Physica C 323 1999.

107114

Macrosegregation of Y2 BaCuO5 particles in top-seeded melt textured monoliths

M.P. Delamare a , H. Walter b, B. Bringmann c , A. Leenders
a

b,c,)

, H.C. Freyhardt

b,c

Uniersite de Quebec, INRS-Energie et Materiaux, 1650, Bd Lionel Boulet, Varennes, Quebec City, Quebec, Canada b Zentrum fur Funktionswerkstoffe Gottingen, Windausweg 2, D-37073, Gottingen, Germany c Institut fur Materialphysik, Uniersitat Gottingen, Windausweg 2, D-37073, Gottingen, Germany Received 7 July 1999

Abstract Y2 BaCuO5 Y-211. particles distributed in the textured matrix play an important role for the superconducting properties. The Top-Seeded Melt Growth TSMG. process always leads to a macrosegregation of Y-211. For TSMG and Multi-Seeded Melt Growth MSMG. monoliths, the characterization of the distribution of the Y-211 particles was performed over slices in the 001. plane and 001. direction, respectively. As soon as the growth commences, a zone with a low content of less than 10 mol% of Y-211 appears. The low content of Y-211 can mainly be explained by the pushingrtrapping model. This model relates the radii of the smallest trapped Y-211 particles to the growth rate. Furthermore, when the undercooling DT reaches 258C, the growth front stops to push the particles and starts to trap them. q 1999 Elsevier Science B.V. All rights reserved.
PACS: 81.10.Aj; 74.72.Bk; 61.72.Ss Keywords: Melt-textured superconductors; Y-Based cuprates; Pushingrtrapping; Macrosegregation

1. Introduction There is a constant progress since several years to process HTS YBCO superconductors by the TopSeeded Melt Growth TSMG. technique w1x for technological applications. Indeed, this technique is one of the best ways to reduce weak links by a suitable grain enlargement and by growing highly textured materials. Thus, a significant potential for the applications of this material can be envisaged for tiles of
Corresponding author. Institut fur Materialphysik, Universitat Gottingen, Windausweg 2, D-37073, Gottingen, Germany. Tel.: q 49-551-50717-30; fax: q 49-551-50717-50; e-m ail: leenders@umpsun1.gwdg.de
)

the simplest shapes such as those employed for magnetic bearings w2,3x or permanent magnets w4x, to more complex shapes, e.g., for flywheels kinetic energy storage systems. w5,6x or HTS hysteresis motors w7x. The latter requires the joining of two or more single-domain monolith which leads to a high connectivity w8x between them in order to obtain a high intragranular current through the low-angle. grain boundary w9x. In the TSMG process, a seed crystal with a higher melting point than the precursors is placed on the top of a sintered monolith. Single crystalline SmBa 2 Cu 3 O x Sm-123. w10x or NdBa 2 Cu 3 O x Nd123. are usually used as seeds since these compounds have similar lattice structures as YBa 2 Cu 3 O x

0921-4534r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 1 - 4 5 3 4 9 9 . 0 0 4 4 5 - 1

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Y-123.. Besides, Shi et al. w11x have shown that the levitation force can be increased considerably by the use of CdNdAlO4 or SrLaGaO4 seed crystals. The solidification with seeds can be mainly divided into three steps. i. First, the sympathetic nucleation on the five 0014 surfaces except the 001. surface on the top. Indeed the partially molten mixture of 211 q liquid is in contact with an 001. surface at the bottom of the seed and 100.r010. surfaces of the seed crystal due to the surface tension. Thus, five domains can grow from the seed material. ii. A facet deelopment and iii. a continuous growth can take place. Thus, Y-123 grows continuously from the seed crystal over the entire monolith. However, a macrosegregation of Y2 BaCuO5 Y211. particles is induced during the seeded melt growth. Several groups w1214x, e.g., Endo et al. w15x, have argued that this macrosegregation depends on the growth direction and the growth rate R . as a function of undercooling, DT. The understanding of the phenomenon of the Y-211 macrosegregation is crucial for the interpretation of the irreversible superconducting properties. Indeed, the value of the critical current density, Jc , is strongly influenced by the size distribution and the content of the Y-211 particles w1618x. The aim of this study is to determine the distribution of Y-211 particles on many different cross-sections in the 100. and 001. directions in monoliths prepared by the TSMG and the Multi-Seeded Melt Growth MSMG. techniques.

down to 9958C and further down to room temperature in several ramped steps with an average cooling rate of 0.58Crh. For the TSMG, only one Sm seed was placed on the top of the pellet. The temperature profile was the same as the one cited above. The final monoliths were cut either parallel to the c direction or along the ab . plane. These slices were first polished with SiC grinding paper discs and finished with diamond paste. The Y-211 distribution was investigated by Scanning Electron Microscopy SEM. Cambridge Stereoscan 360. coupled with an Energy Dispersive Spectroscopy EDS. analyser Link, Oxford Instrument.. The Y-211 content was evaluated from the EDS data. The measurements were performed over a rectangular area of 100 = 75 mm2 and every millimeter along the width and the height of the slices. Y-123 and Y-211 phases were observed as the two main phases. Furthermore, the size of Y-211 particles in the MSMG monolith was determined with a linear intercept method w21x from SEM photographs.

3. Results 3.1. Characterization of the Y-211 content in the TSMG sample Each side of the seed w010. or 100.x enables the growth of four domains Fig. 1a.. Furthermore, a R 001 growth leads to a fifth domain Fig. 1b.. Thus, a five-domain structure is obtained. The domains are usually separated by boundaries. This structure is commonly called fie-domain leitators w12x. EDS analyses carried out all over the 001. plane reveals the presence of a zone with less than 5 mol% of Y-211 Fig. 2a. hereafter called zone A.. This slice is located ; 1.5 mm beneath the seed. On the other hand, the average content of Y-211 in the rest of the sample corresponds to 2530 mol% hereafter called zone B.. A second slice ; 3 mm beneath the seed exhibits the same distribution of the Y-211 content. However, the size of the zone A is increased Fig. 2b.. Consequently, this zone grows from the seed and pushes the Y-211 particles in the 001. and the 010.r100. directions. Besides, transport measurements already shown in a previous paper by Walter et al. w22x were performed in the zone A.

2. Experimental details The precursors for the melt-texturing process were supplied by Aventis Research and Technologies. The precursors were square shaped with dimensions of 40 = 40 = 14. mm3 and possessed a composition of YBa 2 Cu 3 O 7yx Y-123. q 25 mol% Y2 O 3 q 1 wt.% CeO 2 . The seed crystals were cut from melt-textured SmBa 2 Cu 3 O 7yx Sm-123. monoliths w10x. For the MSMG w8,19,20x, four Sm-123 seeds were placed on top of the square-shaped monolith. The whole arrangement was heated up to 10438C in a box furnace in order to ensure a good peritectic decomposition. Then, the sample was rapidly cooled

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seeds, exhibit a 001. orientation right through each domain. The five-domain levitator structure does not appear. However, EDS analyses reveal the presence of a zone with a low content of Y-211 on each side of the grain boundary Fig. 3.. Indeed, the zone grown from the seed-crystal exhibits the lowest content of Y-211 particles zone A. i.e., less than 8 mol%. After 8 mm in depth, Y-211 particles are stopped to be pushed by the growth front. Thus, the Y-211 content is increased up to 36 mol%. In contrast on each side of the zone A, the Y-211 content ranges from 20 to 30 mol% Fig. 3a.. In this way, the analyse of the Y-211 content points out a five-domain levitator-like growth.

Fig. 1. Schematic drawing of the five-domain levitator morphology a. in the 001. plane and b. along the 001. direction. The five domains are separated by grain boundaries.

Surprisingly, the measurements exhibit to our knowledge one of the best values of the critical current density of 1.3 = 10 5 Arcm2 at 77 K. EDS analyses performed on grain boundaries which separate the five domains Fig. 1., reveal no segregation of Y-211 particles. The content of Y-211 is either less than 5 mol% or approximately 25 mol% according to the location of the zones A or B. On the other hand, a certain amount of porosity mostly located in the center of the slices can be observed. This location corresponds to the zone A. The mean size of the pores is of the order of 47 mm w22x. 3.2. Characterization of the Y-211 content in the MSMG sample The MSMG monolith already described elsewhere w8x seems not to exhibit the fie-domain leitators structure. The four domains grown from the four

Fig. 2. EDS analyses performed in the 001. plane of the TSMG monolith. a. The slice located just ;1.5 mm beneath the Sm seeds, exhibits the lowest content of Y-211, i.e., less than 5 mol% visualized in grey. In contrast, the zone B depicts a content of order of 30 mol%. b. The second slice is located at ; 3 mm beneath the seed.

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Fig. 4. Schematic drawing of the zone A of a fie-domain leitator. Due to its conic shape this zone tends to vanish near the edge of the sample.

high or low content of Y-211 inclusions can be easily observed, respectively.

Fig. 3. EDS analyses performed in the 001. direction of the MSMG monolith. a. The slice is located at the position of the two Sm seeds. b. The second slice is 4 mm away from cut a.. c. The third slice is near the edge of the monolith. The zone A -8 mol%. is visualized in grey while the zone B 3035 mol%. is shown in white.

Four millimeters away from the last slice toward the edge of the monolith, the Y-211 content keeps the same distribution. However, as shown in Fig. 3b, the size of the zone A tends to decrease due to the conic shape of the zone A Fig. 4.. This feature is more obvious for the slice located near the edge of the monolith as depicted in Fig. 3c. The zone A appears and vanishes at 4 and 8 mm, respectively. Fig. 5 exhibits an example of the textured matrix of the zone A Fig. 5a. and the zone B Fig. 5b.. The

Fig. 5. SEM micrographs of a. the zone A in which a high content of Y-211 particles can be observed and b. the zone B in which the Y-211 content is strongly decreased.

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Fig. 6. Size distribution of Y-211 particles in the textured matrix of one of the slices of the MSMG monolith cf. Fig. 3c.. The dashed lines delimit the zone A.

Consequently, zone A corresponds to the R 001. growth whereas on each side of this zone, the growth is of R 100.rR 010. growth type. The Y-211 particles are pushed in the 001. direction up to a distance of 8 mm from the seed. The pushing of the Y-211 particles in the 100.r010. directions seems to follow a different behavior. Furthermore, the distribution of the pore size is similar to that of the previously investigated samples. The presence of the porosity is closely related to the low content of Y-211. Indeed, the distribution of the porosity reflects the shape of the zone A. Furthermore, some cracks between the Y-123 platelets are present throughout zone A pointing out a low density of this region Fig. 5b.. The size distribution of the Y-211 particles was determined by averaging of the particle size for an area of 50 = 35. mm2 from SEM photographs. This study was performed in steps of 1 mm for the slice depicted in Fig. 3c. The size distribution follows a bell shaped curve. The mean size amounts to 0.51 mm for the zone B. In contrast, the mean particle size rises to 2 mm for the zone A Fig. 6..

interface. Thus, yttrium diffuses toward the interface where it is consumed by the growth. The compositional difference in the liquid at the liquidrY-211 and liquidrY-123 interfaces leads to driving forces for the solute diffusion of yttrium. The occurrence of the driving forces is explained by the curvature of the Y-211 particles DCr i.e., liquidrY-211 interface., the effect of undercooling at the interfaces DCDT i.e., liquidrY-123 interface. and the effect of the temperature gradient DCG . The yttrium diffusion caused by such an interface undercooling is assumed to be the rate limiting factor for the growth of the Y-123 phase Fig. 7.. In addition, the interface kinetics is also considered to be an important factor in determining the growth of Y-123. A crystal growth with faceted interface needs a driving force, such as the undercooling. The value of the undercooling not only influences the value of the growth rate but also the distribution of Y-211 particles in the textured matrix. The macrosegregation of Y-211 particles can partly be explained by the close relationship between the growth rate R and the undercooling DT. According to the growth mechanism proposed by Cima et al. w23x, the undercooling, DTp , for a plane front solidification can be written as: DTp s Rl Dl
123 P CS y C L . y

Gl

m123 m 211 l l

m 211 m211 y m123 l l l

, 1.

with DTp s t q DT0 where 1.4 = 10y4 Krs. is the cooling rate, t the time and DT0 is the initial

4. Discussion Several groups w23,24x have proposed different growth models to clarify the growth mechanism of Y-123 crystals from the partially molten state Y-211 q liquid.. To summarize, the Y-211 particles dissolve into the liquid in the region just ahead of the liquidrY-123

Fig. 7. Schematic phase diagram of the yttrium concentration w19x.

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undercooling namely 158C in our case. G 1000 Krm. is the thermal gradient, R the growth rate, l 10y6 m. the distance between a Y-211 particle and the Y-123 growth front, D l 10y7 cm2rs. w23x the 123 diffusivity of yttrium in the liquid, CS 9.4 = 10y3 P 3. molrcm the concentration of yttrium in Y-123, C L y4 3. 3.2 = 10 molrcm the concentration of yttrium in the liquid at the peritectic temperature, m123 1.6 l = 10 5 K cm3rmol. the equilibrium liquidus Y-123 slope and m211 4.3 = 10 5 K cm3rmol. the l metastable liquidus Y-211 slope. In the MSMG monolith, the pushing of Y-211 particles by the growth front of zone A stops in a depth of 8 mm. According to the relationship 1., this depth corresponds to an undercooling DT of approximately 258C. This result is in good agreement with the conclusion of the study of Endo et al. w15x. They have established that the value of DTc s 308C is a threshold undercooling. Below this value, R 001 is lower than R 100 whereas above DTc , R 001 is higher than R 100 . This difference of growth rate leads to a macrosegregation phenomenon. However, the close relationship between the growth rate and the undercooling is not sufficient to explain the macrosegregation. The interaction of the advancing solidliquid interfaces and the particles in the melt w2527x must be taken into account. Two kinds of forces can act on the particles. The first one is a long-range repulsie force, K n , which is considered to be a Van der Waals force in the model proposed by Potschke and Rogge w27x. The particle can be accelerated until it is finally swept ahead of the liquidsolid interface Fig. 8a.. The second one corresponds to a drag force, K n , which is exerted by the particle on the migrating solid liquid interface Fig. 8b.. This force is due to the viscous flow around the particle: 6ph Rr l
2

Fig. 8. Schematic drawing of the pushingrtrapping mode. a. K n - K r leads to the pushing mode whereas b. K n ) K r leads to the trapping mode. The length of the arrows is proportional to the strength of the forces.

the drag force becomes higher than K r leading to the entrapment of the particle. However, according to Eq. 3., the entrapment also depends on the number of particles in the vicinity of the solidliquid interface clearly shown in Eq. 3.. If the liquidsolid interface is in contact with an amount of 2 rNv particles, where Nv is the number of particles per unit volume, the drag force, Pd , per unit area of interface is given by: Pd s 2p r 2 Nv a 2p r 2 R l .

3.

Kn s

2.

where h is the melt viscosity, r the particle radius, R the growth rate and l the distance of the particle from the liquidsolid interface. In addition, a critical growth rate R c must be considered. This rate is inversely proportional to the particle radius. When the growth rate is higher than the critical growth rate

Nv can be considered to be inversely proportional to the distance, l, of the particle from the liquidsolid interface. To summarize, the drag force K n involves three important parameters, namely the particle radius, the growth rate and the number of particles per unit volume in the vicinity of the growth front. According to the microstructure of the zones A and B, two critical growth conditions can be considered. i. When 158C F DT F 258C, both growth rate and Nv exhibit a low value. Consequently, fulfilling the

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Fig. 9. Evolution of the growth rate R full circles. and the viscous drag force full triangles. vs. the distance from the upper part of the slice in the 001. direction. The dashed line indicates the beginning of trapping of the Y-211 particles.

trapping condition K n ) K r , only the largest particles can be trapped. ii. On the contrary, for DT G 258C, the undercooling is increased leading to an increase of the growth rate. Therefore, the growth rate has reached a new critical value corresponding to a new critical particle radius. Thus, also the smallest particles can be trapped. This trapping behavior is in good agreement with the model proposed by Bolling and Cisse w26x. They have clearly estab lished that the radii of the smallest trapped particles inversely evolves as a function of the growth rate R. At the same time, the drag force is enhanced by the increase of the number of particles in the vicinity of the growth front Eq. 3... Fig. 9 depicts two curves from empiric calculations of the growth rate Eq. 1.. and the viscous drag force Eq. 2.. in order to correlate these two values. It is emphasized that the trapping mode occurs as soon as the viscous drag force increases. In contrast, along the 100.r010. growth direction, the critical value continuously evolves according to the undercooling. Indeed, the increase of the undercooling leads to a continuous increase of the critical growth rate inducing the conical morphology of the zone A. The low content of Y-211 in the zone A leads to a lowered density of the textured matrix due to the

presence of cracks between Y-123 platelets and the spherical pores. Several groups w2830x have claimed that the increase of the volume fraction of Y-211 leads to a decrease of the platelet thickness. Furthermore, Y-123rY-211 composite samples with small Y-211 particles in the textured matrix do not exhibit planar defects such as microcracks w28,30x. Finally, the presence of spherical pores is mainly due to gas evolution during the melt processing. The gas is trapped within the liquid and formes spherical pores or bubbles.

5. Conclusion To summarize, the TSMG and MSMG processes lead to the growth of zones with a content of Y-211 less than 10 mol%. These zones are closely connected to a certain amount of spherical pores and cracks between the Y-123 platelets. This kind of microstructure was mainly explained by a pushingr trapping model which relates the radii of the smallest trapped Y-211 particles to the growth rate of the Y-123 phase. However, Walter et al. w22x have, to our knowledge, achieved with 1.3 = 10 5 Arcm2 at 77 K one of the best values of the critical current density in TSMG YBCO even though the measured

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M.P. Delamare et al.r Physica C 323 (1999) 107114 w11x D. Shi, K. Lahari, J.R. Hull, D. Leblanc, M.A.R. Leblanc, A. Dabkowski, Y. Chang, Y. Liang, Z. Zhang, H. Fan, Physica C 246 1995. 253. w12x P. Diko, V.R. Todt, D.J. Miller, K.C. Goretta, Physica C 278 1997. 192. w13x Y. Nakamura, A. Endo, Y. Shiohara, J. Mater. Res. 11 1996. 1094. w14x A. Endo, S.H. Chauhan, T. Egi, Y. Shiohara, J. Mater. Res. 11 1996. 795. w15x A. Endo, S.H. Chauhan, Y. Nakamura, Y. Shiohara, J. Mater. Res. 11 1996. 1114. w16x M.P. Delamare, M. Hervieu, J. Wang, J. Provost, I. Monot, K. Verbist, G. Van Tendeloo, Physica C 262 1996. 220. w17x A. Leenders, M. Ullrich, H.C. Freyhardt, presented at the ASC 98, accepted for publication in IEEE Trans. Appl. Supercond. w18x N. Vilalta, F. Sandiumenge, S. Pinol, X. Obradors, J. Mater. Res. 12 1997. 38. w19x S. Schaetzle, G. Krabbes, G. Stoever, G. Fuchs, D. Schlaefer, Supercond. Sci. Technol. 1998. preprint. w20x M. Ullrich, A. Leenders, H.C. Freyhardt, J.H. Albering, S. Gauss, Inst. Phys. Conf. Ser. 158 1997. 1033. w21x Kingery, Bowen, Ulhmann, Wiley-Interscience, 2nd edn., p. 523. w22x H. Walter, M.P. Delamare, B. Bringmann, A. Leenders, H.C. Freyhardt, submitted to J. Mater. Res. w23x J.M. Cima, M.C. Flemings, A.M. Figueredo, M. Nakade, H. Ishii, H.D. Brody, S. Haggerty, J. Appl. Phys. 72 1992. 179. w24x Y. Nakamure, Y. Shiohara, J. Mater. Res. 11 1996. 2450. w25x D.R. Uhlmann, B. Chalmers, A. Jackson, J. Appl. Phys. 35 1964. 2986. w26x G.F. Bolling, J. Cisse, J. Cryst. Growth 10 1971. 56. w27x J. Potschke, V. Rogge, J. Cryst. Growth 94 1989. 726. w28x P. Mc Ginn, W. Chen, N. Zhu, M. Lanagan, U. Balachandran, Appl. Phys. Lett. 57 1990. 1455. w29x R.L. Meng, Y.Y. Sun, P.H. Hor, C.W. Chu, Physica C 179 1991. 149. w30x P. Diko, W. Gawalek, T. Habisreuther, T. Klupsch, P. Gornert, Phys. Rev. B 52 1995. 13658.

material exhibits the lowest content of Y-211. Thus, the control of the pushingrtrapping phenomenon will allow one to avoid the Y-211 macrosegregation phenomenon and to improve the superconducting properties of top-seeded melt grown Y-123 HTS.

Acknowledgements This work was supported by TMR program of the EU under contract N ERBFMRXC98-0189.

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