INSTITUTE OF PHYSICS PUBLISHING SUPERCONDUCTOR SCIENCE AND TECHNOLOGY

Supercond. Sci. Technol. 14 (2001) 832–838 PII: S0953-2048(01)23993-1

Influence of combined Pt and CeO2

additions on microstructure and magnetic
properties in (Nd, Eu, Gd)–Ba–Cu–O
M Muralidhar, M Jirsa1 , S Nariki and M Murakami
Superconductivity Research Laboratory, ISTEC-SRL, Division 3, 1-16-25 Shibaura,
Minato-ku, Tokyo 105, Japan
E-mail: miryala1@istec.or.jp

Received 18 April 2001, in final form 16 July 2001

Published 13 September 2001
Online at stacks.iop.org/SUST/14/832

Abstract
We studied the effect of the combined addition of Pt and CeO2 on the
dispersion of secondary phase Gd2 BaCuO5 (Gd-211) particles in
melt-processed (Nd0.33 Eu0.33 Gd0.33 )Ba2 Cu3 Oy (NEG-123) by varying the
CeO2 content from 0 to 3%. Scanning electron microscopy revealed that
submicrometre-sized Gd-211 particles were distributed uniformly
throughout the NEG-123 matrix for additions of up to 2 mol% CeO2 . The
critical current density (Jc ) increased with increasing CeO2 content,
particularly at low magnetic fields. The zero-field Jc value reached its
maximum of 100 kA cm−2 at 77 K for 1 mol% CeO2 . An improvement in
low-field Jc was attributed to the refinement of Gd-211 particles.

1. Introduction superconductors, the largest Jc values have been achieved

Large-grain RE–Ba–Cu–O (RE: Y, Nd, Sm, Eu, Gd)
bulk superconductors have significant potential for many
engineering applications, such as superconducting permanent
magnets, flywheel energy storage systems, magnetic bearings,
current leads and non-contact transport systems [1–4]. For
successful applications, the improvement of the critical current
density (Jc ) and mechanical properties is now of primary
importance.
Many attempts have been made to enhance the
critical current density by means of electron, neutron and
heavy-ion irradiation or chemical doping by Pt, Pr, Rh
and Ni [5–11]. Recent reports have shown that fine
clusters of RE1+x Ba2−x Cu3 Oy solid solution (RE-123ss)
can serve as effective pinning centres in the RE–Ba–Cu–
O systems [12–15]. The dispersion of RE-rich RE-123ss
clusters in the RE-123 matrix can be controlled by controlling
the oxygen partial pressure (pO2 ) during the melt-growth
process [16–18]. This process, usually referred to as the
oxygen-controlled melt-growth (OCMG) process, was found
to be also effective for almost all the RE-123 superconductors
where RE site is compounded with the elements selected
from Nd, Sm, Eu and Gd [13]. Among these RE-123
1 Present address: Institute of Physics, ASCR, CZ-182 21 Praha 8,
Czech Republic.
in the ternary system (Nd0.33 Eu0.33 Gd0.33 )Ba2 Cu3 Oy ‘NEG-
123’ [19–25]. In NEG-123 doped with different amounts
of the secondary phase NEG-211 ((Nd, Eu, Gd)2 BaCuO5),
submicrometre-sized particles were formed during the OCMG
process [19–21]. Transmission electron microscopy revealed
that the smallest RE-211 particles contained Gd, while most
of the larger particles consisted of NEG-211 with the chemical
ratio of 1:1:1. Since the smaller particles are the more effective
in enhancing Jc values, we prepared NEG-123 samples with
an addition of only Gd-211 and achieved a very fine dispersion
of Gd-211 particles in the NEG-123 matrix [21, 26].
For the refinement of secondary-phase particles an
addition of Pt or CeO2 has been found to be effective.
We proved that a combined addition of Pt and CeO2 is
more effective in refining NEG-211 particles in a NEG-123
matrix [27]. In this study we varied the amount of CeO2 from
0 to 3 mol% in NEG-123 with 30 mol% Gd-211 containing
0.5 mol% Pt, and studied the effect of CeO2 content on the
size and distribution of the Gd-211 and the Jc –B performance
at 77 K.
2. Experiment
Precursor powders of (Nd0.33 Eu0.33 Gd0.33 )Ba2 Cu3 Oy were
prepared by repeated calcining and grinding using a mixture

0953-2048/01/100832+07$30.00 © 2001 IOP Publishing Ltd Printed in the UK 832

 Influence of combined Pt and CeO2 additions in (Nd, Eu, Gd)–Ba–Cu–O

of Nd2 O3 , Eu2 O3 , Gd2 O3 , BaCO3 and CuO. The details of the

NEG powder preparation have been reported elsewhere [19].
All the composites were made from NEG-123 powder with
grain size of 32 µm. 30 mol% of commercial Gd-211 powder
with a diameter less than 1 µm was added to sintered NEG-123
powder. 0.5 mol% Pt and CeO2 of 0, 1, 2 and 3 mol% were
added to refine the secondary-phase particles.
The peritectic decomposition temperature determined
with differential thermal analysis (DTA) measurements was
used to schedule the heat treatment profile of the OCMG
process for different NEG samples. The melt growth was
performed in flowing 0.1% O2 /99.9% Ar. The details of the
heat treatment schedule were published in [19]. Rectangular
platelets with dimensions of a × b × c ≈ 1.5 × 1.4 × 0.4 mm3
were cut from central parts of as-grown crystals for the
comparative study of the Jc –B data. The oxygen annealing
(a)
was performed in flowing oxygen gas in a temperature range
of 300–600 ◦ C [19].
Microstructural observations were performed with a
scanning electron microscope on polished surfaces of the
samples. Measurements of the superconducting transition
temperature, Tc , were performed with a commercial SQUID
magnetometer (Quantum Design, model MPMS-7) at 1 mT.
Magnetization hysteresis loops (MHLs) were measured at
T = 77 K in fields up to 7 T applied parallel to the c-axis. The
Jc values were calculated based on the extended Bean critical
state model, Jc = (20 M)/[a{1 − a/(3b)}], where M is the
magnetization hysteresis during the increasing and decreasing
field processes, a and b (a < b) are the cross-sectional
dimensions of the sample perpendicular to the field [28].
For trapped-field measurements we used a superconduct-
ing magnet with the samples cooled by a cryo-cooler. First, the
sample was cooled to 77 K in the presence of 5 T with the field (b)
directed parallel to the c-axis. Then the field distribution was
measured by scanning a Hall probe sensor set 5 mm above the
sample surface as the external field was gradually reduced from
5 to 0 T in 0.5 T steps. Details of the measurement procedure
are described in [29].

3. Results and discussion

3.1. Microstructure analysis

Figures 1(a)–(c) show scanning electron microscopy (SEM)
micrographs of NEG-123 samples with 30 mol% Gd-211,
0.5 mol% Pt and 1–3 mol% CeO2 . It is evident that the
secondary phase particles are homogeneously dispersed in the
NEG-123 matrix and a combined addition of Pt and CeO2 is
effective in refining the Gd-211 particles.
The sample with 1 mol% CeO2 addition showed the (c)
most uniform network of secondary phase particles. Low-
Figure 1. Low-magnification scanning electron micrographs of
concentration regions of Gd-211 were almost absent in this NEG-123 with 30 mol% of Gd-211 and 0.5 mol% of Pt prepared in
sample, showing that this doping level is optimal from 0.1% O2 : (a) 1 mol% of CeO2 , (b) 2 mol% of CeO2 and (c) 3 mol%
microstructural viewpoints. An increase of CeO2 content of CeO2 .
over 2 mol% did not result in further particle refinement.
Microstructural observation proved that a combined addition
of CeO2 and Pt is very effective in refining Gd-211 particles and Figures 2(a)–(d) show high-magnification SEM micro-
thus in increasing the uniformity of the pinning microstructure. graphs of the NEG-123 samples with 0, 1, 2 and 3 mol% of
These results proved that the present technique led to the CeO2 . In all cases very finely dispersed, round secondary-
production of the samples with homogeneous microstructure phase particles appeared. Their mean size and quantity de-
in the entire pellet 2 cm in diameter and 1 cm in thickness [30]. pended on the initially added CeO2 content. It is also no-

833
M Muralidhar et al
(a)
(c)
Figure 2. High-magnification scanning electron micrographs of NEG-123 with 30 mol% of Gd-211 and 0.5 mol% of Pt prepared in
0.1% O2 : (a) CeO2 -free, (b) 1 mol% of CeO2 , (c) 2 mol% of CeO2 and (d) 3 mol% of CeO2 .
table that submicrometre-sized Gd-211 particles with high con-
centration are distributed in the samples with 1 and 2 mol%
CeO2 .
In the CeO2 -free composite, round particles were
homogeneously dispersed in the NEG-123 matrix, as shown
in figure 2(a). In the sample with 1 mol% of CeO2 , the Gd-
211 particles were round and their mean size was less than
1 µm (figure 2(b)). The sample with 2 mol% CeO2 exhibited
a similar secondary-phase morphology to the sample with
1 mol% CeO2 , but the mean diameter of the Gd-211 particles
slightly increased over 1 µm. In the sample with 3 mol%
CeO2 the particle shape drastically changed and large particles
appeared (figure 2(d)).
We calculated the volume fraction of the second phase
trapped in the NEG-123 matrix from SEM micrographs using
an image processing system, and the results are presented in
figures 3(a)–(d). In the sample without CeO2 , the average Gd-
211 particle size was about 0.5 µm. The addition of 1 mol%
CeO2 led to the particle size reduction to 0.1 µm range. The
sample with 2 mol% CeO2 exhibited a similar distribution of
the Gd-211 to the sample with 1 mol% CeO2 , with a slight
decrease of the number of particles in the 0.1 µm range. A
further increase of the CeO2 content resulted in a significant
increase of the average particle size.
834
(b)
(d)
3.2. Magnetic characterization
Figure 4 represents the temperature dependence of the dc
susceptibility for the NEG-123 samples in a magnetic field of
1 mT. All the samples showed the onset of the superconducting
transition in the range 92.7–93.8 K and transition widths within
1.5 K. Slightly higher onset Tc values (by about 0.9 K) in the
samples with 1 and 2 mol% of CeO2 may be attributed to the
refinement of secondary-phase particles, since refined Gd-211
particles embedded in the NEG-123 matrix reduce the number
of the defects otherwise produced by thermal stresses around
large secondary-phase particles. This results in a quality
improvement of the 123 matrix and consequently in an increase
of Tc . A Tc decrease in the sample with 3 mol% CeO2 can then
be understood as a consequence of the coarsening of Gd-211
particles. This is in accord with some recent works where the
authors linked the reduction of Tc in Y-123 to a contamination
of the Y-123 matrix [31].
Figure 5(a) shows the critical current density (Jc ) as a
function of applied field for various concentrations of CeO2 .
In the CeO2 -free sample, the highest remnant value of Jc was
75 kA cm−2 and the secondary peak value recorded at 3 T
was 50 kA cm−2 . In the sample with 1 mol% CeO2 Jc was
100 kA cm−2 at zero field. The previous remnant Jc value,
 Influence of combined Pt and CeO2 additions in (Nd, Eu, Gd)–Ba–Cu–O

Figure 3. Size distribution of Gd-211 secondary phase in OCMG-processed NEG-123 sample fabricated with addition of 0.5 mol% of Pt
and (a) CeO2 -free, (b) 1 mol% of CeO2 , (c) 2 mol% of CeO2 and (d) 3 mol% of CeO2 .

Figure 4. Temperature dependence of the normalized dc susceptibility for OCMG-processed NEG-123 plus 30 mol% of Gd-211 and
0.5 mol% of Pt with various CeO2 concentrations.

835
M Muralidhar et al
(a)
(b)
Figure 5. Field dependence of Jc (T = 77 K, Ha  c-axis) for
NEG-123 plus 30 mol% of Gd-211 and 0.5 mol% of Pt with different
amounts of CeO2 . (a) Jc determined from hysteresis measurements,
and (b) Jc normalized to the value at zero applied field, Jc (0 T).
75 kA cm−2 , was achieved at 0.6 T. The remnant value of Jc
reached a maximum at 2 mol% and Jc dropped again above this
836
concentration. Such behaviour is in good agreement with the
change in the Gd-211 phase morphology. Figure 5(b) presents
the field dependence of the Jc normalized to the current density
at zero field, Jc (0). In this representation the Jc enhancement
in low fields with increasing content of CeO2 is evident. In
high fields the Jc values were hardly influenced by varying the
CeO2 content, giving evidence that the fine Gd-211 particles
are an effective pinning medium especially in low fields. The
pinning mechanism is evidently different from that of the
clusters responsible for the second peak. A similar effect of
CeO2 doping was also observed in the YBCO system [31, 32].
4. Trapped-field measurements
The NEG-123 sample with 1 mol% CeO2 possessing the
best Jc –B performance was employed for the study of the
trapped-field distribution in a pellet of 22 mm in diameter. It
is, however, well known that RE-123 materials suffer from
enormous mechanical forces induced during magnetization
cycles that often overcome the mechanical strength of the
material which leads to a fatal fracture [33]. To improve the
mechanical properties of the pellet, we added 10 wt% Ag2 O. In
our recent paper [34] we demonstrated that an addition of Ag2 O
did not significantly affect the electromagnetic performance of
the material. Before the measurement, the sample was field
cooled with liquid nitrogen in the presence of 5 T. The trapped
field was measured at several stages as the external field was
reduced from 5 to 0 T in 0.5 T steps.
In figure 6(a) one can see four superconducting domains
divided by two boundaries crossing approximately in the centre
of the pellet, which clearly reflects crack formation during
the magnetization process. Figure 6(b) shows a side view
of the trapped-field distribution, which shows that the field
profile, although structured, remained continuous. In other
words, the cracks did not propagate completely throughout the
sample. Further experiments are under way to employ more
silver and/or epoxy resin impregnation in order to improve the
mechanical properties.
The field dependence of the maximum trapped field B0 in
the largest grain is shown in figure 7. The trapped-field value
at the remnant state was 0.63 T; we believe that this value will
be doubled after successfully fabricating and magnetizing an
unfractured NEG-123 pellet of the same (2 cm) diameter. In
our present sample the maximum trapped fields of 0.54 and
0.50 T were achieved in the largest grain at applied fields of
1 and 2 T, respectively. This proves that the NEG-123 sample
has a large enough field-trapping capability in high applied
magnetic fields and thus it has potential for uses as a high-field
superconducting magnet.
5. Conclusions
We studied the effect of CeO2 addition on the microstructure
and the Jc –B performance of a OCMG-processed NEG-123
composite with 30 mol% of Gd-211. The SEM observations
confirmed that a combined addition of Pt and CeO2 is effective
in reducing the size of the secondary-phase particles. The
high-magnification SEM analysis proved that a combined Pt
plus CeO2 addition improves the uniformity of the Gd-211
particles distribution in the NEG-123 matrix via reducing

Figure 6. Top and side views of the trapped-field distribution in the
sample NEG-123 plus 30 mol% of Gd-211, 0.5 mol% of Pt, 1 mol%
of CeO2 and 10 wt% of Ag2 O at 77 K (the remnant state).
Figure 7. The trapped field versus applied field in NEG-123 plus
30 mol% of Gd-211, 0.5 mol% of Pt, 1 mol% of CeO2 and 10 wt%
of Ag2 O at 77 K. Note that the high trapped-field value of 0.5 T was
achieved at 2 T even in a fractured sample.
low-concentration regions of the secondary phase. However,
when the content exceeded 2 mol%, Jc decreased in a wide
temperature range. The best results with respect to both
microstructure and Jc were achieved with the addition of
Influence of combined Pt and CeO2 additions in (Nd, Eu, Gd)–Ba–Cu–O
1 mol% CeO2 . The trapped-field measurements indicated
that NEG-123 materials are suitable for high-magnetic-field
applications.
Acknowledgments
This work was supported by the New Energy and Industrial
Technology Development Organization (NEDO) as a part of
its Research and Development of Fundamental Technology
for Superconductor Applications. MJ greatly appreciates the
JSPS fellowship covering his stay at Iwate University and
the collaboration with ISTEC. Partial support was provided
by the grant No. A1010919/99 of the Grant Agency of the
ASCR, M Muralidhar acknowledges support from the NEDO
fellowship.
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