Physica B 472 (2015) 3440

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Physica B
journal homepage: www.elsevier.com/locate/physb

Superconducting and mechanical properties of the bulk Bi(pb)SCCO

system prepared via solid state and ammonium nitrate precipitation
methods
S. Safran a,b,n, E. Klarslan a,b, H. Ozturk a,b, M. Alp b, M. Akdogan b,c, E. Asikuzun d,e,
O. Ozturk d,e, A. Kl a,b
a
Ankara University, Faculty of Science, Department of Physics, Tandoan, Ankara 06100, Turkey
b
Center of Excellence for Superconductivity Research, 50 Year Campus, Golba, Ankara, Turkey
c
Abant zzet Baysal University, Department of Physics, Bolu, Turkey
d
Kastamonu University, Department of Physics, Kastamonu, Turkey
e
Kastamonu University, Research and Application Center, Kastamonu, Turkey

art ic l e i nf o a b s t r a c t

Article history: We have investigated the effect of preparation method on superconducting and mechanical properties of
Received 13 April 2015 Bi(Pb)-2223 bulk samples using Bi1.85Pb0.35Sr2Ca2Cu3O10 7 y stoichiometry. Solid-state reaction and am-
Accepted 7 May 2015 monium nitrate precipitation methods have been used for fabrication of the bulk samples. In addition,
Available online 12 May 2015
the effect of annealing time on BSCCO samples have been studied. Structural, electrical, magnetic and
Keywords: microhardness analyses of samples are performed by the X-ray powder diffraction (XRD), the Scanning
Superconductors Electron Microscopy (SEM), DC resistivity, AC susceptibility and Vickers microhardness test. The critical
Electrical properties transition temperature, phase purity, surface morphology and crystallinity of the prepared bulk samples
Magnetic properties are compared with each other. Elasticity (E), brittleness (Bi), fracture toughness (KIC) and yield strength
Mechanical properties
(Y) values are also determined according to annealing time, applied load and production parameters of
materials.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction The purpose of this paper is to make comparison structural,

Many preparation and processing methods such as conven-
tional solid state reaction, solgel, polymeric, ammonium nitrate
precipitation, micro-emulsion-based etc. techniques have been
applied to improve the critical parameters of Bi-based high-tem-
perature ceramic superconductors [18]. Solid state reaction
method has a simple route so it is the most known and widely
used technique among these preparation methods. In this method,
starting powders are grinded, calcined and annealed in stoichio-
metric ratio. However, in order to obtain a chemically homogenous
mixture, ammonium nitrate precipitation method has been used
[9,10]. In this method, appropriate amount of starting powders
were dissolved in liquid ammonium nitrate at about 170 C. Then
ammonium nitrate was evaporated at about more than 210 C in
the form of H2O and N2O.
n
Corresponding author at: Ankara University, Faculty of Science, Department of
Physics, Tandoan, Ankara 06100, Turkey. Fax: 90 312 485 16 05.
E-mail addresses: safran@science.ankara.edu.tr,
safranserap@gmail.com (S. Safran).
electrical, magnetic and mechanical characterizations of super-
conducting Bi(Pb)-2223 bulk samples prepared via solid state and
ammonium nitrate precipitation methods. We also investigate the
effect of annealing time on BSCCO system. The methods used in
analyzing data and the results are given in the following sections.
2. Experimental
In this study, solid state reaction (SS) and ammonium nitrate
precipitation (AN) methods use for preparation of super-
conducting samples with chemical composition
Bi1.85Pb0.35Sr2Ca2Cu3Oy. We have used Bi2O3, PbO, SrCO3, CaCO3
and CuO with purities of more than 99.9% as starting powders. The
powders are mixed using ball-milling machine for 3 h at 75 rpm.
The milling procedure is maintained in a tungsten carbide jar to-
gether with tungsten carbide balls. Two calcination procedures are
performed at 775 C for 12 h and at 810 C for 24 h. The powders
are grinded after each calcination by using ball milling with same
procedure. Then, powders are pressed into pellets with

http://dx.doi.org/10.1016/j.physb.2015.05.006
0921-4526/& 2015 Elsevier B.V. All rights reserved.
 S. Safran et al. / Physica B 472 (2015) 3440 35

1  3  12 mm3 dimensions under the pressure of 5 tons like rec-

tangular bars. The furnace is heated from room temperature to
845 C with 5 C/min heating rate. The samples are kept for 48 h
and 120 h at this temperature and then cooled by 1 C/min rates
from annealing temperature to 200 C in air atmosphere. However,
to obtain chemically homogenous mixture, appropriate amount of
ammonium nitrate is added to the milled powders and is heated at
250 C for the ammonium nitrate precipitation methods. The other
procedure is same for two methods. According to preparation
methods, the pellets are called A group and C group for SS and AN
methods, respectively.
XRD measurements are carried out using a Rigaku D/Max-IIIC
diffractometer with CuK radiation in the range 2 360 with a
scan speed of 3/min and a step increment of 0.02. Microstructural
analyses are taken using a Jeol JSM-5300 SEM. Surface micro-
structure are performed on outer surfaces of the bulk samples. The
AC magnetic susceptibility as a function of temperature is mea-
sured by means of a Lake Shore 7130 AC magnetometer in the
temperature range 40120 K in various magnetic elds, at 125 Hz.
The details of the measuring system of the AC susceptibility was
described in [11,12]. The electrical resistivity is determined by the
four-probe method on a Cryodine CTI-Cryogenics closed cycle
cryostat working in the temperature range of 60140 K. The
electrical contacts are realized by application of silver paint on
rectangular bars. Vickers microhardness measurements are con-
ducted at room temperature in air by using a digital microhard-
ness tester (SHIMADZU HVM-2) to obtain information about the
mechanical properties of the BSCCO samples prepared at different
conditions. A rigid Vickers pyramidal indenter is applied for 10 s
using different load in the range from 0.245 to 2.940 N and the
diagonals of indentation are measured with an accuracy of
70.1 mm. The Vickers microhardness measurements are per-
formed with an average of 10 readings at different locations of
sample surfaces to obtain reasonable mean values for each applied
load.

3. Results and discussion Fig. 1. XRD patterns of the (a) A and (b) C groups of samples annealed at 845 C in
air for 48 h and 120 h.

Fig. 1a and b display the XRD patterns which demonstrate

phase formations of the A and C groups of BSCCO samples an- Table 1
nealed at 845 C in air for 48 h and 120 h, respectively. The de- Volume fraction, Tc data and preparation technique of BSCCO samples.
tected major phases are Bi-2223 and Bi-2212, with the fraction of
Sample Annealing Volume frac- Tc (K) Preparation
the latter being higher except for A-120 sample. Traces of non- name time (hours) tion (%) technique
superconducting Ca2PbO4 and one unknown phase is also detected
in all samples. The relative volume fractions of the Bi-2223 and Bi- Bi- Bi- Bi- Bi-
2223 2212 2223 2212
2212 phases in all the samples were estimated from the peak
heights of the reections belonging the same particular crystal- A-48 48 27 73 106.1 76.3 SS
lographic plane, using the following well-known expressions A-120 120 51 49 106.2 76.2 SS
[13,14]: C-48 48 20 80 106.2 63.0 AN
C-120 120 21 79 107.4 73.0 AN
IH (hkl)
f(2223) =
IH (hkl) + IL (hkl) (1)
SEM analysis. Surface micrographs of the prepared samples are
IL (hkl) shown in Fig. 2. It is observed that the microstructures of A and C
f(2212) = group samples exhibit a common feature of strip-like grains. The
IH (hkl) + IL (hkl) (2)
grains are randomly distributed. Powders from SS method show
Here IH(hkl) and IL(hkl) are the intensities of the (hkl) diffraction grain sizes about 10 mm diameter and the grain sizes of A group of
lines for Bi-2223 and Bi-2212 phases (Fig. 1a and b). The results are samples are relatively bigger than the other samples. Additionally,
listed in Table 1. Considering the annealing time, there is no ef- there are some voids and signs of partial melting on the micro-
fective differences in the volume fractions of the samples prepared graph of C group of samples prepared by AN method.
by AN method. However, in A series of samples, it is observed that In Fig. 3, we have plotted the normalized ac susceptibility
Bi-2223 phase increases with increasing annealing time. According curves as a function of temperature at Hac 640 A/m, frequency
to XRD results, to obtain Bi-2223 phase, SS method has better f 125 Hz. Note that, there exists two-step change to full dia-
performance than AN method. magnetism in-phase component of the fundamental suscept-
The surface morphology of the prepared samples is studied by ibilities, , of two groups of samples. The rst drop, near Tc,
36 S. Safran et al. / Physica B 472 (2015) 3440
Fig. 2. Surface micrographs of the A and C groups of samples.
corresponds to Bi-2223 phase. The superconducting grains shields
the applied magnetic eld just below the Tc. Another drop at low
temperatures indicates to Bi-2212. The whole volume is super-
conducting below 60 K for A group of samples, therefore T
curves saturate. However, saturation is not observed for the C
group of samples which can be needed to cool more. The shape of
the transition on the in-phase component plays a very important
role on critical superconducting parameters of the high-Tc super-
conductors. The sharper transition, the better interconnectivity of
the grains. In our study, a broad magnetic transition is observed
for both group of samples. However, the A group of samples have a
slightly sharper transition compared with the C group. These re-
sults indicate that the A group of samples prepared by the SS
method have better inter-granular coupling between grains. Si-
milarly, two peaks are observed in the out-of-phase component of
the fundamental susceptibilities. These two peaks correspond to
presence of two phases.
The derivation of versus temperature is shown inset of Fig. 3.
These curves present superconducting transition temperatures (Tc)
of the Bi-2223 and Bi-2212 phases. Tc values of the two group of
samples are given in Table 1. The Bi-2223 and Bi-2212 Tc of the A
group is determined to be about 106 K and 76 K, respectively. The
inuence of the annealing time is negligible for A group. For C
group, there is a minor difference on Tc of Bi-2223 phase, however,
Tc of Bi-2212 phase is changing between 63 K to 73 K depending
on annealing time.
In Fig. 4a and b, AC susceptibility measurements are shown to
investigate the dependence of the applied magnetic eld for the
A-120 and C-120 samples, respectively. The superconducting
transition temperatures are about 106 K and 107 K for A-120 and
C-120 sample, respectively. This temperature is independent of the
applied magnetic eld amplitudes. It can be said that the
difference of Tc is not so depend on the preparation technique.
However, Tc of Bi-2212 phase changes with increasing of the ap-
plied eld.
DC electrical resistance behavior (RT) of the both group of
samples is represented in Fig. 5. For both series, all samples exhibit
a metallic-like character in the normal state. Above the super-
conducting transition, the resistance of A group of samples are
higher than C group of samples. Only one single step of transition
to the superconducting state is seen in our samples. Zero-re-
sistivity transition temperatures are determined as 108 K and
111 K for A group and C group of samples, respectively. In addition,
the dependence of annealing time is insignicant for both group of
samples. A group of samples have sharper transitions than C group
of samples. This can be interpreted that C group of samples have
more grain boundaries and weak links between superconducting
grains compare to A group. These results are compatible with AC
susceptibility and SEM measurements.
Hardness tests are more widely used than other mechanical
tests due to the following reasons:
(1) It is simple and low cost. There is no need to prepare a specic
sample in general.
(2) It is non-destructive testing. Damage or excessive deformation
does not occur on the surface of sample, the only deformation
is caused by a small trace.
The determination of the hardness of a material is very im-
portant for technological applications. There are some advantages
as follows:
(1) It gives information about the origin of the material.
(2) It gives information about the other properties of the material.
 S. Safran et al. / Physica B 472 (2015) 3440 37

Fig. 3. Plot of real ( ) and imaginary () components of AC susceptibility as a function of temperature for A and C groups of samples. dT graphs are given inset of the
gure.

For example, hardness can be shown the processability prop-
erties of the material. Usually there is an inverse relationship
between the hardness and processability properties. In other
words, it is difcult to process of hard materials.
In Vickers microhardness measurement, a very small diamond
tip that has pyramid geometry is immersed on the surface of
sample. The applied loads are much smaller than Rockwell and
Brinell and are changed between 1 and 1000 g. After measure-
ment, indentation size that occurs on the surface is measured
under a microscope equipped with image analysis software and
then the hardness value was calculated. Hardness measurements

Fig. 4. Plot of real ( ) and imaginary () components of AC susceptibility as a function of temperature of (a) A-120 and (b) C-120 sample taken at applied AC eld
amplitudes H, ranging from 80 to 1280 A/m at a frequency f125 Hz.
38 S. Safran et al. / Physica B 472 (2015) 3440
Fig. 5. DC resistance as a function of temperature curves for prepared samples.
can be made from soft material to hard material in a wide range by
using method mentioned above. Vickers hardness measurement
method is the most sensitive hardness method. Many trace should
be measured for an average value of d that represents to hardness
of a material. Vickers microhardness value is calculated by using
Eq. (3) [1518]
1854.4F
Hv = F /A GPa
d2
Measured values and calculated microhardness values are gi-
ven in Fig. 6 and Table 2, respectively. While the sample that is
annealed for 48 h exhibits reverse indentation size effect (RISE)
behavior in A group materials produced by the SS method, in-
dentation size effect (ISE) behavior is observed with increasing
annealing time up to 120 h. Also, the microhardness values de-
crease with increasing annealing time. Microhardness values of
the C group samples produced by AN method increase with in-
creasing the annealing time. Furthermore, RISE behavior is ob-
served in C group samples. In addition, elastic deformation is ob-
served as well as plastic deformation in A group materials, except
for A-48 sample [19]. But, only plastic deformation is observed in C
group materials. There is no elastic recovery. Also, the behavior of
material is determined by Meyer law.
0,2
0,15
0,1
0,05
A-48
A-120
C-48
C-120
0 annealed for 48 h. Moreover, E, Y, KIC ve Bi values of A-48 sample
0 0,5 1 1,5 2 2,5
F (N)
Fig. 6. The variations of microhardness with load for the samples.
In addition, microhardness values have reached the plateau
(saturation region) around about 2 N for the all samples. A sig-
nicant change is not observed in microhardness values of the
material for further loading [20].
Optical trace photographs of the samples are given in Fig. 7
under 2.940 N applied load. Compared to the A group samples, the
optic trace image of samples annealed for 120 h is smaller than
48 h. This means that the indenter is put into deeper. The hardness
of the material is smaller. This result is also supported by the
calculated hardness values. Similarly, when C group samples are
compared with each other, it can be say that the optic trace image
of samples annealed for 48 h is smaller than 120 h. Indenter enters
more on the surface of sample and therefore this result conrms
that the microhardness of samples produced for 48 h is smaller.
3.1. Meyer law
Meyers law given by Eq. (4) is a simple experimental expres-
sion that was developed to investigate the ISE or RISE behavior of a
sample [21].
F = Ad n (4)
A-120 except for sample for all samples, Meyer index, n value is
higher than 2 (Table 3) which conrms that RISE behavior is ob-
served in these samples (Fig. 8). Additionally, in A-120 sample,
no 2 conrms that ISE behavior is observed in this one. According
to data in the literature, if the n value is between 1 and 1.6, the
(3) sample is dened as hard. But if this value is higher than 1.6, the
sample is grouped as soft [22]. n values given in Table 3 show
that the samples are soft.
Parameters such as modulus of elasticity (E), brittleness (Bi),
fracture toughness (KIC), yield strength (Y) and ductility (D) that
are as important as hardness to mechanical characterizations of
materials are also calculated and values of these parameters are
given in Table 2.
The elasticity modulus (E) is a measure of elastic deformation
of the material under force.
E = 81.9635 HV (5)
While E values of A group samples produced by the SS method
decrease with increasing annealing time from 48 h to 120 h. E
values of the C group samples produced by the AN method in-
crease with increasing the annealing time.
The toughness of a material is maximum amount of energy that
is absorbed before fracture. Brittleness (Bi), in technical using, is
the tendency against fracture of a material which is exposed to
very little fracture or shows no predetermined deformation. Brit-
tleness is the opposite of ductility (D). Ductility is the ability of a
material to permanent deformation. Yield strength (Y) refers the
transition point from elastic deformation to plastic deformation.
KIC = 2E (6)
Bi = Hv /KIC (7)
D = 1/Bi (8)
Y HV /3 (9)
As can be seen from the table, elastic modulus (E), yield stress
(Y), fracture toughness (KIC) and brittleness (Bi) values of the A
material annealed for 120 h are partially smaller than the material
3
increased with increasing applied load. However, these values
decreased with the increase of the applied load in A-120 sample.
This result is related with ISE behavior.
 S. Safran et al. / Physica B 472 (2015) 3440 39

Table 2
Calculated values of Hv, E, Y, KIC, Bi and D for the samples under varying applied loads.

Sample name F (N) Hv (GPa) E (GPa) Y (GPa) KIC  103 (Pa/m1/2) Bi  104 (m1/2) D (m  1/2)

A-48 0.245 0.096 7.90 0.032 19.391 49.715 0.0201

0.490 0.138 11.31 0.046 23.202 59.477 0.0168
0.980 0.151 12.39 0.050 24.285 62.248 0.0160
1.960 0.161 13.21 0.053 25.075 64.291 0.0155
2.940 0.162 13.34 0.054 25.198 64.612 0.0154

A-120 0.245 0.190 15.61 0.063 27.258 69.702 0.0143

0.490 0.155 12.71 0.051 24.596 63.016 0.0158
0.980 0.140 11.52 0.046 23.416 59.785 0.0167
1.960 0.116 9.547 0.038 21.317 54.415 0.0183
2.940 0.115 9.490 0.038 21.253 54.107 0.0184

C-48 0.245 0.018 1.489 0.006 16.925 10.635 0.0940

0.490 0.048 3.974 0.016 27.651 17.359 0.0576
0.980 0.114 9.411 0.038 42.552 26.790 0.0373
1.960 0.141 11.56 0.047 47.160 29.898 0.0334
2.940 0.144 11.85 0.048 47.748 30.158 0.0331

C-120 0.245 0.064 5.256 0.021 31.800 20.125 0.0496

0.490 0.075 6.184 0.025 34.493 21.743 0.0459
0.980 0.153 12.56 0.051 49.158 31.123 0.0321
1.960 0.164 13.48 0.054 50.926 32.203 0.0310
2.940 0.174 14.29 0.058 52.434 33.184 0.0301

Fig. 7. The optical trace photographs of the samples under 2.940 N.

40 S. Safran et al. / Physica B 472 (2015) 3440

Table 3 values are obtained by the AC susceptibility and DC resistivity

Regression analysis of experimental data according measurements. The microhardness values of A-120 sample pro-
to Meyers law.
duced by using the SS method decrease with increasing applied
Sample name n load. This material exhibits ISE behavior. The microhardness of
A-48 sample increase with increasing applied load. RISE behavior
A-48 2.44 is observed in this sample. As a result, it can be say that increasing
A-120 1.73 of annealing time changes the behavior of materials. Also, in-
C-48 2.95
C-120 3.34
creasing of annealing time led to decreasing of hardness of the
material. In addition, the microhardness values of C group samples
produced by using the AN method increase with increasing ap-
1,5 plied load and annealing time. C group samples exhibit RISE be-
havior and increasing of annealing time led to increasing of
hardness of the material.
1

Acknowledgements
0,5

This work has been supported by Turkish Research and Scien-

0 tic Council (TUBITAK) under Grant contract no.: 113F150. We also
acknowledge the Ministry of Development, Republic of Turkey
under Project no. 2010K120520.
-0,5

-1
-1,5
3,8 4 4,2 4,4 4,6 4,8 5 5,2
Ind ( m)
Fig. 8. Variation of ln F with ln d for A-48, A-120, C-48 and C-120 samples.
E, Y, KIC ve Bi values of C group samples that exhibit RISE be-
havior increase with increasing the annealing time and applied
load. The microhardness values of these samples increase with
increasing annealing time and applied load. Thus it is an expected
result that these values of samples increase. As a result, micro-
hardness is an important parameter for all of them (E, Y, KIC vs Bi
values).
4. Conclusion
In this study, we have performed structural, electrical, magnetic
and mechanical characterizations of BSCCO samples prepared by
SS and AN method. Also the effect of annealing time on BSCCO
samples have been studied. Structural, electrical and magnetic
properties of the BSCCO superconductors with the measurements
are determined to be strongly dependent on the fabrication
methods. We observed that SS method has better performance
than AN method for obtaining Bi-2223 phase. Additionally, when
the annealing time increases, Bi-2223 phase is higher for both
groups. Two-step change exists in ac susceptibility measurements.
This indicates that presences of Bi-2223 and Bi-2212 phases. Tc
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