ on
the structural and magnetic properties of Cu nanosized ferrites for potential ap-
plications, J. Rare Earths 36 (2018) 156–164, https://doi.org/10.1016/j.jre.2017.
09.003.
[27] L. Andjelković, M. Šuljagić, M. Lakić, D. Jeremić, P. Vulić, A.S. Nikolić, A study of
the structural and morphological properties of Ni–ferrite, Zn–ferrite and
Ni–Zn–ferrites functionalized with starch, Ceram. Int. 44 (2018) 14163–14168,
https://doi.org/10.1016/j.ceramint.2018.05.018.
[28] C. Virlan, F. Tudorache, A. Pui, Tertiary NiCuZn ferrites for improved humidity
sensors: a systematic study, Arab. J. Chem. (2018), https://doi.org/10.1016/j.
arabjc.2018.03.005.
[29] A.C. Druc, A.I. Borhan, G.G. Nedelcu, L. Leontie, A.R. Iordan, M.N. Palamaru,
Structure-dielectric properties relationships in copper-substituted magnesium fer-
rites, Mater. Res. Bull. 48 (2013) 4647–4654, https://doi.org/10.1016/j.
materresbull.2013.08.002.
[30] L. Lutterotti, Total pattern fitting for the combined size-strain-stress-texture de-
termination in thin film diffraction, Nucl. Instrum. Methods Phys. Res. Sect. B Beam
Interact. Mater. Atoms 268 (2010) 334–340, https://doi.org/10.1016/j.nimb.2009.
09.053.
[31] T.X. Huang, L.Z. Li, J. Yang, Structural and static magnetic properties of ce-sub-
stituted NiZnCo ferrite nanopowders, Optoelectron. Adv. Mater. Rapid Commun. 10
(2016) 590–593.
[32] L. Pauling, The Nature of Chemical Bond and the Structure of Molecules and
Crystals, third ed., (1960).
[33] M. Chithra, C.N. Anumol, S.C. Sahoo, Effect of surface coating on magnetic prop-
erties of cobalt ferrite nanoparticles, AIP Conf. Proc. 1728 (2016), https://doi.org/
10.1063/1.4946410.
[34] C. Virlan, O.F. Caltun, D. Lutic, A. Pui, New bio-surfactant used in the synthesis of
functionalized nanoferrites as potential catalysts, Curr. Nanosci. 13 (2017)
247–253, https://doi.org/10.2174/1573413713666170220114206.
[35] S.A. Saafan, S.T. Assar, B.M. Moharram, M.K. El Nimr, Comparison study of some
structural and magnetic properties of nano-structured and bulk Li-Ni-Zn ferrite
samples, J. Magn. Magn. Mater. 322 (2010) 628–632, https://doi.org/10.1016/j.
jmmm.2009.10.027.
[36] A.B. Salunkhe, V.M. Khot, N.D. Thorat, M.R. Phadatare, C.I. Sathish, D.S. Dhawale,
S.H. Pawar, Polyvinyl alcohol functionalized cobalt ferrite nanoparticles for bio-
medical applications, Appl. Surf. Sci. 264 (2013) 598–604, https://doi.org/10.
1016/j.apsusc.2012.10.073.
[37] M. Rozman, M. Drofenik, Sintering of nanosized MnZn ferrite powders, J. Am.
Ceram. Soc. 81 (1998) 1757–1764, https://doi.org/10.1111/j.1151-2916.1998.
tb02545.x.
[38] S. Amiri, H. Shokrollahi, Magnetic and structural properties of RE doped Co-ferrite
(RE=Nd, Eu, and Gd) nano-particles synthesized by co-precipitation, J. Magn.
Magn. Mater. 345 (2013) 18–23, https://doi.org/10.1016/j.jmmm.2013.05.030.
[39] K. Verma, A. Kumar, D. Varshney, Effect of Zn and Mg doping on structural, di-
electric and magnetic properties of tetragonal CuFe2O4, Curr. Appl. Phys. 13 (2013)
467–473, https://doi.org/10.1016/j.cap.2012.09.015.
[40] C. Murugesan, L. Okrasa, G. Chandrasekaran, Structural, AC conductivity, im-
pedance and dielectric study of nanocrystalline MFe2O4(M = Mg, Co or Cu) spinel
ferrites, J. Mater. Sci. Mater. Electron. 28 (2017) 13168–13175, https://doi.org/10.
1007/s10854-017-7152-7.
[41] C.E. Ciomaga, M. Airimioaei, I. Turcan, A.V. Lukacs, S. Tascu, M. Grigoras, N. Lupu,
J. Banys, L. Mitoseriu, Functional properties of percolative CoFe2O4-PbTiO3 com-
posite ceramics, J. Alloy. Comp. 775 (2019) 90–99, https://doi.org/10.1016/j.
jallcom.2018.10.088.