Effects of ZrO, on the texturing and properties of melt-processed

J. Y. Juang, C. L. Wu, S. J. Wang, M. L. Chu, K. H. Wu, T. M. Uen, and Y. S. Gou

Institute of Electrophysics, National Chiao-Tung University, Hsinchu, Taiwan, China
H. L. Chang and C. Wang
Applied Research Laboratory, Telecommunication Laboratories, Ministry of Transportation
and Communications, l? 0. Box 71, Chung-Li, Taiwan, China
M. J. Tsai
Materials Research Laboratory, Industrial Technology and Research Institute, Chutung, Taiwan, China
(Received 30 November 1993; accepted for publication 21 February 1994)
The addition of ZrO, is found to be very effective as the nucleation sites to promote the oriented
growth of YIBa,CusO,-B (YBCO) during peritectic solidification. Extended regions of well-
textured YBCO grains with superior superconducting properties of the YBCO bulk are readily
obtained by a single-step melt process at much lower process temperatures. At 77 K, the platelike
Josephson weak-link behaviors observed in pure melt-processed YBCO have been effectively
eliminated, indicating that the coherency between the spherulitic superconducting YBCO grains
may have been greatly improved by ZrO, additions.

The melt-textured-growth (MTG) process, initially de-
veloped by Jin et al.’ and subsequently modified by many
others,ze6 has been demonstrated as one of the most viable
processes toward practical application of the high-
temperature YBa&u,O,-B (YBCO) superconductors. As a
result, understanding how the superconducting grains evolve
from the incongruent Y,BaCuOs (211. phase) and an off-
stoichiometry liquid phase via a peritectic reaction into its
final microstructure has become a subject of extensive
research.2-8 In MTG and its derivatives such as
melt-powder-melt-growth” and melt-quench-melt-grow&
processes, the fine dispersion of the 211-phase particles right
above the peritectic temperature (~1030 “C) is believed to
be very crucial in obtaining the desired microstructure? The
essence to that is attributed to the effects of the 211 particles
in shortening the diffusion lengths between each constituent
required for maintaining proper stoichiometry as well as in
promoting the directional spherulitic growth of YBCO
grains.7-9 Indeed, results have shown that, with careful con-
trol of 211 dispersions, well-textured platelike grains with
correct composition can be obtained. The critical current
density (J,) of bulk YBCO following such routes has been
successfully raised up to 25 000 A/cm2 at 77 K and 1 T of
magnetic field.” However, it is noted that the complicated
heat treatment schedule used3r4,9and, in particular, the high
process temperature (up to -1300 “C or higher) may become
crucial hindrances for such processes to be practically us&d.
In this letter, we report on an alternative process based
on the notion of heterogeneous nucleation in promoting
spherulitic growth of YBCO during the lower incongruent
peritectic reaction of the system [i.e., the reaction of
211 +L (BaCuO,+CuO)+YBCO at T=1030 “Cl. It is found
that, by adding ZrOz powder (-1 w in diameter) into the
prereacted YBCO powder to serve as the primary nucleation
sites of YBCO grains, the much desired coherently textured
gram structure can be readily obtained by a single-step melt
process at much lower treatment temperatures.
Reagent grade powders of Y,03, BaCOs , and CuO were
mixed and ground with nominal 1:2:3 molar ratio of
YBa:Cu. The mixture was then processed by the standard
solid state sintering procedure to obtain the prereacted
YBCO for subsequent ZrO, doping and melt treatment. Dif-
ferent amounts of ZrO, powder, ranging from 0.05 to 5
wt %, were added to the prereacted YBCO powder to inves-
tigate the effects of the heterogeneous nucleation on peritec-
tic solidification. The mixed and pressed samples were
heated from room temperature to 1030 “C with a heating rate
of 7-“C/min and then stayed there for 30 min. The furnace
was then moved by a controlled step motor to crematethe
necessary temperature gradient for directional solidification.
The total time taken for the samples to go through the growth
temperature domain (1030-940 “C) was about 14 h. Samples
were then kept at 940 “C for another hour before cooling to
550 “C with a rate of 7 “C/min. After holding at 550 “C for
another 12 h for oxygenation, samples were finally cooled to
room temperature at a rate of 10 “Urnin to prevent possible
cracking due to thermal stress. We note that by lowering the
highest treatment temperature to 1030 “C (the peritectic tem-
perature) and making it a continuous single-step process
could be crucial when practical production is considered.
The structure and phases of the obtained samples were
characterized by optical and scanning electron microscopy
along with the energy dispersive spectroscopy (EDS) and
x-ray diffraction (XRD) analysis. It is evident from the XRD
results that, within the composition range studied, the result-
ant materials were essentially single phase YBCO with a
minute amount of unreacted residuals. For transport mea-
surements, samples were cut into rectangular bars with di-
mension of about 1X0.5X 10 mm3 and the standard four-
probe method was adopted. For magnetic measurements,
disks of about 3 mm in diameter and 0.5 mm in thickness
were prepared and measured using superconducting quantum
interference device magnetometer (Quantum Design) in
fields up to 5 T and temperatures ranging from 150 to 5 K.
Typically, the zero-resistance T,‘s measured by transport
method were within the range of 83-85 K, while those mea-

2306 Appl. Phys. Lett. 64 (17), 26 April 1994 0003-6951/94/64(17)/2306/3/$6.00 Q 1994 American Institute of Physics

Downloaded 03 Aug 2006 to 133.11.199.19. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
 ,O 20 LO 60 80 100 120
FIG. 1. The diamagnetic responses for undoped (open symbols) and
ZrOz-doped (solid symbols) melt-processed YBCO samples in 10 G field-
cooled measurements. The inset shows the corresponding normalized R(T)
behaviors of the same samples.
sured magnetically were between 90 and 91 K. As an ex-
ample, Fig. 1 shows the typical magnetization results to-
gether with the R(T) behaviors in the inset for two of the
samples studied. As is evident from Fig. 1, and is typical for
other ZrOz compositions, although the R(T) curve for
ZrO,-doped samples was somewhat deviated from the usual
linear behavior, the diamagnetic effects, nevertheless, sug-
gest that the superconducting YBCO phase was even purer in
the doped samples. In any case, the present results are in-
dicative that the materials obtained by the present simple
melt process were mostly single-phased YBCO. This is a
very important starting point as we proceed to compare other
features manifested by these samples to delineate the effects
of ZrOz addition below.
Figure 2 shows the representative microstructures for
samples various amounts of ZrOz added. For undoped
samples [Fig. 2(a)], although blocks of textured grain struc-
ture are obtainable by the present one-step process, the ori-
entation between each block, however, is not well aligned. In
addition, as revealed by the EDS analysis, there are some
residual 211 phases present in between each block (as indi-
cated in the photograph). In contrast, as can be seen in Fig.
2(b), even with the smallest amount of ZrO, added (0.05
wt % in this case) significant improvement in texturing
growth is clearly demonstrated. Also; as shown in Figs. 2(c)
and 2(d), there is a tendency of getting finer textured grain
structure extended over larger regions when the amount of
ZrO, added was increased. This strongly suggests that one of
the important roles played by the added ZrOz was to act as
the primary nucleation sites for the peritectically grown
YBCO.
With the dramatic effect of the ZrO, addition on the
texturing of YBCO grains described above, the next natural
question to ask is: How would the associated superconduct-
ing properties be affected? Figure 3 shows an example dem-
onstrating such effects. In Fig. 3(a), the shape and field de-
pendencies of the magnetization hysterises (M-H loops) are
essentially the same with no apparent weak-link behaviors
up to a field of 5 T for both undoped and ZrOa-doped
samples at 5 K. However, as is evident from Fig. 3(b), at
higher temperatures (77 K), very different behaviors for;the
Appl. Phys. Lett., Vol. 64, No. 17, 25 April 1994
Downloaded 03 Aug 2006 to 133.11.199.19. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
FIG. 2. The scanning electron microscope results revealing the typical mi-
crostructures of melt-processed YBCO with various amounts of ZrOZ added.
(a) 0 wt %; (b) 0.05 wt %; (c) 0.5 wt 96, and (d) 4.2 wt %. The arrows
indicate the direction of growth in accordance with the temperature gradient
provided.
same samples were observed. The typical weak-link associ-
ated behavior exhibited by the undoped samples (open
circles) were greatly suppressed for ZrO,-doped samples
(solid circles). As we have emphasized, since, in terms of
stoichiometry and intrinsic superconductivity, the obtained
materials were essentially of the same quality, the differences
observed here can only be understood from the modifications
of microstructure. In our measurement configuration, with
the field being perpendicular to texturing orientation, we ex-
pect the circulating supercurrent to flow in the plane of tex-
turing. Consequently, the apparent weak-link behavior exhib-
ited by the undoped samples at higher temperatures is
believed to arise from the boundary area between each tex-
tured block of grains encountered by the flowing currents.
To further delineate that the observed M-H loops are
indeed reflecting the critical current densities and in support
of the above arguments, we have tried to convert the M-H
results into field dependent critical current densities [J,(H)].
However, to do that one must first check if the results are
describable by Bean’s critical state model.” Following
Murakami et al. ,3 the difference in magnetization at a fixed
field, AM(H), as a function of sample thicknesses, D, were
checked for each set of samples. A linear dependence of
AM(H) vs D was observed consistent with that of Ref. 3. In
Fig. 4, we show the J,(H) results for two of the representa-
tive samples at 77 K obtained by applying the expression3
J,=20 AMID. Cl?
Vastly different J,(H) results are, again, evident. The re-
maining question to ask, however, is if the apparent weak-
link behavior for the undoped sample is indeed consistent
with that depicted in the previous paragraph and is in accor-
dance with the grain structure revealed in Fig. 2. As has been
Juang et a/. 2307
 _,I
?’‘ [
“,-;si*
-601 I , I I I 1
-1
1

01
0
l :.4.2%-ZrOz
0:0X-Zr02

1 2 3 L
-6 -4 -2 0 2 4 6
HtTesla 1
H(T)

FIG. 4. The typical J,(H) behaviors at 77 K as derived from the M-H

hysteresis measurements using Eq. (1) for undoped (open symbols) and
.
ZrO,-doped (solid symbols) YBCO samples. The inset shows the log-log
plot of the same data to delineate the exponent of the field dependence of
Jc
8- 1

$0
5 -,
-2 - : L.2%-302
-3
-4
-3 -2 -1 0 1
H(Tesla)
FIG. 3. The typical M-H hysteresis for undoped (open symbols) and
ZrOz-doped (solid symbols) YBCO at (a) 5 K and (b) 77 K.
pointed out by Peterson and Ekin,rr the exact form of J,(H)
depends strongly on the geometry of junctions made of the
boundary weak links. In the framework of this model, the
Fraunhofer diffraction pattern of each junction is described
by the expression
where J, is the first-order Bessel function and 4 and & are
the magnetic flux in the junction area and flux quantum,
respectively. After averaging over different grain size for the
condition of 4%&, Eq. (2) leads to the dependence of
J,alT1 and J,cYH-“~ for platelike and spherical-type junc-
tions, respectively. In the inset of Fig. 4, we plot the J,(H)
results in log-log scale to delineate the functional depen-
dence between the two quantities. As can be seen from the
plot, the J, for the undoped samples displays a clear H-l
dependence over the range of field studied, consistent with
the platelike weak-link picture suggested in Fig. 2. For the
ZrO,-added samples, a more conventional behavior for ho-
mogeneous superconductors with a gradual decrease fol-
lowed by a steep drop near the critical field, Hc2, was
observed.*’ The scaling of pinning force density as a func-
tion of the reduced field following the Feitz-Webb’s
analysisILl is currently underway to delineate the dominant
pinning effects.
In summary, we have demonstrated a new process which
is practically more viable for obtaining the much needed
texturing structure with minimized weak links. The addition
of ZrO, powder appeared to act as primary nucleation sites
during the peritectic reactions and further promote the
spherulitic growth of the YBCO grains to result in extended
2 regions of well-oriented microstructure. The melt-process
treatment temperature has been reduced significantly (from
1400 to 1030 “C) and samples with dramatic improvement in
superconducting properties are obtained.
This work was supported by the National Science Coun-
cil of Republic of China under Grant No. NSC81-0208-
M009-501.
‘S. Jm, T. H. Tiefel, R. C. Sherwood, M. E. Davis, R. B. van Dover, G. W.
Kammlott, R. A. Fastnacht, and H. D. Keith, Appl. Phys. L&t. 52, 2074
(1988).
‘K. Salama, V. Selvamanickam, L. Gao, and K. Sun, Appl. Phys. L&t. 54,
2352 (1989).
3M. Murakami, M. Morita, K. Doi, and K. Miyamoto, Jpn. J. Appl. Phys.
28, 1189 (1989).
4H. Fujimoto, M. Murakami, S. Gotoh, N. Koshixuka, and S. Tanaka, Adv.
Supercond. 2, 285 (1990).
‘P. J. McGinn, W. Chen, N. Zhu, U. Balachandran, and M. T. Lanagam,
Physica C 165, 480 (1990).
“R L Meng, C. Kinalidis, Y. Y. Sun, L. Gao, Y. K. Tao, P. H. Hor, and C.
4. &I, Nature 345, 326 (1990).
7S. Jin, G. W. Kammlott, T. H. Tiefel, T. T. Kodas, T. L. Ward, and D. M.
Kroeger, Physica C 181, 57 (1991).
‘S. Jim, T. H. Tiefel, R. C. Sherwood, R. B. van Dover, M. E. Davis, G. W.
Kammlott, and R. A. Fastnacht, Phys. Rev. B 37, 7850 (1988).
‘M. Murakami, in Processing and Properties of High-T, Superconductors,
Bulk Materials, Vol. 1, edited by S. Jin (World Scientific, Singapore,
1993), Chap. 6, p. 213.
“C. P. Bean, Phys. Rev. L&t. 8, 250 (1962).
l1 R. L. Peterson and J. M. Ekin, Physica C 157, 325 (1989).
I’M. L. Cbu, H. L. Chang, C. Wang, J. Y. Juang, T. M. Uen, and Y. S. Gou,
Appl. Phys. L&t. 59, 1123 (1991).
13WA. Feitz and W. W. Webb, Phys. Rev. 178, 657 (1969).

2308 Appl. Phys. Lett., Vol. 64, No. 17, 25 April 1994 Juang ef al.

Downloaded 03 Aug 2006 to 133.11.199.19. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp