Journal of Alloys and Compounds 485 (2009) L44L46

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

Letter

Effect of ne boron powders prepared with a self-propagating high temperature synthesis on ux pinning properties of the MgB2 /Fe composite wires
Young-Kuk Kim a, , Kookchae Chung a , Jaimoo Yoo a , In-Hyuk Song a , Jaewoong Ko a , Woo-Hyun Chung b , Dong-Ho Kim d , Xiolin Wang c , Shi Xue Dou c , Pyung-Woo Shin e
a

Korea Institute of Materials Science (KIMS), #66 Sangnamdong, Changwon, Kyungnam 641-010, South Korea KISWEL Inc., #58-2 Sungjudong, Changwon, Kyungnam 641-120, South Korea Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522, Australia d Yeungnam University, #214-1 Daedong, Kyungsan, Kyungpook 712-749, South Korea e Changwon National University, #9 Sarimdong, Changwon, Kyungnam 641-773, South Korea
b c

a r t i c l e

i n f o

a b s t r a c t
Fine boron powders were prepared by a self-propagating high temperature synthesis (SHS) based on the reduction of boron oxide by magnesium (3Mg + B2 O3 3MgO + 2B). The synthesized boron powders with SHS process showed small particle size (350 nm) with highly enlarged surface area. The MgB2 /Fe composite wire prepared with SHS-processed boron powders showed enhanced Jc properties under magnetic eld. The major mechanism under this improvement was analyzed to be surface pinning by large number of grain boundaries owing to the small grain size of MgB2 . 2009 Elsevier B.V. All rights reserved.

Article history: Received 19 May 2009 Received in revised form 9 June 2009 Accepted 10 June 2009 Available online 26 June 2009 Keywords: MgB2 SHS Boron Superconducting wires

1. Introduction Considerable efforts have been undertaken to improve the critical current density (Jc ) of MgB2 superconducting wires required for application to high performance electric devices [13]. Much experimental report showed that carbon doping and addition of nanoparticle are effective for high Jc [4,5]. There have been claims that properties of starting powders are also important for the superconductivity of MgB2 wires [6,7]. For example, boron powders with small size and amorphous nature are required for good superconducting performance [6]. That is, the renement of the grain structure is needed to enhance grain boundary pinning and reactivity with magnesium. Strong grain-to-grain supercurrent coupling occurs in MgB2 , and Jc can be raised by reducing the grain size through improving grain boundary pinning. So, various fabrication techniques such as ball milling [8] and plasma arc discharge [9] were introduced to obtain ne boron powders. However, they have problems such as high production cost and incorporation of foreign impurities. Recently, various nanocrystalline boride powders such as TiB2 and B4 C were synthesized with self-propagating high temperature

synthesis (SHS) based on following exothermal reaction [1013]: 3Mg(s) + B2 O3 (s) 3MgO(s) + 3B(s),
H298 K = 550.4 kJ/mol

(1) Since the SHS method uses exothermic reaction by reactant mixture, high temperature reaction is possible within a few seconds without any external heating. Thus, various materials with technological importance can be synthesized with this cost-effective and fast processing route. In this study, we employed SHS route to synthesize ne boron powders with sub-micron size distribution and applied them to in situ processing of MgB2 /Fe superconducting composite wires.
2. Experimental Fine boron powders were synthesized by SHS based on exothermic reaction of Mg (99%) and boron oxide (99%) mixture. The reactant mixture of magnesium and boron oxide was ignited by electrical heating of nickelchromium resistance wires. In this study, we performed high temperature synthesis reaction under Ar atmosphere with pressure of 50 bar. The reaction product was cooled to room temperature and leached with hydrochloric acid to remove oxide and unreacted reactant. After removing acid by washing and ltering, the obtained boron powders were dried at 70 C in vacuum oven overnight. The size and composition of obtained boron powders were checked with scanning electron microscopy (SEM), dynamic laser light scattering (DLS), induction-coupled plasma (ICP) analysis. The surface area of boron powders was measured by BrunauerEmmettTeller (BET) method.

Corresponding author. Tel.: +82 55 280 3343; fax: +82 55 280 3392. E-mail address: voice21@kims.re.kr (Y.-K. Kim). 0925-8388/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2009.06.126

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Fig. 2. X-ray diffraction patterns of MgB2 synthesized with (a) BA-97 and (b) B-SHS.

Fig. 1. (a) X-ray diffraction patterns of boron powders. The arrows in the diffraction pattern indicate magnesium boride phase. SEM photos of boron powders: (b) BA-97 and (c) B-SHS. The large particles indicated by circles are Mg-rich phase identied from EDS analysis.

MgB2 /Fe composite wires were fabricated with conventional powder-in-tube (PIT) method. The boron powders were mixed with magnesium and lled in the iron tube with 13 mm in diameter. After swaging and drawing, the diameter of the lled iron tube was reduced to 1.4 mm and MgB2 /Fe composite wires were fabricated after annealing at 800 C for an hour under Ar/H2 atmosphere. The superconducting properties of the MgB2 /Fe composite wire was checked with a Physical Properties Measurement System (PPMS, Quantum Design Inc.) after removing Fe sheaths mechanically and Jc was estimated from hysteresis curve by analysis based on Beans model. The irreversibility eld (Birr ) was obtained by linear extrapolation to zero of Jc in Kramers plot, B vs. J1/2 B1/4 [14].

3. Results and discussions Fig. 1(a) shows X-ray diffraction patterns of the commercially available boron powders (BA-97, Tangshan Weihao Co.) and SHS-processed boron powders (B-SHS) for comparison. The Xray diffraction pattern of BA-97 powders contains many sharp peaks indicating existence of crystalline boron particles. On the other hands, the X-ray diffraction pattern of B-SHS powders shows relatively smaller boron peaks and some magnesium boride (MgB2 , MgB4 ) peaks. As shown in Fig. 1(b) and (c), the size of typical particles in BA-97 powders is more than 1 m and B-SHS powders are mainly composed of powders smaller than 0.5 m. However, there observed to be large particles in the SEM image of B-SHS powders and the EDS analysis pointed on the large particles also supported the existence of magnesium boride. The properties of SHS-processed boron powders (B-SHS) are summarized in Table 1. The size of B-SHS powders measured by
Table 1 Summary of properties of boron powders. Boron powders Source Size (nm)

DLS method is 350 nm which is much smaller than that of BA-97 (the average size measured with DLS method is more than 1 m). The large surface area of B-SHS measured by BET absorption curve also supports their small particle size. The abrupt temperature rise and very short duration of high temperature reaction in SHS processing explain the small particle size of B-SHS powders. However, B-SHS powder contains more Mg-rich impurities as indicated by ICP analysis result displayed in Table 1. Combining information from X-ray diffraction, SEM/EDS and ICP analysis of B-SHS support the existence of magnesium boride particles. Since the maximum temperature available with adiabatic condition, an adiabatic combustion temperature for the SHS reaction in Eq. (1) is calculated to be about 2400 C from thermodynamic data [13], the temperature rise during SHS reaction is very high even though heat ow should be considered. Thus, the reaction is performed in a nonequilibrium manner. In addition to this, difference between Gibbs free energies for MgB2 formation (4Mg + B2 O3 3MgO + MgB2 , G(T) = 666,940 + 123.19T (J/mol)) and boron formation G = 574,290 + 112.55T (J/mol)) are (3Mg + B2 O3 3MgO + 2B, less than 100 kJ/mol which is much smaller than Gibbs free energy for either two reaction [13,15]. Thus, although the duration of high temperature reaction is very short (a few seconds), magnesium borides are inevitably incorporated in SHS processing of boron powders. Fig. 2 shows X-ray diffraction patterns of in situ processed MgB2 using BA-97 and B-SHS as boron precursors. Both of diffraction patterns show well-developed MgB2 phase and no meaningful change in lattice parameters was observed. Only MgO is incorporated in the MgB2 and no MgB4 , MgB7 phases are identied. As shown in the enlarged view of diffraction patterns in Fig. 2, the full-width at half maximum (FWHM) of diffraction peaks for MgB2 synthesized with B-SHS powders is meaningfully broader than that of MgB2 synthesized with BA-97. Thus, the particle size of MgB2 synthesized with B-SHS was estimated to be much smaller than that of MgB2 synthesized with BA-97 [16]. The superconducting transition temperature (Tc (onset)) of MgB2 cores were checked by the electrical transport measurement by the 4-probe technique was 36 and 37.5 K for MgB2 from SHS-B and BA97 boron powders, respectively. The lower Tc (onset) of MgB2 from SHS-B can be attributed to relatively larger amount of impurity in the SHS-B compared with BA-97. Fig. 3 displays the magnetic eld

Surface area (m2 /g)

ICP B Mg 0.84% 3.2% Fe 0.43% 0.78% Si 1.25% 0.98%

B-A97 B-SHS

Tangshan Weihao Co. This study (SHS)

1500 350

13 24

97.5% 95.0%

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of MgB2 samples in this study, the peaks of the normalized pinning force are located at near b = 0.2. Moreover, the normalized pinning force vs. the reduced eld data for MgB2 can be nearly reproduced with the model function for grain boundary pinning, Fp /Fp (max) b0.5 (1 b)2 as shown in Fig. 3. Those results suggest that the grain boundary ux pinning is predominant in the MgB2 samples synthesized in this study and the enhanced Jc property of the MgB2 sample prepared with B-SHS powders can be ascribed to small grain size of this MgB2 . 4. Summary In summary, we synthesized very ne boron powders by a selfpropagating high temperature synthesis (SHS) based on reduction of boron oxide by magnesium. The synthesized boron powders with SHS process showed almost amorphous nature and small particle size (350 nm) with highly enlarged surface area. The MgB2 /Fe composite wire prepared with SHS-processed boron powders showed enhanced Jc properties under magnetic eld. The improvement in Jc was attributed to be surface pinning through increased grain boundary number by small grain size of MgB2 . Acknowledgments This work was supported by the global partnership program (GPP) from the Korea Foundation for International Cooperation of Science & Technology (KICOS) in M60602000012 through a grant provided by the Korean Ministry of Education, Science & Technology (MEST) and partially supported by Changwon National University. References
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Fig. 3. (a) Critical current density (Jc ) of MgB2 /Fe composite wires measured at 4.2 K and (b) dependence of normalized pinning force on reduced eld (b = B/Birr ). The solid line plot is theoretical calculation based on various pinning mechanism.

dependence of Jc for MgB2 cores separated from MgB2 /Fe composite wires converted from magnetic hysteresis data measured at 4.2 K. It shows clear enhancement of Jc for samples processed with B-SHS powders. For example, irreversibility eld for the MgB2 samples estimated from Kramers plot was increased from 5T to 6T by adopting B-SHS powders as boron source in MgB2 and Jc at self-eld condition also improved. Since boron powders obtained by SHS reaction shows small grain size with large surface area and grain boundaries in MgB2 can act as effective ux pinning sites [69], the enhancement of Jc implies that the application of B-SHS powders for MgB2 fabrication provide improved ux pinning and good grain connectivity. Further analysis of ux pinning behavior will provide a deeper insight. The normalized ux pinning forces at 4.2 K for MgB2 cores separated from MgB2 /Fe composite wires fabricated with different boron powders are plotted against the reduced magnetic eld (b = B/Birr ). The general relationship of the normalized ux pinning forces (Fp /Fp (max)) with the reduced eld proposed by Dew-Hughes, Fp /Fp (max) bp (1 b)q is useful to analyze the mechanism of ux pinning where the value of exponent in the relationship is different with ux pinning mechanism [17]. For both