Cryogenics 89 (2018) 53–57

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Cryogenics
journal homepage: www.elsevier.com/locate/cryogenics

Short communication

Bi-based superconductors prepared with addition of CoFe2O4 for the design T

of a magnetic probe
⁎
M.K. Ben Salema, Y. Slimanib, , E. Hannachia, F. Ben Azzouza,c, M. Ben Salema
a
Laboratory of Physics of Materials – Structures and Properties, Department of Physics, Faculty of Sciences of Bizerte, University of Carthage, 7021 Zarzouna, Tunisia
b
Department of Biophysics, Institute for Research and Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi
Arabia
c
College of Science, Department of Physics, Imam Abdulrahman Bin Faisal University, Saudi Arabia

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

Keywords: We have investigated the microstructure and the magnetoresistivity of bismuth based superconductor bulks
BSCCO superconductor added with nano-sized CoFe2O4 particles (10 nm in diameter). Samples were prepared through the solid state
Nanometer CoFe2O4 reaction (SSR) technique by addition of CoFe2O4 nanoparticles during the last step of heat treatment. Phase
Magnetoresistivity examination using X-ray diffraction (XRD), morphology investigation by scanning electron microscope (SEM),
Magnetic fields sensor devices
microstructure and local chemical composition analyses using transmission electron microscope (TEM) coupled
with energy dispersive X-ray spectroscope (EDXS), electrical resistance versus temperature ρ(T) under applied
magnetic fields (B) and electrical resistance versus B at 77 K, ρ(B), were carried out. The CoFe2O4 added sample
shows a great magnetoresistance to weak magnetic field at the temperature of liquid nitrogen (77 K). This result
is attractive for practical, because CoFe2O4 added samples can be utilized as active elements in magnetic fields
sensor devices.

1. Introduction effect in Bi-based superconductor, in which 0.5 wt.% CoFe2O4 was

Among the currently known high-Tc superconductors (HTS), bis-
muth based compounds (BSCCO) seems to be the furthermost promising
candidate for wide variety of applications. One of the characteristics of
HTS materials is the widening of the resistive transition in the presence
of applied magnetic fields. The widening phenomenon releases a new
route of exploration for employing certain of these superconductors as
extremely sensitive magnetic sensors [1,2]. The range of temperature
where the HTS polycrystalline material exhibits the large magnetore-
sistance effect, is typically narrow and below liquid nitrogen tempera-
ture. Several experimental studies through various processing techni-
ques were used in order to make HTS compounds suitable in devices
that request a sensitive magneto-electrical response for weak magnetics
fields. Bulk HTS exhibits much greater sensitivity to weak magnetics
field at liquid nitrogen temperature temperature in comparison to
others ceramics. Several investigations of the influence of nanosized
additions in HTS materials on the magneto-resistivity have been stated
in the literature [3,4]. The method of preparation and the nature of
included nanosized particles have a significant effect on the micro-
structure development and on the magneto-electrical response of the
HTS. In the present work, we report the study of the magnetoresistivity
added in the matrix. The choice of this sample is based on the fact that
its transition temperature is close to that of liquid nitrogen.
2. Experimental
The free and nanometer CoFe2O4 added BSCCO samples were ela-
borated through the solid state reaction (SSR) process using two
thermal cycles with additives at the beginning of each stage.
Description of the samples preparation have been detailed previously in
[5,6]. CoFe2O4 nanoparticles with average size of 10 nm (Fig. 1) were
added to the resulting precursor powders of BSCCO at the beginning of
the last heat cycle. The additional amount of CoFe2O4 in this case re-
presents 0 and 0.5 wt.% of the whole mass of the sample. The phase
identification were analyzed using XRD technique with a diffractometer
“Philips 1710″ with CuKα radiation. The morphology investigation was
performed using scanning electron microscope (SEM). The micro-
structure of samples was characterized using FEI Tecnai G2 transmis-
sion electron microscopy operating at 200 kV with a LaB6 filament.
Local chemical analysis was performed using the energy dispersive X-
ray spectroscopy (EDXS) system attached to the TEM. The measure-
ments of electrical resistivity versus temperature and in the presence of

⁎
Corresponding author at: Institute for Research and Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia.
E-mail addresses: yaslimani@uod.edu.sa, slimaniyassine18@gmail.com (Y. Slimani).

https://doi.org/10.1016/j.cryogenics.2017.11.005
Received 20 September 2017; Received in revised form 12 November 2017; Accepted 15 November 2017
Available online 16 November 2017
0011-2275/ © 2017 Elsevier Ltd. All rights reserved.
M.K. Ben Salem et al. Cryogenics 89 (2018) 53–57

Table 1
Relative volume fractions of (Bi,Pb)-2223, Bi-2212, and other phases for prepared sam-
ples.

Samples Non-added sample Added sample

(Bi,Pb)-2223 82.7 64.1

Bi-2212 14.1 28.8
Ca2PbO4 3.2 3.3
Bi-2201 0.0 4.1

((Bi,Pb)−2223)%
∑ I ((Bi,Pb)−2223)
= × 100
∑ I ((Bi,Pb)−2223) + ∑ I (Bi−2212) + ∑ I (other )

∑ I (Bi−2223)
Fig. 1. TEM micrograph of nano-sized CoFe2O4 particles. (Bi−2212)% =
∑ I ((Bi,Pb)−2223) + ∑ I (Bi−2212) + ∑ I (other )

applied magnetics fields ρ(T,H) were carried out through the conven-
tional four-probe technique using a cryostat system “DMX-19 SCC”. The
pellets were carefully cut into rectangular bars-shaped samples with
almost similar dimensions of 1 × 2 × 5 mm3. Electrical contacts were
made using silver paint and the contact resistance value must ap-
proximately less than 0.5 Ω. The magnetic fields were applied per-
pendicular to the sample wide surface. A small and constant current of
40 µA was injected for the resistivity measurements.
3. Results and discussions
Fig. 2 illustrates the XRD patterns of ceramics sintered without and
with addition of 0.5 wt.% CoFe2O4 for 72 h at the temperature 835 °C.
The characteristic peaks that correspond to diverse phases are labeled
on different patterns. It has found that the different samples are con-
stituted of major (Bi,Pb)-2223 (labeled with “3”) and minor Bi-2212
phases (labeled with “2”) and a very small amount of Ca2PbO4 as sec-
ondary phases. The XRD patterns of the resulting powders were taken
for quantitative analysis about phases presented in samples. The con-
centrations of the (Bi,Pb)-2223, Bi-2212 and secondary phases were
estimated from the X-ray diffraction (XRD) peak intensities according to
the following equations phases [7,8]:
× 100
∑ I (other )
(other )% = × 100
∑ I ((Bi,Pb)−2223) + ∑ I (Bi−2212) + ∑ I (other )
where I((Bi,Pb)−2223) , I((Bi,Pb)−2212) and I(other) are intensities of
the all distinguishable XRD peaks for the corresponding phases, re-
spectively. The estimated concentrations of the different phases are
given in Table 1. The analysis of these diagrams shows that the quantity
of (Bi,Pb)-2223 reduces marginally with addition of CoFe2O4, which
indicates that CoFe2O4 addition conducts to an alteration in the rate of
the reaction which retards marginally the formation of (Bi,Pb)-2223.
This result is consistent with the known behavior of the bulk super-
conductors added with nanoparticles [6,9–11]. Indeeed, the presence of
nanoparticles in the transient liquid forming at the reaction tempera-
ture may affects the viscosity of the liquid and its homogeneity and as a
consequence impedes the spatial (Bi,Pb)-2223 phase growth. Moreover,
Yahya and coworkers [9] support the idea that (Bi,Pb)-2223 phase is
formed from layer by layer intercalation of Ca-Cu-O bi-layers into the
existing (Bi,Pb)-2212. The intercalation process may be inhibited by
nano-magnetic particles when the moving Ca-Cu-O bilayers meet
magnetic nanoparticles embedded in (Bi,Pb)-2212 matrix and thus the
conversion to (Bi,Pb)-2223 is retarded.
Fig. 3a and b illustrate SEM micrographs of samples prepared
without and with 0.5 wt.% CoFe2O4 respectively. It is showed that there

Fig. 2. X-ray powder diffraction patterns of free and

0.5 wt.% of CoFe2O4 added samples. 2: Bi-2212 and 3:
(Bi, Pb)-2223.

54
M.K. Ben Salem et al. Cryogenics 89 (2018) 53–57

Fig. 3. SEM micrographs of free (a) and 0.5 wt.% of

CoFe2O4 (b) added samples.

is no obvious microstructure difference for both samples. For both

Fig. 4. (a) TEM micrograph of 0.5 wt.% CoFe2O4 added sample showing (Fe,Co)-rich
nanophase embedded in the (Bi, Pb)-2223 matrix. (b, c) EDXS collected from the nano-
phases.
samples, the morphology of grains is very comparable containing pre-
dominantly of large platelet-like grains. The existence of granular
morphology with plate-like structure is an indication of the formation
of the phase (Bi,Pb)-2223 from the Bi-2212 matrix supported princi-
pally by the liquid phase existing throughout the heat treatment. Fig. 4a
is a bright field electron micrograph of the (Bi,Pb)-2223 matrix region.
This TEM micrograph of an CoFe2O4 doped sample reveals the presence
of nanometer scale precipitates with average size around 10 nm (in-
dicated by an arrow) incorporated within the (Bi,Pb)-2223 matrix.
EDXS analyses collected from these nanophases clearly reveal that the
secondary phase contain Fe, Co, Bi, Sr, Ca and Cu elements (Fig. 4b).
Fig. 4a reveals also the presence of nanoparticle (limited by a dis-
continuous circle) with average size around 150 nm, inside the (Bi,Pb)-
2223 matrix. Note the presence of dark contrast around the secondary
phase, which is commonly observed at incoherent boundaries when the
two overlapping phases scatter the incident beam with different in-
tensities. EDXS analysis collected from this nanoparticle shows the
presence of Cu, Fe, Co, in high concentrations and a small amount of Ca
(Fig. 4c). It appears that the liquid phase formed during the heat
treatment has reacted with cobalt ferrite to give this type of entity.
Measurements of the resistivity versus temperature in the presence
of an applied magnetic field ρ (T ,H ) of free and 0.5 wt.% added samples
are shown in Fig. 5. It is clear that the addition of cobalt ferrite,
CoFe2O4, affects the intragranular as well as intergranular properties,
indeed, it induces a decrease in the onset critical temperature, T onset c ,
and the offset critical temperature, Tco . T onset
c is relative to the super-
conducting transition of isolated grains from the phase (Bi,Pb)-2223. It
strongly depends on the electronic states, on the oxygen content and on
the ordering of the oxygen atoms. The decrease in T onset c suggests that
cobalt ferrite is incorporated within grains to form inhomogeneities
that may have a magnetic character or to the redistribution of charges
in the superconducting system due to the fluctuation of the oxygen
ordering caused by a possible substituted Cu sites. Tco is the temperature
of the material where the percolation between the superconducting
grains is established. Its value is taken at 5% of ρn , ρn is the normal state
resistivity before the superconducting transition. The resistivity in the
vicinity of Tco is governed by the connectivity between grains (weak
links type Josephson). The electrical resistivity curves in the absence of
applied magnetic field, ρ (T ,0), reveals that Tco is 101 and 84.5 K for free
and 0.5 wt.% added samples respectively. The addition of CoFe2O4
nanoparticles leads to a relatively large superconducting transition,
suggesting that the intergrains are affected by the presence of CoFe2O4.
The addition of magnetic particles can modify the coupling between
grains by increasing the heterogeneities such as the increase in the
concentration of the Bi-2212 phase, the width and/or the degree of
disorder and the variation of the grain boundaries composition. A grain
boundary is a region of structural distortions, where an extra energy

55
M.K. Ben Salem et al.
appears; in order to decrease their energy they tend to attract impurity
atoms. Furthermore, the break of the Cooper pairs by a magnetic effect
leads to decrease Tco . As can be seen in Fig. 5, the resistive transition
shows two different regions: a steep region in the beginning of the
transition region and a tailing region. The steep part is less sensitive to
the applied magnetics fields. The tail part is associated with weak links
type Josephson [12,13]. This part is very sensitive to the applied
magnetics fields and moves to lower temperatures as the magnetic
fields increase. For 0.5 wt.% CoFe2O4 added sample the steep part is
more sensitive to the magnetic fields in comparison to non-added one,
illustrating a larger widening on increasing the field.
Fig. 6 displays the shift of the zero-resistivity temperature
ΔTco = Tco (H = 0)−Tco (H ) versus the applied field for free and 0.5 wt.%
CoFe2O4 added samples. It is well-observed that the CoFe2O4 addition
strengthens ΔTco . The data of transition width are well simulated by the
power law scale expression ΔTco = βH n . This dependence was also re-
ported on others HTS materials [14,15]. The values of the exponent n
are 0.26 and 0.41 respectively for free and 0.5 wt.% CoFe2O4 added
samples. This values are in agreement with other reported in scandium
substituted Ti-2121 [16] and YBCO prepared using ball milling tech-
nique [2]. The β factor values are established to be 6.18 and 2.41 re-
spectively for free and 0.5 wt.% CoFe2O4 added samples. The factor β is
considerably greater in the former case, it is a relevant factor which
informs us about the sensitivity of materials to applied magnetic field.
It’s clear that the adding of 0.5 wt.% cobalt ferrite nanoparticles in-
creases in a significant manner the sensitivity of the superconducting
Fig. 6. Evolution of the shift of the zero-resistivity temperature ΔTco = Tco ( H= 0)−Tco (H)
versus the applied field for free and 0.5 wt.% CoFe2O4 added samples.
56
Cryogenics 89 (2018) 53–57
Fig. 5. Variations of the electrical resistivity with tem-
perature at different applied magnetic fields for free (a)
and 0.5 wt.% CoFe2O4 (b) added samples.
material to the magnetic field.
The relative variation of the resistivity versus the applied field
ρN (B ) = ρ (B )/ ρ (0) (where ρ (0) is the measured resistivity in absence of
magnetic field) of sample was obtained by fixing temperature at 77 K
and plotting ρ (B ) . Fig. 7 shows experimental ρN (B ) curves of 0.0 and
0.5 wt.% CoFe2O4 added samples. In the magnetic field ranging be-
tween −2300 and + 2300 Gauss, the resistivity displays a symmetric
response with respect to the applied magnetic field direction. At low
fields, the ρN (B ) dependence of the 0.5 wt.% CoFe2O4 added sample
shows a very large increase in comparison to its value at B = 0 Gauss
and it rests unaffected within the field. For comparison, ρN (B ) of free
CoFe2O4 added-sample remains unchanged within the applied mag-
netics fields range. Moreover, in the range of low fields up to 100 Gauss
(inset of Fig. 7), the resistivity is well fitted according to the relation
ρN (B ) = [1 + αBm] where the constants m and α are equal to 2 and
1.4 × 10−4 respectively. The obtained value for 0.5 wt.% CoFe2O4
added-samples is similar to that reported in the case of YBa2Cu3O7 thick
films at 77 K [1]. These results suggest that CoFe2O4 nanoparticles in-
clusion into BSCCO compound act as non-superconducting phases that
increase the inter-grain disorder, reduce the coupling between grains
and thus destroy the phase coherence. This idea is supported by TEM
observations. A grain boundary is a region of structural distortions,
where an extra energy appears; in order to decrease their energy they
tend to attract impurity atoms. This phenomenon generates a relatively
large magnetoresistivity and a broader transition to the
Fig. 7. Experimental magnetic field dependence of the resistivity of free and 0.5 wt.%
CoFe2O4 added samples. Inset: plot of the low magnetic ρN (B ) of 0.5 wt.% CoFe2O4
added-sample; the solid line represents a fit according to ρN (B ) = [1 + αBm].
M.K. Ben Salem et al.
superconducting state for weak magnetic fields. This outcome suggests
that the addition of cobalt ferrite nanoparticles promotes the obtaining
of a sensitive magneto-electrical response of the HTS to weak magnetics
fields.
4. Conclusion
Bismuth based superconductor bulks samples have been prepared
using the solid state reaction technique without and with addition of
CoFe2O4 nanoparticles (10 nm in diameter). analyses show that the
inclusion of 0.5 wt.% CoFe2O4 nanoparticles does not affect the struc-
ture and morphology of sample. It has found that the CoFe2O4 added
sample possesses a larger magnetoresistivity in weak magnetic field,
over a large ranging temperature that includes N2 temperature in
comparison to the free added sample. Further investigations will be
performed on the combined influence of magnetic nanoparticles addi-
tion and planetary ball milling technique in order to elaborate samples
with a large magnetoresistance in weak magnetic fields.
Acknowledgments
University of Dammam is acknowledged for their financial support
through the project number 2017-576-IRMC.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
57
Cryogenics 89 (2018) 53–57
online version, at http://dx.doi.org/10.1016/j.cryogenics.2017.11.005.
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