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Energy Procedia 18 (2012) 215 – 224

Influences of Sintering Time on the TC of

Bi2-xCuxPb0.3Sr2Ca2Cu3O10+ High Temperature
Superconductors
M.M.Abbasa*, L.K.Abassa and U.Salmanb
a
Physics department, college of science, Baghdad University,Baghdad, Iraq
b
Physics department ,college of sceince, AL-Muthana University, AL-Muthanna, Iraq

Abstract

Solid state thermodynamical reaction method involving mixing, calcinations and sintering were used
to prepare a high temperature superconductor with a nominal composition Bi2-xCuxPb0.3Sr2Ca2Cu3O10+
for Cu ( 0 x 0.5 ). The effect of sintering time and substituting Cu on Bi sites have been investigated
by X-ray diffraction, resistance measurements and oxygen content to obtain the optimum conditions for
the formation and stabilization of the high TC phase (2223- phase). The results showed that the optimum
sintering time for the composition Bi2-xCuxPb0.3Sr2Ca2Cu3O is 140 hr at sintering temperature 860 oC.
Substitution for Cu equals to 0.2 and 0.3 led to increase the transition temperature to TC =127 K and 130
K respectively but for 0.4, TC decreased to 125 K. The X-ray diffraction (XRD) analysis showed that all
samples have almost two phases: high-TC phase (2223- phase) and low-TC phase (2212- phase) in
addition to the existing of very low phase in the sample x=0.4. It was found that the all samples having an
orthorhombic.
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2010 Published
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Open access under CC BY-NC-ND license.
Keywords: High TC superconductors, Bi2-xCux Pb0.3Sr2Ca2Cu3O10+ sintering time.

* Corresponding author-mail address: muna_moussa@yahoo.com.

1876-6102 © 2012 Published by Elsevier Ltd. Selection and/or peer review under responsibility of The TerraGreen Society.
Open access under CC BY-NC-ND license. doi:10.1016/j.egypro.2012.05.033
216 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224

1. Introduction

The unique properties of superconductors are the basics of a much wider range of applications. The
applications are basically divided into; small scale, categorized as electronic applications, and large scale
applications involving the conduction of large currents. One of the first users of superconducting magnets
was the high energy physicist. A very large superconductor can store a considerable amount of solenoid
magnet of energy. This type of magnet can also store the energies required for very large laser or other
pulsed power applications.
There are three superconducting phases in the Bi–Sr–Ca–Cu–O system which have an ideal
structural formula Bi2Sr2Can 1CunO4+2n, with n = 1, 2 or 3 indicating the number of the CuO2 planes. Each
phase has a different transition temperature to the superconducting state: for n = 1 (2201) TC = 20K, n = 2
(2212) TC = 80K and n = 3 (2223) TC = 110K. The 2212 and 2223 phases are important for technological
applications due to wire/cable application of these materials. But it is rather difficult to obtain them in an
isolated form as the 2212 phase grows prior to the 2223 phase during synthesis.
The structure consists of perovskite-like units containing one, two or three CuO2 planes sandwiched
between Bi-O bilayers. Furthermore the crystal structures consist of two generic building blocks: the vital
are the superconducting copper-oxide layers or planes, and the insulating block layers which can act as
electronically active charge-reservoirs for hole or electron donation to the copper-oxygen layers. The
copper-oxide layers can be thought of as being derived from the perovskite structure-type by denticulation
of oxygen from between the copper-oxide planes, while the insulating block is derived from the rock-salt
structure [1].
Optimizing the carrier concentration could enhance the superconducting properties of these
compounds. The carrier concentration could be controlled with cation substitution and by varying oxygen
contents. TC of superconducting copper-oxide based compounds depends on the density of mobile holes
in the CuO2 planes and thus on the average Cu valance [2].
The formation and stability of the 2223 phase can be modified with many methods by the addition
or substitution of elements of varying ionic radii and bonding characteristics. This variation is thought to
be related to the density of charge carriers in the CuO planes. Weak coupling between BiO–BiO layers in
the BSCCO system enables the substitution of the different oxides for Bi3+ site. Among these, addition or
partial substitution of trivalent Bi with Pb has been found to be the most effective method [3 and 4]. Not
only does it change the holes concentration in CuO2 planes, but also helps to create oxygen vacancies by
being predominantly in a 2+ oxidation state [5 and 6]. It was also reported that lead atoms act as efficient
nucleation and growth sites for the formation of the high- TC phase and enhance the diffusion of the
calcium and copper atoms [7].
Agostinelli and coworkers [8] pointed out that the longer annealing times resulted in more
homogenous samples having a single superconducting transition to zero resistance at 108K.
Dey [9] studied the influences of sintering duration on the electrical resistivity and thermal
conductivity of (Bi0.8Pb0.2)2Sr2Ca2Cu3O9.8+ pellets with 0.11< <0.54 in the range of (10-150) K. He
found a gradual transformation of the 2212 phase to the 2223 phase and this transformation starts within
5h of sintering in air at 840 oC.
Since the reaction kinetics of the Bi-(2223) phase formation is slow, long periods of sintering at
temperatures close to its decomposition temperature are required [10]. Many factors, including
composition, phase assemblage of the precursor powder, lead content, grain alignment, intergrain
connectivity, sintering parameters and doped ions, significantly influence the heat treatment parameters
and hence final physical properties of the samples [11].
However, we have not seen at least to the best of our knowledge any research on the influences of
sintering time on the TC for the Bi2Pb0.3Sr2Ca2Cu3Oy when it is doped with Cu instead of some Bi atoms.
 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224 217

The main purpose of this work is to get optimum conditions for the high TC -phase structure (2223)
using solid state reaction method, as well as to investigate the influence of partial substitution of Cu on Bi
sites, on the formation of the high-TC phase, in the Bi2-xCuxPb0.3Sr2Ca2Cu3O compounds with
(0

2. Experimental

The system (Bi2-xCuxPb0.3Sr2Ca2Cu3O ) with (0

method. First of all the molar ratios of high purity powders of Bi2O3, Pb3O4, Sr(NO3)2, CaCO3 and CuO
were taken accurately. Then the powders were well mixed using agate mortar. A sufficient quantity of 2-
propane was used to homogenize the mixture. The mixture was ground to a fine powder and then calcined
in air at 800 oC for (20-24) h with repeated intermediate re-grinding. The powder pressed into disc-shaped
pellets with 13mm in diameter and (25-28) mm thickness using a manually hydraulic press type (Specac)
under different pressures around 0.5 GPA.
Series of pellets were prepared with different conditions in order to investigate the effect of sintering
time, which acts on the superconducting properties.
First series; is sintered at 860 oC for 120 h then air cooling to room temperature (process 1).
Second series: sintered at 860 oC for 140 h then air cooling to room temperature (process 2).
Third series; sintered at 860 oC by two steeps, 1st for 120 h subsequent then air cooling to room
temperature, 2nd after that sintered at 860 oC for 40 h then air cooling to room temperature (process 3).
Forth series: sintered at 860 oC for 200 h with subsequent slow air cooling to room temperature (process
4).
The rate of heating and cooling was 2 oC/min. All samples in the present investigations were
subjected to gross structural characterization by X-ray diffraction (XRD). The DC electrical resistance
was measured with the four- probe technique [12]. Iodometric titration was used to access the oxygen
content in the samples.

2. Results and discussion

The XRD patterns of the Bi2-xCuxPb0.3Sr2Ca2Cu3O10+ of the prepared samples showed miller indices
of orthorhombic structure as exhibited in Figs. (1 and 2). Most of them exhibited two main phases, i.e.,
high-TC phase (2223), low-TC phase (2212) and very low-TC phase (VLTP) in the sample with x=0.4.The
indices of the patterns are similar to refs. [13-15].
It should be noted that we observed a high shift in peaks position and some of the peaks disappeared
when increased the sintering time above 140 h likewise, resulted defects in the structure as well as losing
the high TC superconducting state. Some intensity of the high-TC phase reflections is higher than those of
the low-TC phase; the peaks belong to high TC (2223). This case appears more clearly with increasing Cu
content and it indicates the increasing of the crystalline arrangement degree [16].
Interestingly, the same peaks in Fig. 2 for sample with x=0.3 and sintered at (120+40) h are much
sharper, indicates there is an improvement in the structure. In the same time, one can infer that the size of
the crystallites has increased. Since the sharpness of the peaks of 2223-phase are ordinarily related to the
crystallite sizes.
The lattice constants (a, b, c), cell volume (V) of the samples are listed in Table (1) which shows
that the lattice parameter a decreases with the increasing the sintering time. On the other hand the samples
showed random variation in both of lattice constant a- and c- with the increasing of Cu content and this
behavior may be explained by the differences in the ionic radii for both of Cu and Bi, which resulted in
the c-axis elongation, then heightening of the high-TC phase.
218 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224

1600 1600 0.1

0.0

H(020)
L(105)
H-High phase

H(107)
1200 L-Low phase 1200
In ten sity ( a .u )

In ten sity (a.u )

H(0012)

H(222)
L(1110)
H(1111)
H(111)
L(103)

800 800

H(0014)

H(0020)
400 400

0 0
20 25 30 35 40 45 50 55 20 25 30 35 40 45 50 55
2 O 2 O

1600 1600
0.2 0.3

1200 1200
)
Intensity (a.u)

u
.
a(
800 yt 800
is
n
et
n
I
400 400

0 0
20 25 30 35 40 45 50 55 20 25 30 35 40 45 50 55
2 O O
2

1600 1600
0.4 0.5
V-Very low phase
1200 1200
Intensity (a.u)
In tensity (a .u)

800 800
V(105)
V(107)

400 400

0 0
20 25 30 35 20 25 30 35 40 45 50 55
2 O 40 45 50 55
2 O

o
Fig.1: XRD patterns for the samples with (0 s=860 C for 140 h.

2500

2000
Intensity (a.u)

1500

1000

500

0
20 25 30 35 40 45 50 55
O
2

Fig.2: XRD patterns for the samples with x= 0.3 at Ts=860 oC for (120+40) h.
 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224 219

Table .1: Sintering time tS, substitution concentrates and lattice parameters.

t S (h) x a(Å) b(Å) c(Å) V ( Å )3

140 0.0 5.4759 5.3830 37.0553 1092.2705

0.1 5.4879 5.3758 37.1231 1095.2002

0.2 5.3836 5.4633 37.1068 1091.3934

0.3 5.4740 5.3883 37.1453 1095.6212

0.4 5.3893 5.4450 37.0952 1088.5489

0.5 5.4547 5.3848 37.1362 1090.7818

120 + 40 0.0 5.4316 5.4038 37.0956 1088.8033

0.1 5.4183 5.3949 37.0105 1081.8608

0.2 5.4106 5.4236 37.1294 1089.5596

0.3 5.3842 5.4347 37.1777 1087.8757

0.4 5.3796 5.4314 37.1561 1085.6551

0.5 5.4709 5.3898 37.1416 1095.1964

160 0.0 5.3863 5.4326 37.1755 1087.8151

0.1 5.4108 5.4236 37.1325 1089.6908

0.2 5.4106 5.4236 37.1294 1089.5596

0.3 5.3733 5.4437 37.1618 1087.0061

0.4 5.3808 5.4348 37.2363 1088.9224

0.5 5.3824 5.4524 37.2227 1092.3744

The effects of sintering time on the electrical resistivity are shown in Fig. (3), where it can be clearly
seen that for the compositions Bi2-xCuxPb0.3Sr2Ca2Cu3O10+ with x=0.0, 0.2 and 0.4 with the optimum
sintering time 140 h and TC is found to be (100, 127 and 125K) respectively. While for the composition
Bi1.7Cu0.3Pb0.3 Sr2Ca2Cu3O10+ increasing the sintering time to (120+40) h (two steeps), raised T C from 130
K to 140 K, this could mainly due to the strong link and increasing of the contact areas between the grains
during the sintering process in other words decrease of porosity [17] moreover this data suggests that long
sintering-to certain limit depending on the material- time is necessary to form the high-TC phase Honda et
al. [18].
On the other side, the resistivity of the most samples decreasing nearly linearly albeit to a certain
limit although a complete zero-resistance hasn’t been observed.
However sintering for 200h the resistivity did not decrease did not decreased this could attribute to :
Firstly: long sintering time leads to a loss in the elements constituting the compound, especially (Bi and
220 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224

Cu), which causes the destruction of the high –temperature phase 2223 in agreement with previous work
[19]. Secondly: low -temperature phase grows on the account of the HTSc phase, consequently this infers
that the holes in the Cu-O and or Cu-O2 planes have decreased ; therefore, the sintering temperature is
considered to be critical for the growth of high TC phase.
In general increasing Cu concentration increases TC as can be deduced from results listed in Table
(1) and as exhibited in Fig. (4). Samples prepared by process 1 with x=0.1, 0.2, 0.3 and 0.4 revealed a
superconductor behavior, and TC is found to be (100, 127, 125 and 130K) respectively.

120 h
120 h
140 h
140 h
(120+ 40)h

x 10
(120+ 40)h
X 160 h
X 160 h
200 h
-3
200 h ( .cm)

X=0.0 X=0.1

120 h 120 h
140 h 140 h
(120+ 40)h
x 10

(120+ 40)h

x 10
X 160 h X 160 h
200 h
-3

200 h

-3
( .cm)

( .cm)
X=0.2 X=0.3

120 h
140 h 120 h
(120+ 40)h 140 h
x 10

x 10

X 160 h (120+ 40)h

200 h X 160 h
-3

-3

200 h
( .cm)

( .cm)

X=0.5
X=0.4

Fig. 3: Temperature dependence of resistivity for Bi2-xCuxPb0.3Sr2Ca2Cu3O with different concentra-

ion sintered at ts=860 oC for various periods of time.

Another feature that found from those figures is that compound at x=0.0 has TC (onset) =110K and
TC (offset) =90K. The reason may be attributed to the existence of a mixed state from the two phases
{LTP and HTP}. A sharp drop of resistivity was observed for the composition that has x=0.2 with TC
 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224 221

(offset) =125K and TC (onset) =130K. This can be explained due to the transition within grains and the
presence of low-TC (2212) phase. For the composition that has (x=0.3and 0.4) the superconducting
transition were not sharp and they had TC (offset) =110K for both of them while TC (onset) equal 150 K
and 140 K respectively. However the samples with (x=0.3 and x=0.2) show a sharp decrease for the
resistivity with decreasing temperature, revealing that the sample consists of predominantly of (2223)
phase, this trend is also a good evidence of the homogeneity of the (2223) phase [20].

0.0
0.1
0.2
X 0.3
• 0.4
0.5

Fig.4: Temperature dependence of resistivity for Bi2-xCuxPb0.3Sr2Ca2Cu3O with

different concentration sintered at ts=860 oC and periods of time =140 h.

C increased in general, although not systematic,

with increasing x to x=0.2 and 0.3 and 0.4, then reduced for further increasing of substitution. It has been
suggested [22 and 23] that TC is related to the percentage of Cu+3 present in the compound. We expect the
addition of oxygen lead to increase in the mean valence of copper ion may be attributed to the additional
oxygen. Thus increasing of the substitution will increase the amount of Cu+3 with respect to other
valences, (Cu+2 and Cu+1). Holes are present on oxygen rather than on copper as it pronounced [22] this
could be attributed to the presence of excess oxygen atoms in the CuO2 layers and these atoms will create
more holes in the perovskite layers [24]. The creation of holes in the CuO2 sheet will shorten the Cu-O
bond length and tend to improve the transition temperature. In other words, the results suggest that the
addition of Pb and substitution of Cu for Bi changes the charge balance in the Cu-O planes and that the
superconducting properties were strongly affected by changes in the hole concentration induced by the
amount of doping. Similar behavior of oxygen content with the transition temperature for
Bi1.6Pb0.4Sr2Ca3Cu4O10+ system was indicated by Zhao et al. [25].
222 M.M.Abbas et al. / Energy Procedia 18 (2012) 215 – 224

Table 2: Sintering time, substitution concentration, oxygen content and T C.

t S (h) x TC (K)
140 0.0 100 -0.5595
0.1 <77 -0.4274
0.2 127 -0.3705
0.3 130 -0.3155
0.4 125 -0.4023
0.5 <77 -0.5555
120+40 0.0 <77 -0.4125
0.1 <77 -0.4274
0.2 <77 -0.2986
0.3 140 -0.2445
0.4 <77 -0.2624
0.5 <77 0.1368
160 0.0 <77 -0.4861
0.1 <77 -0.5724
0.2 <77 -0.1543
0.3 <77 -0.2445
0.4 <77 -0.4721
0.5 <77 -0.4182

4. Conclusion

It has become clear that the physical properties of HTSc Bi2-xCux Pb0.3Sr2Ca2Cu3O10+ for Cu (0.1
x
of the preparational method. Samples sintered for 140 h with substitution of 0.3 exhibited maximum
values of TC; 130 K, while for x= 0.2 and 0.4 is found 127 K and 125 K respectively with increasing
oxygen content and is explained in terms of the concept of average copper valence.
On the other hand, increasing the sintering time to (120+40) h enhances the high-TC 2223 phase
formation and improves the value of TC; 140 K for Bi1-7Cu0.3Pb0.3Sr2Ca2 Cu3O10+ . XRD analysis
showed an orthorhombic structure and there is an increase of c –axis lattice constant for the
superconductor samples.

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