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Physica C 323 Ž1999.


Macrosegregation of Y2 BaCuO5 particles in top-seeded melt textured monoliths
M.P. Delamare a , H. Walter b, B. Bringmann c , A. Leenders


, H.C. Freyhardt


UniÕersite 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, UniÕersitat Gottingen, Windausweg 2, D-37073, Gottingen, Germany ¨ ¨ ¨ ¨ Received 7 July 1999

Abstract Y2 BaCuO5 ŽY-211. particles distributed in the textured matrix play an important role for the superconducting properties. The Top-Seeded Melt Growth ŽTSMG. process always leads to a macrosegregation of Y-211. For TSMG and Multi-Seeded Melt Growth ŽMSMG. monoliths, the characterization of the distribution of the Y-211 particles was performed over slices in the Ž001. plane and Ž001. 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 ŽTSMG. 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:

the simplest shapes such as those employed for magnetic bearings w2,3x or permanent magnets w4x, to more complex shapes, e.g., for flywheels Žkinetic 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 Žlow-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 ŽSm-123. w10x or NdBa 2 Cu 3 O x ŽNd123. 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 Ž 9 9 . 0 0 4 4 5 - 1

.20x. The solidification with seeds can be mainly divided into three steps. and Ž001. Y-123 grows continuously from the seed crystal over the entire monolith. a macrosegregation of Y2 BaCuO5 ŽY211. Jc . particles is induced during the seeded melt growth. Besides. Thus. plane. Žhereafter called zone A. 3 mm beneath the seed exhibits the same distribution of the Y-211 content. DT. The measurements were performed over a rectangular area of 100 = 75 mm2 and every millimeter along the width and the height of the slices. Consequently. surfaces of the seed crystal due to the surface tension.. Indeed the partially molten mixture of 211 q liquid is in contact with an Ž001. 1b.. w11x have shown that the levitation force can be increased considerably by the use of CdNdAlO4 or SrLaGaO4 seed crystals.19. and the Ž010. Y-123 and Y-211 phases were observed as the two main phases. A second slice . For the MSMG w8. This slice is located . 2b.. surface at the bottom of the seed and Ž100. The understanding of the phenomenon of the Y-211 macrosegregation is crucial for the interpretation of the irreversible superconducting properties. the average content of Y-211 in the rest of the sample corresponds to 25–30 mol% Žhereafter called zone B. techniques. Endo et al. the size of the zone A is increased ŽFig. monoliths w10x. EDS analyses carried out all over the Ž001. The seed crystals were cut from melt-textured SmBa 2 Cu 3 O 7yx ŽSm-123. 2a. The final monoliths were cut either parallel to the c direction or along the Ž ab . 3. The whole arrangement was heated up to 10438C in a box furnace in order to ensure a good peritectic decomposition. transport measurements already shown in a previous paper by Walter et al.rŽ100. this zone grows from the seed and pushes the Y-211 particles in the Ž001. the size of Y-211 particles in the MSMG monolith was determined with a linear intercept method w21x from SEM photographs. the value of the critical current density.5 mm beneath the seed. w22x were performed in the zone A. a continuous growth can take place.r Physica C 323 (1999) 107–114 ŽY-123.1. a five-domain structure is obtained. mm3 and possessed a composition of YBa 2 Cu 3 O 7yx ŽY-123. This structure is commonly called fiÕe-domain leÕitators w12x. e. Indeed. only one Sm seed was placed on the top of the pellet. directions.P. Experimental details The precursors for the melt-texturing process were supplied by Aventis Research and Technologies. However. The Y-211 content was evaluated from the EDS data. or Ž100. 1a. the sample was rapidly cooled .58Crh. Oxford Instrument. 2. ŽCambridge Stereoscan 360. Thus. directions in monoliths prepared by the TSMG and the Multi-Seeded Melt Growth ŽMSMG. plane reveals the presence of a zone with less than 5 mol% of Y-211 ŽFig. down to 9958C and further down to room temperature in several ramped steps with an average cooling rate of 0. The temperature profile was the same as the one cited above. Furthermore. five domains can grow from the seed material.g.. Thus. 1.% CeO 2 . Then. First.. Besides. surface on the top. the sympathetic nucleation on the five Ä 0014 surfaces except the Ž001. The domains are usually separated by boundaries. On the other hand. A facet deÕelopment and Žiii. The aim of this study is to determine the distribution of Y-211 particles on many different cross-sections in the Ž100.x enables the growth of four domains ŽFig. The Y-211 distribution was investigated by Scanning Electron Microscopy ŽSEM. Žii.. Furthermore. Delamare et al. w15x. For the TSMG.rŽ010. The precursors were square shaped with dimensions of Ž40 = 40 = 14. four Sm-123 seeds were placed on top of the square-shaped monolith. q 25 mol% Y2 O 3 q 1 wt. a R 001 growth leads to a fifth domain ŽFig.. Characterization of the Y-211 content in the TSMG sample Each side of the seed wŽ010. is strongly influenced by the size distribution and the content of the Y-211 particles w16–18x. Shi et al. Results 3. coupled with an Energy Dispersive Spectroscopy ŽEDS. Ži. Several groups w12–14x. as a function of undercooling. analyser ŽLink. have argued that this macrosegregation depends on the growth direction and the growth rate Ž R . However. These slices were first polished with SiC grinding paper discs and finished with diamond paste.108 M.

The slice located just .. Surprisingly. Characterization of the Y-211 content in the MSMG sample The MSMG monolith already described elsewhere w8x seems not to exhibit the fiÕe-domain leÕitators structure. In contrast on each side of the zone A.r Physica C 323 (1999) 107–114 109 seeds. The mean size of the pores is of the order of 47 mm w22x.e. direction. exhibit a Ž001. On the other hand. In this way..M. The five-domain levitator structure does not appear. Žb. the zone B depicts a content of order of 30 mol%. Thus. Fig. 3. 2. the analyse of the Y-211 content points out a five-domain levitator-like growth. Indeed. 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. 3. the measurements exhibit to our knowledge one of the best values of the critical current density of 1. a certain amount of porosity mostly located in the center of the slices can be observed. 3 mm beneath the seed. EDS analyses reveal the presence of a zone with a low content of Y-211 on each side of the grain boundary ŽFig.2. 1. plane and Žb. along the Ž001.1. In contrast. EDS analyses performed on grain boundaries which separate the five domains ŽFig. Delamare et al. plane of the TSMG monolith. The five domains are separated by grain boundaries. After 8 mm in depth. i. less than 8 mol%. 3a. the Y-211 content ranges from 20 to 30 mol% ŽFig. orientation right through each domain. Schematic drawing of the five-domain levitator morphology Ža. EDS analyses performed in the Ž001..P. in the Ž001. reveal no segregation of Y-211 particles.3 = 10 5 Arcm2 at 77 K. .5 mm beneath the Sm seeds. This location corresponds to the zone A. Ža.e. The second slice is located at .. The four domains grown from the four Fig. less than 5 mol% visualized in grey. 1. Y-211 particles are stopped to be pushed by the growth front. However. the zone grown from the seed-crystal exhibits the lowest content of Y-211 particles Žzone A.. i. exhibits the lowest content of Y-211. the Y-211 content is increased up to 36 mol%.

The zone A Ž -8 mol%. This feature is more obvious for the slice located near the edge of the monolith as depicted in Fig. Schematic drawing of the zone A of a fiÕe-domain leÕitator. 5 exhibits an example of the textured matrix of the zone A ŽFig.. the zone B in which the Y-211 content is strongly decreased. The third slice is near the edge of the monolith. Fig. respectively. SEM micrographs of Ža.r Physica C 323 (1999) 107–114 Fig. 4. Žb. 3. is visualized in grey while the zone B Ž30–35 mol%.P. Delamare et al. is shown in white. 4. as shown in Fig. However. respectively. The zone A appears and vanishes at 4 and 8 mm. The second slice is 4 mm away from cut Ža.. 3b. 5b. 5. . Ža.110 M. 3c. Due to its conic shape this zone tends to vanish near the edge of the sample. the Y-211 content keeps the same distribution. The slice is located at the position of the two Sm seeds. The Fig. high or low content of Y-211 inclusions can be easily observed. Fig. and the zone B ŽFig. the size of the zone A tends to decrease due to the conic shape of the zone A ŽFig. 5a. direction of the MSMG monolith. the zone A in which a high content of Y-211 particles can be observed and Žb.. EDS analyses performed in the Ž001. Žc. Four millimeters away from the last slice toward the edge of the monolith.

the distribution of the porosity reflects the shape of the zone A. Furthermore. Size distribution of Y-211 particles in the textured matrix of one of the slices of the MSMG monolith Žcf.M. The Y-211 particles are pushed in the Ž001. To summarize. yttrium diffuses toward the interface where it is consumed by the growth. Fig. the distribution of the pore size is similar to that of the previously investigated samples.... with DTp s ´ t q DT0 where ´ Ž1. Ž 1. liquidrY-123 interface. Schematic phase diagram of the yttrium concentration w19x. 3c. The size distribution of the Y-211 particles was determined by averaging of the particle size for an area of Ž50 = 35.5–1 mm for the zone B. 6. . w23x. zone A corresponds to the R Ž001. According to the growth mechanism proposed by Cima et al. 7.r Physica C 323 (1999) 107–114 111 Fig. The size distribution follows a bell shaped curve. The macrosegregation of Y-211 particles can partly be explained by the close relationship between the growth rate R and the undercooling DT. the interface kinetics is also considered to be an important factor in determining the growth of Y-123. the mean particle size rises to 2 mm for the zone A ŽFig. Consequently. some cracks between the Y-123 platelets are present throughout zone A pointing out a low density of this region ŽFig.24x have proposed different growth models to clarify the growth mechanism of Y-123 crystals from the partially molten state ŽY-211 q liquid. is the cooling rate. Delamare et al. direction up to a distance of 8 mm from the seed. The dashed lines delimit the zone A. 7. In contrast. growth whereas on each side of this zone. 3c. the Y-211 particles dissolve into the liquid in the region just ahead of the liquidrY-123 Fig. Indeed.. liquidrY-211 interface..rR Ž010. The compositional difference in the liquid at the liquidrY-211 and liquidrY-123 interfaces leads to driving forces for the solute diffusion of yttrium. 6.e. The mean size amounts to 0.4 = 10y4 Krs.rŽ010. 5b. directions seems to follow a different behavior. Thus. for a plane front solidification can be written as: DTp s Rl Dl 123 P Ž CS y C L . The pushing of the Y-211 particles in the Ž100.. growth type. In addition. DTp . interface. the undercooling. A crystal growth with faceted interface needs a driving force. mm2 from SEM photographs.e. 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. Furthermore. the effect of undercooling at the interfaces DCDT Ži. t the time and DT0 is the initial 4. The presence of the porosity is closely related to the low content of Y-211. 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 ŽFig. such as the undercooling. The occurrence of the driving forces is explained by the curvature of the Y-211 particles DCr Ži. the growth is of R Ž100.P.. Discussion Several groups w23. y Gl m123 m 211 l l m 211 m211 y m123 l l l . This study was performed in steps of 1 mm for the slice depicted in Fig.

D l Ž10y7 cm2rs. R the growth rate and l the distance of the particle from the liquid–solid interface. where h is the melt viscosity. namely the particle radius. the l metastable liquidus Y-211 slope. the entrapment also depends on the number of particles in the vicinity of the solid–liquid interface clearly shown in Eq. molrcm the concentration of yttrium in Y-123. R 001 is lower than R 100 whereas above DTc . both growth rate and Nv exhibit a low value. the close relationship between the growth rate and the undercooling is not sufficient to explain the macrosegregation. This result is in good agreement with the conclusion of the study of Endo et al. Consequently. Ž 3. fulfilling the . R 001 is higher than R 100 .3 = 10 5 K cm3rmol.r Physica C 323 (1999) 107–114 undercooling namely 158C in our case. the drag force K n involves three important parameters. two critical growth conditions can be considered. Ž3. where Nv is the number of particles per unit volume. The first one is a long-range repulsiÕe force. which is exerted by the particle on the migrating solid– liquid interface ŽFig.. w15x. When 158C F DT F 258C. K n . which is considered to be a Van der Waals force in the model proposed by Potschke and Rogge w27x.. Two kinds of forces can act on the particles. per unit area of interface is given by: Pd s 2p r 2 Nv a 2p r 2 R l . CS Ž9. 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. w23x the 123 diffusivity of yttrium in the liquid. The interaction of the advancing solid–liquid interfaces and the particles in the melt w25–27x must be taken into account. Ž3. R the growth rate. This rate is inversely proportional to the particle radius. They have established that the value of DTc s 308C is a threshold undercooling. l. 8a. To summarize. K n . If the liquid–solid interface is in contact with an amount of 2 rNv particles. Below this value. Ž 2. However. Ža. C L y4 3. the drag force. When the growth rate is higher than the critical growth rate Nv can be considered to be inversely proportional to the distance.P.6 l = 10 5 K cm3rmol. the distance between a Y-211 particle and the Y-123 growth front. this depth corresponds to an undercooling DT of approximately 258C. the pushing of Y-211 particles by the growth front of zone A stops in a depth of 8 mm. 8b. K n ) K r leads to the trapping mode.K r leads to the pushing mode whereas Žb.2 = 10 molrcm the concentration of yttrium in the liquid at the peritectic temperature.. 8.4 = 10y3 P 3. Ž3. l Ž10y6 m. Ži. The ¨ particle can be accelerated until it is finally swept ahead of the liquid–solid interface ŽFig. of the particle from the liquid–solid interface. This difference of growth rate leads to a macrosegregation phenomenon. The second one corresponds to a drag force. r the particle radius. the growth rate and the number of particles per unit volume in the vicinity of the growth front. According to the relationship Ž1. Pd . According to the microstructure of the zones A and B. This force is due to the viscous flow around the particle: 6ph Rr l 2 Fig. Schematic drawing of the pushingrtrapping mode. Kn s . G Ž1000 Krm..112 M. the equilibrium liquidus Y-123 slope and m211 Ž4. is the thermal gradient. In addition. K n .. m123 Ž1. However. Delamare et al. In the MSMG monolith. according to Eq. a critical growth rate R c must be considered.

Evolution of the growth rate R Žfull circles. trapping condition K n ) K r .r Physica C 323 (1999) 107–114 113 Fig. the drag force is enhanced by the increase of the number of particles in the vicinity of the growth front ŽEq. the presence of spherical pores is mainly due to gas evolution during the melt processing. the undercooling is increased leading to an increase of the growth rate. the critical value continuously evolves according to the undercooling. to our knowledge. The gas is trapped within the liquid and formes spherical pores or bubbles. Ž1. in order to correlate these two values. for DT G 258C.30x. the TSMG and MSMG processes lead to the growth of zones with a content of Y-211 less than 10 mol%. However.. only the largest particles can be trapped. Furthermore.P. growth direction. 5. 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.rŽ010. also the smallest particles can be trapped. the distance from the upper part of the slice in the Ž001. achieved with 1. and the viscous drag force Žfull triangles. Ž2.. Finally. Therefore. the growth rate has reached a new critical value corresponding to a new critical particle radius.M. w22x have. vs. direction. Žii. 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 dashed line indicates the beginning of trapping of the Y-211 particles. Ž3. This trapping behavior is in good agreement with the model proposed by Bolling and Cisse w26x. and the viscous drag force ŽEq. Thus. On the contrary. In contrast. 9. Y-123rY-211 composite samples with small Y-211 particles in the textured matrix do not exhibit planar defects such as microcracks w28. 9 depicts two curves from empiric calculations of the growth rate ŽEq.. Conclusion To summarize. Several groups w28–30x have claimed that the increase of the volume fraction of Y-211 leads to a decrease of the platelet thickness. along the Ž100. 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. Delamare et al. Walter et al.3 = 10 5 Arcm2 at 77 K one of the best values of the critical current density in TSMG YBCO even though the measured .. At the same time. It is emphasized that the trapping mode occurs as soon as the viscous drag force increases. Fig. They have clearly estab´ lished that the radii of the smallest trapped particles inversely evolves as a function of the growth rate R.

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