Magnetic properties of polycrystalline KClO3 -doped Y(1 0:2x)Ba(2 0:2x)Kx Cu3 Oy (x = 0 0.40) superconductors Michael R. Koblischka, Anjela Veneva, and Masato Murakami Superconductivity Research Laboratory, Internarional Superconductivity Technology Center 16-25 Shibaura 1-chome, Minato-ku, Tokyo 105-0023, Japan The eect of KClO3 -addition on the magnetic properties of polycrystalline hightemperature superconductors with nominal composition Y(1 0:2x) Ba(2 0:2x) Kx Cu3 Oy (x = 0 0.40) was investigated. DC susceptibility as function of temperature was measured in eld-cooled cooling and eld-cooled warming modes in magnetic elds in the range 10 mT 0 Ha 7 T on KClO3 -doped and pure YBCO samples. From the Meissner curves measured at a eld of 10 mT, we deduce that the samples are single-phase. However, the low-temperature behaviour of the samples with KClO3 additions at large applied elds is dierent from pure YBCO. Abstract: Key words: YBCO HTSC, KClO3 -addition, magnetic properties, ux pinning INTRODUCTION Investigating the inuence of the dierent additions on the magnetic and electrical properties and microstructure of the high-Tc superconductors (HTSC) is of interest, as much for the understanding of the intergranular phenomena, as for solving technological problems. A special interest is associated with doping of YBa2 Cu3 O7 Æ (YBCO) superconducting materials by alkali-chlorinecontaining additions, which improve the superconducting properties [1{4]. A Tc of 96 K has been observed for Y1 Ba2 x Kx Cu3 Oy samples (x = 0.2) with KCl [4]. The aim of this work is to investigate the eect of KClO3 -addition on the magnetic properties of polycrystalline YBCO HTSC. Here, we present eld-cooled cooling (FCC) and -warming (FCW) measurements of KClO3 -doped and pure YBCO HTSC in magnetic elds up to 7 T. EXPERIMENTAL Polycrystalline KClO3 -doped YBCO high-temperature superconductors (HTSC) with nominal composition Y(1 0:2x) Ba(2 0:2x) Kx Cu3 Oy (x = 0 0.40) were synthesized by a solid state reaction in air [3]. Powders of Y2 O3 , BaCO3 , CuO, all with a purity 99.99 % and KClO3 (more than 99.9 %), were mixed, pressed into pellets and heated at 880 Æ C for 24 h. The reacted pellets were reground, pressed again and sintered at 915 Æ C for 20 h. They were annealed at 600 Æ C for 14 h, before being cooled to room temperature. A detailed study on the thermal behavior of the samples was performed by dierential thermal analysis (DTA) on the starting mixtures. The phase content, microstructure and morphology of the crystalline grains were characterized using X-ray powder diraction (XRD) and scanning electron microscopy (SEM) coupled with an electron probe microanalyzer (EPMA). Temperature scans in both FCC and FCW modes were carried out in various elds between 10 mT and 7 T. The measurements were performed in a commercial SQUID magnetometer (Quantum Design model XL), enabling to measure in a continuous temperature sweep mode with a controlled temperature sweep rate dT=dt = 35 mK/min; the datapoints are recorded in steps of 50 mK in (a) (b) 0 -1 YBCO pure 7T χ DC [10 χ DC [10 -3 ] -3 ] 0 -2 6T 7T 5T 6T 4T 5T 3T 4T 3T 2T 1T 0.5 T 2T -4 1T 0.5 T -2 YBCO doped 20 40 60 80 100 120 T [K] 20 40 60 80 100 120 T [K] Fig. 1. (a): Temperature scans (FCC) of the DC susceptibility DC of a pure YBCO sample in applied elds between 0.1 T and 7 T; the FCW data are omitted for clarity. Note that all curves are monotonuous in contrast to NdBa2 Cu3 O7 Æ crystals [5] in all applied elds. Further, at low temperatures there is an upturn of DC due to the paramagnetic contribution of Cu. (b): The same experiments on the KClO3 doped sample with x = 0.30. Again, all curves are monotonous, but at low T , their behaviour is dierent from the pure sample as marked by arrows. the transition region. All DC (T ) curves are measured between 1.7 K and 120 K. Note that the temperature sweep is not halted for taking a datapoint as in a conventional SQUID magnetometer. No averaging of the signal is performed, and the scan length is 1 cm. This procedure ensures a large number of datapoints even in a sharp superconducting transition. More details of the measurement procedure are given by Koblischka et al. [5]. RESULTS AND DISCUSSION After the second heat treatment the XRD data showed that in all cases the KClO3 -doped samples are pure 123 phase materials with only an indication of traces of CuO for the sample with x = 0.40. We would like to emphasize that the X-ray diraction patterns of the doped samples do not contain any such extra lines within the detection limit of the X-ray method (normally the detection limit of XRD for impurities is estimated around 4-5 %, so it is not possible to detect minor impurities). And, no chlorine or other impurity phases related with chlorine or potassium are found in the KClO3 -doped samples. We have carried out detailed microstructural studies and SEM-EPMA revealed traces of potassium and chlorine in the grain boundaries of the samples with addition [3]. The values of the lattice parameters of KClO3 -doped samples are comparable to the data published for the desired YBCO orthorhombic structure [6]. The inuence of KClO3 on the superconducting properties depends on the concentration of the addition in the initial batch. AC susceptibility data of these samples are given by Veneva et al. [3]. The grain size of the pure YBCO sample is 28 m; that of the KClO3 -doped samples 40 m. In Fig. 1 (a), DC of the pure YBCO sample is plotted for various applied elds; in (b) the same experiment is shown for the KClO3 -doped sample with x = 0.30. All DC curves are monotonous, and no secondary step in the transitions can be observed in elds above 4 T as in some YBCO single crystals and all NdBa2 Cu3 O7 Æ samples investigated in a similar way [5]. This demonstrates that the polycrystalline YBCO samples with their relatively small grains do not contain oxygen vacancy clusters providing a spatial distribution of Tc , in contrast to bulk samples. At low temperatures (T < 15 K), all FCC curves of the pure sample exhibit a clear upturn of the DC curves, which is due to the paramagnetic moment of Cu2+ . These are located in the Cu-O-chains [7], and their number depends on the oxygenation state. In stark contrast to this behaviour, the doped sample in (b) exhibits a downturn of the FCC/FCW curves towards more negative (= diamagnetic) values, which develops with increasing applied eld. This may point to a change in the copper valence, or, more likely, to the fact that the grain boundary regions become more strongly superconducting. In case that the coupling strength of the grains increases, shielding currents can ow on a larger length scale [8], which results in an increased diamagnetic signal. This latter explanation is in accordance with previous results obtained from AC susceptibility studies [3], where it was concluded that the KClO3 addition leads to a modication of the coupling strength between the grains and to an alteration of the pinning eectiveness for the intergranular ux lines. It was shown in Ref. [3] that the grain connectivity is indeed improved by the KClO3 -addition, if small amounts of KClO3 -additions (x = 0.20 0.30) are employed. This stronger superconducting signal may then completely mask the paramagnetic contribution of the copper. CONCLUSIONS We have presented FCC/FCW measurements on pure YBCO and KClO3 -doped samples in elds between 10 mT and 7 T. All DC curves are found to be monotonous, but the doped samples exhibit a clear downturn to more diamagnetic values at low temperatures. This indicates that the increasing KClO3 -addition leads to a modication of the coupling strength of the grains. Acknowlegdments. This work is partially supported by New Energy and Industrial Technology Development Organization (NEDO). AV and MRK gratefully acknowledge support from the Japanese Science and Technology Agency (STA). 1. B. Okai, Jpn. J. Appl. Phys. 29, L2193-L2195 (1990). 2. A. Veneva, I. Iordanov, L. Toshev, A. Stoyanova and D. Gogova, Physica C 308, 175-184 (1998). 3. A. Veneva, M. R. Koblischka, N. Sakai and M. Murakami, presented at the MOS'99 conference, 28.7.2.8.99, Stockholm, Sweden, to be published in J. 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