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IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 25, NO.

3, JUNE 2015

6800604

Effect of Laser Treatments on the Microstructure


and Physical Properties of Bi-2212 and
Gd-123 Bulk Samples
F. Rey-Garca, V. Lennikov, H. Amaveda, C. Laliena, M. Mora, E. Martnez,
C. Bao-Varela, L. A. Angurel, and G. F. de la Fuente

AbstractA laser furnace (LF) apparatus, which applies laser


irradiation to the surface of a material while it is moving inside
a high temperature roller furnace, has been recently patented
and demonstrated unprecedented potential in the development of
ceramic materials. This apparatus has been used in this study
to texture Bi-2212 bulk samples in planar geometries with dimensions of several centimeters. The process can be scaled-up to
dimensions that could be interesting from a technological point
of view. The influence of laser emission and furnace processing
parameters, as well as the application of an electrical current, has
been studied to define parameters which yield an improvement
of the superconducting properties. These studies have also been
initiated in Gd-123 bulk samples, analyzing the changes that a
LF treatment is able to induce in their microstructure using an
infiltration approach.
Index TermsBi-2212, Gd-123, laser processing, texture.

I. I NTRODUCTION

ASER induced solidification is a powerful tool to modify


the microstructure of ceramic materials, and, in particular,
that of Bi2 Sr2 CaCu2 O8+X (Bi-2212) superconductors. Laser
Floating Zone (LFZ) techniques have been used to develop
Bi-2212 superconducting fibers or rods with attractive transport
properties as a consequence of the well-aligned grain orientation that was induced after solidification [1], [2]. More recently,
it has been observed that the simultaneous application of an
electrical current can modify the crystallization interface [3],
[4]. This technique, called Electrically Assisted Laser Floating

Manuscript received August 11, 2014; accepted October 12, 2014. Date
of publication October 28, 2014; date of current version January 27, 2015.
This work was supported in part by the Spanish Ministerio de Economa y
Competitividad and the European FEDER Program (project MAT2011-22719)
and by the Gobierno de Aragn (research groups T12 and T87) and by
CERAMGLASS project (EU LIFE program LIFE11 ENV/ES/560).
F. Rey-Garca is with the Instituto de Ciencia de Materiales de Aragn
(CSIC), Universidad de Zaragoza, 50018 Zaragoza, Spain, and also with the
Unidad Asociada de Microptica and ptica GRIN (CSIC-ICMA), Facultade
de ptica e Optometra, Universidade de Santiago de Compostela, 15782
Santiago De Compostela, Spain.
V. Lennikov, H. Amaveda, C. Laliena, M. Mora, E. Martnez,
L. A. Angurel, and G. F. de la Fuente are with the Instituto de Ciencia
de Materiales de Aragn (CSIC), Universidad de Zaragoza, 50018 Zaragoza,
Spain (e-mail: angurel@unizar.es).
C. Bao-Varela is with Unidad Asociada de Microptica and ptica
GRIN (CSIC-ICMA), Facultade de ptica e Optometra, Universidade de
Santiago de Compostela, 15782 Santiago De Compostela, Spain.
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TASC.2014.2365411

Zone (EALFZ), allows more control over phase distribution and


grain alignment.
The technique was more recently modified to process superconducting materials in planar geometries [5], [6], because
these opened new possibilities towards the development of
technological applications, as compared to the previous rod
geometries. The combination of different cylindrical lens sets
allows transforming a laser beam into a thin, high power
density line that produces the molten zone on the precursor.
Because of the laser line energy distribution, this Laser Zone
Melting (LZM) technique has been used to texture samples of
1 cm width. To process larger area samples, however, it was
necessary to develop a new laser melting technique based on
laser line scanning [7]. In this case, the laser beam scans across
the sample surface with a high speed. By controlling the laser
parameters, it is possible to maintain a thin molten zone along
the scanning direction.
This processing method induces high thermal stresses that
can induce cracks in these ceramic materials. This is particularly important in these superconductors, because the appearance of these defects can deteriorate their transport properties.
This problem can be overcome by performing the laser treatment inside a furnace at high temperatures [8]. A recently
patented laser furnace apparatus [9][11] allows focusing a
laser beam on a sample that is moving inside a high temperature
furnace, at temperatures avoiding crack generation. The use
of a laser furnace apparatus for processing 4 cm diameter,
round Bi-2212 plates, is presented in this paper. In the case
of the rare earth based materials REBa2 Cu3 O7x (RE-123),
preliminary results obtained with similar laser furnace processing, combined with an infiltration method [12], [13], are
presented.
II. E XPERIMENTAL
A. Precursor Preparation
Bi-2212 (4 cm in diameter and a thickness of 2.1 mm) disk
precursors with stoichiometry Bi2.02 Sr2.02 Ca0.98 Cu1.99 OX /
2.9 wt.% Ag nominal composition (Nexans Superconductors
GmbH) were prepared by axial pressing at 140 MPa during
7 minutes. In each sample, 14 g of superconducting powder
were used. Precursors were annealed in air at 750 C for
6 h. After laser treatment, samples were annealed at 820 C for
60 h, followed by 12 h at 800 C.

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6800604

IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 25, NO. 3, JUNE 2015

Fig. 1. Photograph of the superconducting sample inside the furnace during


laser treatment. The image clearly shows that the width of the scaned laser line
is longer than the sample width.

In the case of GdBa2 Cu3 O7X (Gd-123) samples, an infiltration approach was used. After drying for 6 h at 350 C,
mixtures of Gd2 O3 , BaCO3 , and CuO with nominal compositions Gd2 BaCuOX (Gd-211) and Ba3 Cu5 Ox were prepared.
These mixtures were thermally annealed at 850 C (16 h), 900

C (20 h) and 900 C (24 h). After each annealing sequence,


the powder was milled again. Two plates (2 cm in diameter)
were pressed with each composition. In addition, a third plate of
Gd2 O3 was prepared and used as support for the laser treatment.
The Ba3 Cu5 OX plate was placed on top. After laser treatment,
samples were annealed in O2 atmosphere at 450 C for 96 h.

Fig. 2. Photograph of a Bi-2212 sample after laser treatment. An initial laser


treatment was performed at 500 mm/h (upper part of the sample) followed by a
second one at 30 mm/h (central and lower part of the sample).

Transport critical current values were measured at 77 K in the


Bi-2212 materials with the sample immersed in liquid nitrogen
and the electrical current applied in the perpendicular direction
to the solidification front. The Ic values were determined using
the 1 V/cm criterion. Tc values in the Gd-123 samples were
obtained from (T ) measurements with an ac field amplitude
of 79.6 A/m and a frequency of 120 Hz.
III. R ESULTS IN Bi-2212 M ATERIALS

B. Laser Processing
The LZM process was performed inside a furnace, at temperatures of 450 C for Bi-2212 and 650 C for Gd-123 samples,
respectively. A Rofin-Sinar 350 W SLAB-type pulsed CO2
laser, emitting at a wavelength = 10.6 m, was used in this
work. The laser output beam was steered with a galvanometer
mirror system. With a diameter of 0.8 mm at a focal distance of
950 mm, it was displaced along the y-direction with a steering
speed in the range of 7.518.75 m/s. As can be observed in
Fig. 1, this allows transforming the circular laser beam into
a long laser line at the focus. This beam line was directed
to the sample surface at an angle of 15 with respect to the
samples vertical. Modifying the line width allows controlling
the amount of energy that is deposited on the surface. It is
important to control all these parameters to be able to maintain
the molten volume constant, even when the laser beam is out of
the sample, so as to obtain a flat solidification front.
The sample is displaced in the x-direction, with the traverse
rate determining the speed at which the molten zone travels
along the sample. One of the limitations of the equipment used
in this work is that its minimum sample displacement speed is
25 mm/h. This fact is determinant in the case of the Gd-123
samples, where much lower rates would be desirable.
C. Sample Characterization
The microstructure and phase composition of the LZM samples were analyzed with a field-emission scanning electron
microscope (FESEM, Carl Zeiss MERLIN) using secondary
and angle-selective secondary backscattered electrons, as well
as energy-dispersive X-ray spectroscopy.

Fig. 2 shows a Bi-2212 sample after a two-step LZM experiment. In the first step, the sample was moved at 500 mm/h.
The upper part of the photograph shows approximately the last
6 mm of the sample surface after this initial treatment. The rest
of the sample was processed again at 30 mm/h in a second step,
with a line scan width of 250 mm and a laser beam scanning rate
of 18.75 m/s. A transversal quenched melt band can be clearly
observed between the surfaces obtained in steps 1 and 2 above.
The melt bands width is ca. 1.6 mm and it is uniform along the
complete sample width. The furnace temperature was fixed at
450 C during both steps, since cracks may appear in parts of
the samples at lower temperatures. After the texturing process,
sample thickness is reduced to 1.73 mm and the laser induces
texture in a thickness of 750 m.
Due to density differences along the thickness profile of
the sample, between the upper laser melted region and the
precursor in contact below, the sample sometimes bends during
the LZM texturing process. This problem can be avoided by
performing the laser treatment on both sides of the sample.
Best results are obtained when the full sample cross-section is
affected by these two laser treatments.
Fig. 3 shows the differences in microstructure obtained
in two samples processed with two LZM rates: 30 mm/h
(Fig. 3(a)) and 60 mm/h (Fig. 3(b)). In this second sample,
the region textured by the laser is reduced to 525 m. Two
main phases are present in the as-grown samples, corresponding to light grey Bi2 Sr2 CuOX (Bi-2201) and dark grey
(Sr1x Cax )CuOX . The latter phase determines the orientation of the Bi-2212 grains after annealing [2], [6] and, as a
consequence, improved texture of the final superconducting
phase is obtained in the sample textured at 30 mm/h. The
left part of the photograph presented in Fig. 3(a) corresponds

REY-GARCA et al.: EFFECT OF LASER TREATMENTS ON Bi-2212 AND Gd-123 BULK SAMPLES

6800604

Fig. 4. Longitudinal cross section of a Bi-2212 sample textured (a) without


applying an external electrical current and (b) applying 1A in the direct
configuration.

Fig. 3. Top view of the microstructure of a sample processed at (a) 30 mm/h


and (b) 60 mm/h before final annealing.

to the quenched molten volume. It shows that with the laser


parameters imposed, a very flat solidification front is obtained
and, consequently, the grains are very well aligned with the a-b
plane parallel to the x-direction. In some regions, a maximum
deviation of 15 with respect to the x-axis has been measured.
In contrast, when faster processing rates are used (Fig. 3(b)),
the misalignment increases and misorientation angles up to 40
have been observed in many regions of the sample.
The IV characteristics at 77 K have been measured in the
sample processed at 30 mm/h, obtaining a potential dependence
with Ic (77 K) = 158 A and the exponent n = 6.7. It is known
[8] that, because of the generated thermal gradients, the LZM
process in planar geometries induces a well-textured region of
grains parallel to the sample surface and within a fraction of
the total affected thickness. Although the current mainly flows
within this limited cross section, the total laser-textured thickness has been used to calculate the engineering critical current
density, yielding a value of 6.5 106 A/m2 . This value is similar
to previous results obtained in smaller Bi-2212 samples [8].
The effect of applying an external electrical current during
the texturing process has also been checked in 7 mm wide
samples. Two configurations are possible, direct current, where
the direction of the current is from the melt towards the textured
region; and inverse current, in the opposite sense. As it can be
observed in Fig. 4, an applied electrical current of 1 A improves
the alignment of the grains, which results in a 50% increase
of Ic (77 K) values. In the case of the inverse configuration, a
slight reduction of Ic (77 K) was observed. It must be noted
that the electrical resistivity of the as-grown textured region is
2.5 times higher that that of the precursor. As a consequence,
the electrical current does not flow completely through the
crystallization interface. In our case it has ben calculated that
only a 25% of the applied electrical current would affect

Fig. 5. Microstructure of a sample processed with a mass ratio between the


Ba3 Cu5 OX and the Gd-211 phase of (a) 1 and (b) 0.5.

the texturing process. For this reason, this technique will be


more useful to texture superconducting coatings on insulator
substrates. In these cases, the molten zone can cover all the
sample thickness and all the electrical current will pass through
the molten volume.
IV. F IRST R ESULTS ON Gd-123 M ATERIALS
As previously mentioned, in the case of Gd-123 materials
an infiltration approach has been used. This material requires
more energetic processing conditions to be able to induce liquid
phase formation with low enough viscosity to percolate inside
the Gd-211 plate during the characteristic times of the involved
processes. First, the furnace temperature has been increased,
at least up to 650 C. In addition, the laser line scan width
has been reduced to values of the order of 160 mm, which
also reduces the beam steering speeds to values of the order of
12 m/s. Results presented in Fig. 5 show the microstructure of

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IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 25, NO. 3, JUNE 2015

Fig. 6. Small Gd-211 particle inside the Gd-123 grains.

two samples in which the ratio between Ba3 Cu5 Ox and Gd-211
in the precursor was lower than the stoichiometric one. In the
case of Fig. 5(a), a mass ratio of 1 was used while, in the second
one (Fig. 5(b)), this ratio was reduced to 0.5. It is important
to notice that, after laser treatment, the Ba3 Cu5 Ox phase does
not appear in most of the observed samples cross-section, and
only Gd-211 (light grey) and Gd-123 (dark grey) are present.
This shows that, after a laser treatment at 30 mm/h, the liquid
phase has penetrated inside the Gd-211 plate, leading to the
formation of the Gd-123 phase in many regions of the sample.
The composition of these Gd-123 grains is very close to the
stoichiometric one: Ba/Gd = 2.15 0.15 and Cu/Gd = 3.00
0.15. (T ) shows that Tc = 91.5 K, although the transition
is very broad with (T )/(5 K) = 0.5 at T = 69 K. These
samples are multigrained due to the high cooling rates involved
in the process.
As shown in Fig. 5, the main difference between both samples corresponds to the amount and grain size of both phases,
with larger and more abundant Gd-123 grains in the case of the
sample presented in Fig. 5(a). In addition, as presented in Fig. 6,
some small Gd-211 particles, with dimensions lower than
12 m, are also observed inside the Gd-123 grains. Additional
work is underway to determine if it is possible to reduce the
number of cracks that are observed in Figs. 5(a) and 6 by
increasing the temperature, or by modifying laser parameters
accordingly.
V. C ONCLUSION
LZM, performed within a recently patented Laser Furnace
Apparatus [9][11] that allows simultaneous external heating
and sample movement, is demonstrated as a powerful technique to process ceramic superconductors. This method can be
scaled-up to obtain very large samples and its use improves
the temperature homogeneity within the sample, reducing crack
formation.
Laser Furnace LZM has thus been successfully used in the
processing of 4 cm diameter circular Bi-2212 plates, exhibiting
similar superconducting properties than previously published
conventional LZM smaller samples. This technique could yield
significantly improved results in large area samples, when
applied to the processing of superconducting coatings instead
of bulk samples.

This is more evident if an electrical current is applied to


improve the texture reached with LZM. In the case of the
monoliths, where the melted volume only covers a fraction of
the sample thickness, part of the applied current does not flow
through the molten volume and, as a consequence, it is not
employed to improve the texture. In contrast, if the technique is
used to process coatings on insulator substrates, all the current
will flow through the solidification front and the benefits should
be more evident.
The laser furnace method offers similar advantages for
processing Gd-123 samples using infiltration approaches. Although lower processing rates than those used in this work
are required, it is nevertheless possible to obtain significant
amounts of the superconducting phase at 30 mm/h rates. Additional stimuli to induce texture are also required here. This
can be achieved by using an appropriate seed, or by applying
an external electrical current.

ACKNOWLEDGMENT
The authors acknowledge the use of Servicio General de
Apoyo a la Investigacin-SAI, Universidad de Zaragoza.

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