Beruflich Dokumente
Kultur Dokumente
3, JUNE 2015
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I. I NTRODUCTION
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
1051-8223 2014 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
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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
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
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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.
ACKNOWLEDGMENT
The authors acknowledge the use of Servicio General de
Apoyo a la Investigacin-SAI, Universidad de Zaragoza.
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