Preparation of CaB<sub>6</sub> powder via calciothermic reduction of boron carbide

Yu Wang; Guo-hua Zhang; Yue-dong Wu; Xin-bo He

doi:10.1007/s12613-019-1873-y

Volume 27 Issue 1

Jan. 2020

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Article Navigation > International Journal of Minerals, Metallurgy and Materials > 2020 > 27(1): 37-45

Yu Wang, Guo-hua Zhang, Yue-dong Wu, and Xin-bo He, Preparation of CaB₆ powder via calciothermic reduction of boron carbide, Int. J. Miner. Metall. Mater., 27(2020), No. 1, pp. 37-45. https://doi.org/10.1007/s12613-019-1873-y

Cite this article as:

Yu Wang, Guo-hua Zhang, Yue-dong Wu, and Xin-bo He, Preparation of CaB6 powder via calciothermic reduction of boron carbide, Int. J. Miner. Metall. Mater., 27(2020), No. 1, pp. 37-45. https://doi.org/10.1007/s12613-019-1873-y

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Research Article

Preparation of CaB₆ powder via calciothermic reduction of boron carbide

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Corresponding author:
Guo-hua Zhang E-mail: ghzhang0914@ustb.edu.cn
Received: 16 March 2019; Revised: 30 May 2019; Accepted: 3 June 2019; Available online: 21 October 2019

Abstract

Abstract

The method of calciothermic reduction of B₄C was proposed for preparing CaB₆. The phase transition and morphology evolution during the reaction were investigated in detail. The experimental results reveal that Ca first reacts with B₄C to generate CaB₂C₂ and CaB₆ at a low temperature and that the CaB₂C₂ subsequently reacts with Ca to produce CaB₆ and CaC₂ at a high temperature. After the products were leached to remove the byproduct CaC₂, pure CaB₆ was obtained. The grain size of the prepared CaB₆ was 2–3 μm, whereas its particle size was 4–13 μm; it inherited the particle size of B4C. The residual C content of the product was decreased to 1.03wt% after the first reaction at 1173 K for 4 h and the second reaction at 1623 K for 4 h.
- borides;
- carbides;
- particle size;
- powders;
- calcium hexaboride

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References

[1]	Nisso Tsushinsha, ed., Handbook on High-melting-point Composites, Nisso Tsushinsha, Ehime, 1977.
[2]	R.A. Cutler, Engineered Materials Handbook, Vol. 4, S.J. Schneider Jr. ed., ASM International, The Materials Information Society, Metals Park, Ohio, 1991, p. 787.
[3]	P.A. Dearnley and T. Bell, Engineering the surface with boron based materials, Surf. Eng., 1(1985), No. 3, p. 203. doi: 10.1179/sur.1985.1.3.203
[4]	H.J. Tromp, P. Van Gelderen, P.J. Kelly, G. Brocks, and P.A. Bobbert, CaB₆: a new semiconducting material for spin electronics, Phys. Rev. Lett., 87(2001), art. No. 016401.
[5]	D.P. Young, D. Hall, M.E. Torelli, Z. Fisk, J.L. Sarrao, J.D. Thompson, H.R. Ott, S.B. Oseroff, R.G. Goodrich, and R. Zysler, High-temperature weak ferromagnetism in a low-density free-electron gas, Nature, 397(1999), p. 412. doi: 10.1038/17081
[6]	L.H. Bao, X.P. Qi, L.M. Chao, and O. Tegus, Synthesis, and magnetic and optical properties of nanocrystalline alkaline-earth hexaborides, CrystEngComm, 18(2016), p. 1223. doi: 10.1039/C5CE02060C
[7]	H. Razavi-Zadeh and S. Mirdamadi.T, Deoxidizing copper with CaB₆, JOM, 39(1987), No. 2, p. 42. doi: 10.1007/BF03259470
[8]	K.G. Schmitt-Thomas, A. Lipp, and K. Schwetz, Process for the Production of Oxygen-Free Copper Casting and Moldings, United States Patent, Appl. 738819, 1976.
[9]	T. Rymon-Lipinski, B. Schmelzer, and S. Ulitzka, Tests on the oxidation-inhibiting effect of CaB₆ in refractory MgO–C materials, Steel Res., 65(1994), No. 6, p. 234. doi: 10.1002/srin.199401063
[10]	J.W. Butler, Neutron-absorbing bricks made from CaB₆, Nucl. Instrum. Methods, 7(1960), No. 2, p. 201. doi: 10.1016/0029-554X(60)90129-4
[11]	M.T. Zheng, H.W. Dong, Y. Xiao, S.T. Liu, H. Hu, Y.R. Liang, L.Y. Sun, and Y.L. Liu, Facile one-step and high-yield synthesis of few-layered and hierarchically porous boron nitride nanosheets, RSC Adv., 6(2016), No. 51, p. 45402. doi: 10.1039/C6RA07455C
[12]	B.A. Galanov, V.V. Kartuzov, O.N. Grigoriev, L.M. Melakh, S.M. Ivanov, E.V. Kartuzov, and P. Swoboda, Penetration resistance of B₄C–CaB₆ based light-weight armor materials, Procedia Eng., 58(2013), p. 328. doi: 10.1016/j.proeng.2013.05.037
[13]	P. Seenuvasaperumal, A. Elayaperumal, and R. Jayavel, Influence of calcium hexaboride reinforced magnesium composite for the mechanical and tribological behviour, Tribol. Int., 111(2017), p. 18. doi: 10.1016/j.triboint.2017.02.042
[14]	Y. Gao, Z.D. Liu, Q. Wang, and Y.T. Wang, Microstructure and mechanical properties of Nb–Mo–ZrB₂ composites prepared by hot-pressing sintering, Int. J. Miner. Metall. Mater., 25(2018), No. 7, p. 824. doi: 10.1007/s12613-018-1631-6
[15]	Y.R. Zhang, Q. Cai, Y.C. Liu, Z.Q. Ma, C. Li, and H.J. Li, Evaluation of precipitation hardening in TiC-reinforced Ti₂AlNb-based alloys, Int. J. Miner. Metall. Mater., 25(2018), No. 4, p. 453. doi: 10.1007/s12613-018-1591-x
[16]	L. Zhang, G.H. Min, and H.S. Yu, Reaction mechanism and size control of CaB₆ micron powder synthesized by the boroncarbide method, Ceram. Int., 35(2009), No. 8, p. 3533. doi: 10.1016/j.ceramint.2009.05.032
[17]	M. Kakiage, S. Shiomi, I. Yanase, and H. Kobayashi, Low-temperature synthesis of calcium hexaboride powder via transient boron carbide formation, J. Am. Ceram. Soc., 98(2015), No. 9, p. 2724. doi: 10.1111/jace.13771
[18]	D. Yilmaz, U. Savaci, N. Koç, and S. Turanb, Carbothermic reduction synthesis of calcium hexaboride using PVA-calcium hexaborate mixed gels, Ceram. Int., 44(2018), No. 3, p. 2976. doi: 10.1016/j.ceramint.2017.11.050
[19]	M. Kakiage, S. Shiomi, T. Ohashi, and H. Kobayashi, Effect of calcium carbonate particle size on formation and morphology of calcium hexaboride powder synthesized from condensed boric acid-poly (vinyl alcohol) product, Adv. Powder Technol., 29(2018), No. 1, p. 36. doi: 10.1016/j.apt.2017.10.004
[20]	K. Bao, L.X. Lin, H. Chang, and S.W. Zhang, Low-temperature synthesis of calcium hexaboride nanoparticles via magnesiothermic reduction in molten salt, J. Ceram. Soc. Jpn., 125(2017), No. 12, p. 866. doi: 10.2109/jcersj2.17102
[21]	Ö. Balcı, D. Ağaoğulları, İ. Duman, and M.L. Öveçoğlu, Synthesis of CaB₆ powders via mechanochemical reaction of Ca/B₂O₃ blends, Powder Technol., 225(2012), p. 136. doi: 10.1016/j.powtec.2012.03.051
[22]	X. Huang, J.C. Zhong, L.S. Dou, and K. Wang, Combustion synthesis of CaB₆ powder from calcium hexaborate and Mg, Int. J. Refract. Met. Hard Mater., 28(2010), No. 2, p. 143. doi: 10.1016/j.ijrmhm.2008.11.009
[23]	X. Wang and Y.C. Zhai, An electrochemical method for the preparation of CaB₆ crystal powder, J. Appl. Electrochem., 39(2009), p. 1797. doi: 10.1007/s10800-009-9881-7
[24]	W. Weng, M.Y. Wang, X.Z. Gong, Z. Wang, D. Wang, and Z.C. Guo, Electrochemical conversions of soluble borates to CaB₆ with superior optical property in NaCl–CaCl₂ melt, J. Electrochem. Soc., 165(2018), No. 10, p. E477. doi: 10.1149/2.0821810jes
[25]	S. Angappan, M. Helan, A. Visuvasam, L.J. Berchmans, and V. Ananth, Electrolytic preparation of CaB₆ by molten salt technique, Ionics, 17(2011), No. 6, p. 527. doi: 10.1007/s11581-011-0531-9
[26]	S.Q. Zheng, G.H. Min, Z.D. Zou, H.S. Yu, and J.D. Han, Synthesis of calcium hexaboride powder via the reaction of calcium carbonate with boron carbide and carbon, J. Am. Ceram. Soc., 84(2001), No. 11, p. 2725. doi: 10.1111/j.1151-2916.2001.tb01083.x
[27]	B. Albert and K. Schmitt, CaB₂C₂: Reinvestigation of a semiconducting boride carbide with a layered structure and an interesting boron/carbon ordering scheme, Inorg. Chem., 38(1999), No. 26, p. 6159. doi: 10.1021/ic9907821
[28]	J. Akimitsu, K. Takenawa, K. Suzuki, H. Harima, and Y. Kuramoto, High-temperature ferromagnetism in CaB₂C₂, Science, 293(2001), No. 5532, p. 1125. doi: 10.1126/science.1061501
[29]	A.V. Blinder, S.P. Gordienko, É.V. Marek, and V.B. Muratov, Thermodynamic properties of calcium hexaboride, Powder Metall. Met. Ceram., 36(1997), No. 7-8, p. 409. doi: 10.1007/BF02676002
[30]	W. Ostwald, Über die vermeintliche Isomerie des roten und gelben Quecksilberoxyds und die Oberflächenspannung fester Körper, Z. Phys. Chem., 34(1900), p. 495.
[31]	L. Zhang, G.H. Min, H.S. Yu, H.M. Chen, and G. Feng, The size and morphology of fine CaB₆ powder synthesized by nanometer CaCO₃ as reactant, Key Eng. Mater., 326-328(2006), p. 369. doi: 10.4028/www.scientific.net/KEM.326-328.369
[32]	S.S.N. Murthy, M. Patel, J.J. Reddy, and V.V. Bhanu Prasad, Influence of B₄C particle size on the synthesis of ZrB₂ by boro/carbothermal reduction method, Trans. Indian Inst. Met., 71(2018), No. 1, p. 57. doi: 10.1007/s12666-017-1155-1