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RARE METALS, SEMICONDUCTORS
ArticleName Calciothermic powders of rare metals and intermetallic compounds
DOI 10.17580/nfm.2020.02.05
ArticleAuthor Kasimtsev A. V., Levinsky Yu. V., Yudin S. N.
ArticleAuthorData

LTD Metsintez, Tula, Russia

A. V. Kasimtsev, CEO, e-mail: metsintez@yandex.ru

S. N. Yudin, Head of Technological Bureau, e-mail: Sergey-USN@mail.ru

 

Merzhanov Institute of Structural Macrokinetics and Materials Science of Russian Academy of Sciences, Chernogolovka, Russia:
Yu. V. Levinsky, Leading Researcher, Laboratory of Physical Stimulation of Physico-Chemical Processes, e-mail: levinsky35@mail.ru

Abstract

This paper presents a profound review of scientific and technical literature on the issues of calciothermic production of powders of rare metals, intermetallic compounds, composite materials and refractory oxygen-free compounds (carbides, nitrides). Calciothermic reduction is a metallothermic synthesis method for those substances where calcium or its derivatives, such as calcium hydride or calcium carbide, are used as a reducing agent. Thermodynamics aspects of a reduction process are covered in the paper broadly, with particular emphasis on assessing the reduction depth of original oxide raw materials, as TiO2. The mechanism and kinetics of calciothermic synthesis of single-component and multi-component alloys are described. Presented are both technological means of obtaining materials and hardware resources of many varieties of calciothermic method. The key features of the work are generalization and systematization of properties (chemical, physical, technological) of materials synthesized by calciothermic method. The data are accumulated in the appropriate tables and divided by substance classes (powders of metals and alloys, powders of intermetallic compounds, powders of carbides, powders of nitrides, and powders of composite materials). Methods of calciothermic powder making in case of the singlecomponent and complex multi-component systems are briefly described. This work will be interesting to the students of metallurgical profile and specialists whose scientific interests are in the field of material synthesis by methods of powder metallurgy.

keywords Calcium thermal reduction, calcium hydride method, powder metallurgy, intermetallic compounds, powders of metals and alloys, properties, synthesis, literature review
References

1. Kroll W. J. Method for Manufacturing Titanium and Alloys Thereof. US Patent. 2205854, 1940.
2. Kroll W. J. Transactions of The Electrochemical Society. Vol. 78, Iss. 1. pp. 35–47. DOI: 10.1149/1.3071290
3. Jacob K. T., Gupta S. JOM. 2009. Vol. 61, Iss. 5. pp. 56–59. DOI: 10.1007/s11837-009-0072-0
4. Kasimtsev A. V., Levinsky Yu. V. Calcium-Hydride Powders of Metals, Intermetallic Compounds, refractory compounds and composite materials. Moscow : MITKhT, 2012. 247 p.
5. Meerson G. A., Katz G. A., Khokhlova A. V. Zhurnal Neorganicheskoy i Prikladnoy Khimii. 1940. Vol. 13, No. 12. pp. 1770-1776.
6. Chen G. Z., Fray D. J., Farthing T. W. Nature. 2000. Vol. 407, Iss. 6802. pp. 361–364. DOI: 10.1038/35030069
7. Jiang K., Hu X., Ma M., Wang D., Qui G., Jin X., Chen G. Z. Angewandte Chemie International Edition. 2006. Vol. 45, Iss. 3. pp. 428–432. DOI: 10.1002/anie.200502318
8. Li Wei, Wong Ying, Tang Ren-Heng, Xiao Fang-Ming. Materials Research and Application. 2010. Vol. 4, Iss. 4. pp. 555–558.
9. Katsutoshi Ono, Ryosuke O. Suzuki. JOM. 2002. Vol. 54, Iss. 2. pp. 59–61. DOI: 10.1007/bf02701078
10. Katsutoshi Ono. Materials Transactions. 2004. Vol. 45, Iss. 5, pp. 1660–1664. DOI: 10.1007/bf02701078
11. Moxson V. S., Senkov O. N., Froes F. H. JOM. 2000. Vol. 52, Iss. 5. pp. 24–26. DOI: 10.1007/s11837-000-0027-y
12. He-Li Wan, Bao-Qiang Xu, Yong-Nian Dai, Bin Yang, Da-Chun Liu, Wei Sen. Journal of Central South University. 2012. Vol. 19, Iss. 9. pp. 2434–2439. DOI: 10.1007/s11771-012-1293-x
13. Okabe T. H., Sadoway D. R. Journal of Materials Research. 1998. Vol. 13, Iss. 12. pp. 3372–3377. DOI: 10.1557/jmr.1998.0459
14. Okabe T. H., Uda T. Titanium Japan. 2002. Vol. 50. pp. 325–330.
15. Bayat O., Khavandi A. R., Ghasemzadeh R. International Journal of Self-Propagating High-Temperature Synthesis. 2012. Vol. 21, Iss. 3. pp. 151–155. DOI: 10.3103/s1061386212030028
16. Okabe T. H., Oda T., Mitsuda Y. Journal of Alloys and Compounds. 2004. Vol. 364, Iss. 1-2. pp.156–163. DOI: 10.1016/s0925-8388(03)00610-8
17. Suzuki R. O., Ikezawa M., Okabe T. H., Oishi T., Ono K. Materials Transactions, JIM. 1990. Vol. 31, Iss. 1. pp. 61–68. DOI: 10.2320/matertrans1989.31.61
18. Yamaguchi K., Kim D.-Y., Ohtsuka M., Itagaki K. Journal of Alloys and Compounds. 1995. Vol. 221, Iss. 1-2. pp. 161–168. DOI: 10.1016/0925-8388(94)01422-1
19. Tanabe T., Takahashi K., Yoshida H., Asaki Z. Materials Transactions, JIM. 1994. Vol. 35, Iss. 8. pp. 516–521. DOI: 10.2320/matertrans1989.35.516
20. Tanabe T., Nagai Y., Kubota T., Asaki Z. Materials Transactions, JIM. 1992. Vol. 33, Iss. 12. pp. 1163–1170. DOI: 10.2320/matertrans1989.33.1163
21. Suzuki R. O., Inoue S. Metallurgical and Materials Transactions: B. 2003. Vol. 34, Iss. 3. pp. 277–285. DOI: 10.1007/s11663-003-0073-2

22. Liu S. F., Lin J. H., Qian X. L., Bayi J. M., Su M. Z. Chemistry of Materials. 1996. Vol. 8, Iss. 11. pp. 2545–2547. DOI: 10.1021/cm950513i
23. Mukherjee T. K., Kamat G. R., Gupta C. K. JOM. 1970. Vol. 22, Iss. 2. pp. 50–53. DOI: 10.1007/bf03355939
24. Li Z., Yasuda K., Itagaki K. Journal of Alloys and Compounds. 1993. Vol. 193, Iss. 1-2. pp. 26–28. DOI: 10.1016/0925-8388(93)90299-3
25. Ilayaraja M., Berchmans L. J., Sankaranarayanan S. R. Metallurgical and Materials Engineering. 2014. Vol. 20, Iss. 1. pp. 35–40. DOI: 10.5937/metmateng1401035i
26. Guilherme E. da G., Hechenberg H. R., Pascoal J. O. A. Materials Science Forum. 2006. Vol. 530-531. pp. 181–186. DOI: 10.4028/www.scientific.net/msf.530-531.181
27. Chen C.-Q., Kim D., Choi C. Journal of Magnetism and Magnetic Materials. 2014. Vol. 355. pp. 180–183. DOI: 10.1016/j.jmmm.2013.12.023
28. Ilayaraja M., Berchmans L. J., Sankaranarayanan S. R. Metallurgical and Materials Engineering. 2015. Vol. 21, Iss. 2. pp. 65–72. DOI: 10.30544/96
29. Chen H.-B., Zheng J.-W., Qiao L., Ying Y., Jiang L.-Q., Che S.-L. Rare Metals. 2015. Vol. 37, Iss. 11. pp. 989–994. DOI: 10.1007/s12598-015-0584-4
30. Travessini D., Favero T. A. C., Teixeira C. S., Wendhausen P. A. P. IEEE Transactions on Magnetics. 2013. Vol. 49, Iss. 8. pp. 4634–4637. DOI: 10.1109/tmag.2013.2258141
31. Deng G., Jing Q., Wang X., He G., Ye X. Journal of Rare Earths. 2010, Vol. 28. pp. 420–424. DOI: 10.1016/s1002-0721(10)60357-2
32. Dzneladze Zh. I., Shchegoleva R. P., Golubeva L. S. et al. Powder Metallurgy of Steels and Alloys. Moscow : Metallurgiya, 1978. 264 p.
33. Meerson G. A., Kolchin O. P. Сollected Scientific Papers of the Moscow Institute of Nonferrous Metals and Gold named after M. I. Kalinin. Moscow : Metallurgizdat, 1955. No. 25. pp. 195–208.
34. Levinsky Yu. V. Phase Diagrams of Metals with Gases. Moscow : Metallurgiya, 1975. 296 p.
35. Levinsky Yu. V. Pressure Dependent Phase Diagrams of Binary Alloys. Vol. 1, ASM. Materials Park, OH 44073. 1997, 920 p.
36. Levinsky Yu. V. P-T-x Phase Diagrams of Binary Systems. Moscow : Metallurgiya, 1982. 111 p.
37. Kasimtsev A. V., Zhigunov V. V. Izvestiya Vuzov. Poroshkovaya Metallurgiya i Funktsional’nye Pokrytiya. 2009. No. 3. pp. 5–12.
38. Doronin N. A. Calcium. Мoscow : Gosatomizdat, 1962. 192 p.
39. Bayat O., Khavandi A. R., Ghasemzadeh R. Russian Journal of Non-Ferrous Metals. 2012. Vol. 53, Iss. 6. pp. 476–482. DOI: 10.3103/s1067821212060028
40. Byun J.-Y., Kim Y.-S., Shim J.-D. Shigen-to-Sozai. 1994. Vol. 110, Iss. 15. pp. 1203–1208. DOI: 10.2473/shigentosozai.110.1203
41. Suzuki R. O., Aizawa M., Ono K. Journal of Alloys and Compounds. 1999. Vol. 288, Iss. 1-2. pp. 173–182. DOI: 10.1016/s0925-8388(99)00116-4
42. Xu B., Yang B., Jia J., Liu D., Xiong H., Deng Y. Journal of Alloys and Compounds. 2013. Vol. 576. pp. 208–214. DOI: 10.1016/j.jallcom.2013.04.107
43. Suzuki R.O., Ueki T., Ikezawa M., Okabe T. H., Oishi T., Ono K. Materials Transactions, JIM. 1991. Vol. 32, Iss. 3. pp. 272–277. DOI: 10.2320/matertrans1989.32.272
44. Ono K., Okabe T. H., Ogawa M., Suzuki R. O. Tetsu-to-Hagane. 1990, Vol. 76, Iss. 4. pp. 568–575. DOI: 10.2355/tetsutohagane1955.76.4_568
45. Levinsky Yu. V., Lebedev M. P. Theoretical Bases Of Metal Powder Sintering Processes. Moscow : Nauchnyi Mir, 2014. 372 p.
46. Geguzin Ya. E. Physics of Sintering. 2nd ed. Moscow : Nauka, 1984. 311 p.
47. Gupta C. K., Jena P. K. Journal of the Less Common Metals. 1965. Vol. 8, Iss. 2. pp. 90–98. DOI: 10.1016/0022-5088(65)90100-1
48. Suzuki N., Tanaka M., Noguchi H., Natsui S., Kikuchi T. Suzuki R. O. Materials Transactions. 2017. Vol. 58, Iss. 3. pp. 367–370. DOI: 10.2320/matertrans.mk201613
49. Suzuki R. O., Nagai H., Oishi T., Ono K. Journal of Materials Science. 1987. Vol. 22, Iss. 6. pp. 1999–2005. DOI: 10.1007/bf01132930
50. Lindemann I., Herrich M., Gebel B., Schmidt R., Stoeck U., Uhlemann M., Gebert A. Scripta Materialia. 2017. Vol. 130, pp. 256–259. DOI: 10.1016/j.scriptamat.2016.11.018
51. Frau D. J. JOM. 2001. Vol. 53. pp. 26–31.
52. Kamali A. R., Aboutalebi M. R., Farhang M. R. International Journal of Self-Propagating High-Temperature Synthesis. 2008. Vol. 17, Iss. 4. pp. 233–236.
53. Oh J.-M., Lee B.-K., Suh C.-Y., Cho S.-W., Lim J.-W. Powder Metallurgy. 2012. Vol. 55, Iss. 5. pp. 402–404. DOI: 10.1179/1743290112y.0000000013
54. Oh J.-M., Kwon H., Ki W., Lim J.-W. Thin Solid Films. 2014. Vol. 551. pp. 98–101. DOI: 10.1016/j.tsf.2013.11.076
55. Kasimtsev A. V., Shuitsev A. V., Yudin S. N., Levinsky Yu. V., Sviridova T. A., Alpatov A. V., Novosvetlova E. E. Metally. 2017. No. 5. pp. 52–63.
56. Sehra J. C., Rakhasia R. H., Shah V. D. High Temperature Materials and Processes. 1997. Vol. 16. pp. 123–132. DOI: 10.1515/htmp.1997.16.2.123
57. Baba M., Kikuchi T., Suzuki R. O. J. Journal of Physics and Chemistry of Solids. 2015. Vol. 78. pp. 101–109. DOI: 10.1016/j.jpcs.2014.11.014
58. Baba M., Ono Y., Suzuki R. O. Journal of Physics and Chemistry of Solids. 2005. Vol. 66, Iss. 2-4. pp. 466–470. DOI: 10.1016/j.jpcs.2004.06.042
59. Niiyama H., Tsukihashi F., Sano N. Journal of Alloys and Compounds. 1992, Vol. 179, Iss. 1-2. pp. L1–L5. DOI: 10.1016/0925-8388(92)90193-d
60. Mukherjee A., Awasthi A., Krishnamurthy N. Mineral Processing and Extractive Metallurgy. 2016. Vol. 125, Iss. 1. pp. 26–31. DOI: 10.1179/1743285515y.0000000017
61. Cupta C. K., Krishramurthy N. Minerals and Metallurgical Processing. 2013. Vol. 30, No. 1, pp. 38–44.
62. Spedding F. H., Daane A. H. JOM. 1954. Vol. 6, Iss. 5. pp. 504–510. DOI: 10.1007/bf03398865

63. Spedding F. H., Wilhelm H. A., Keller W. H., Ahmann D. H., Daane A. H., Hach C. C., Ericson R. P. Industrial & Engineering Chemistry. 1952. Vol. 44, Iss. 3. pp. 553–556. DOI: 10.1021/ie50507a034
64. Sharma R. A. JOM. 1987. Vol. 39, Iss. 2. pp. 33–37. DOI: 10.1007/bf03259468
65. Sharma R. A., Seefurth R. N. Journal of The Electrochemical Society. 1988. Vol. 135, Iss. 1. pp. 66–71. DOI: 10.1149/1.2095591
66. Suzuki R. O., Baba M., Yamamoto K. Proc. 7th Int. Symp. on Molten Salts Chem. and Techn. (29 Aug. – 02 Sept. 2005, Toulouse, France). Vol. 2. pp. 1063–1066.
67. Niiyama H., Tajima Y., Tsukihashi F., Sano N. Journal of the Less Common Metals. 1991. Vol. 169, Iss. 2. pp. 209–216. DOI: 10.1016/0022-5088(91)90069-g
68. Suzuki R. O., Ikezawa., Okabe T. H., Oishi T., Ono K. Materials Transactions, JIM. 1990. Vol. 31, Iss. 1. pp. 61–68. DOI: 10.2320/matertrans1989.31.61
69. Suzuki R. O., Sakamoto H., Oishi T., Ono K. Proc. 6th World Conf. on Titanium, Cannes, France, 1988. Part II. pp. 895–900.
70. Bertheville B., Bidaux J.-E. Journal of Alloys and Compounds. 2005. Vol. 387, Iss. 1-2. p. 211–216. DOI: 10.1016/j.jallcom.2004.06.079
71. Bertheville B., Bidaux J.-E. Scripta Materialia. 2005. Vol. 52, Iss. 6. pp. 507–512. DOI: 10.1016/j.scriptamat.2004.11.002
72. Kasimtcev A. V., Markova G. V., Shuytcev A. V., Levinsky Yu. V., Sviridova T. A., Alpatov A. V. Izvestiya Vuzov. Poroshkovaya Metallurgiya i Funktsional’nye Pokrytiya. 2014. No. 3. pp. 31–37. DOI: 10.17073/1997-308X-2014-3-31-37
73. Markova G. V., Kasimtsev A. V., Volodko S. S., Bubnenkov B. B. Tsvetnye Metally. 2018. No. 11. pp. 75–82. DOI: 10.17580/tsm.2018.11.11
74. Markova G. V., Kasimtsev A. V., Volodko S. S., Bubnenkov B. B. Tsvetnye Metally. 2018. No. 12. pp. 75–81. DOI: 10.17580/tsm.2018.12.11
75. Bayat O., Khavandi A. R., Ghasemzadeh R. Journal of Alloys and Compounds. 2012. Vol. 520. pp. 164–169. DOI: 10.1016/j.jallcom.2011.12.174
76. Suzuki R. O., Yoshinori M. Joint International Conference on “Sustainable Energy and Environment (SEE)”, 1–3 December, 2004. HuaHin, Thailand, pp. 167–170.
77. Tsuchiya T., Yahsuda N., Sasaki S., Okinaka N., Akiyama T. International Journal of Hydrogen Energy. 2013. Vol. 38. pp. 6681–6686. DOI: 10.1016/j.ijhydene.2013.02.106
78. Davids M. W., Lototskyy M., Pollet B. G. Advanced Materials Research. 2013, Vol. 746. pp. 14–22. DOI: 10.4028/www.scientific.net/amr.746.14
79. Okabe T. H., Fujiwara K., Oishi T., Ono K. Metallurgical Transactions B. 1992. Vol. 23, Iss. 4. pp. 415–421. DOI: 10.1007/bf02649659
80. Kasimtsev A. V., Korneev L. I. Izvestiya Vuzov. Tsvetnaya Metallurgiya. 2002. No. 1. pp. 48–52.
81. Pat. RU 2351534. С1, СО1В 3/56, 6/24. Method for Making Reversible Hydrogen-Sorbing Alloy Combination (Versions). Inventor/Proprietor: Kasimtsev A. V. Application: No. 2007124359/15, 29.06.2007; Publication: 10.04.2009, Bull. No. 10
82. Xiao Y., Liu Y., Yuan D., Zang J., Mi Y. Materials Letters. 2006. Vol. 60, Iss. 21-22. pp. 2558–2560. DOI: 10.1016/j.matlet.2006.01.036
83. Kim C. W., Kim Y. H., Cha H. G., Kang Y. S. Physica Scripta. 2007. Vol. 129. pp. 321–325. DOI: 10.1088/0031-8949/2007/t129/071
84. Chen C.-Q., Kim D., Choi C. Journal of Magnetism and Magnetic Materials. 2014. Vol. 355. pp. 180–183. DOI: 10.1016/j.jmmm.2013.12.023
85. Sidhu R. K. Journal of Alloys and Compounds. 2002. Vol. 346, Iss. 1-2. pp. 250–254. DOI: 10.1016/s0925-8388(02)00496-6
86. Gabay A. M., Hu X. C., Hadjipanayis G. C. Journal of Alloys and Compounds. 2013. Vol. 574. pp. 472–476. DOI: 10.1016/j.jallcom.2013.05.155
87. Kasimtsev A. V., Yudin S. N., Logacheva A. I., Sviridova T. A. Neorganicheskiye Materialy. 2015. Vol. 51, No. 1. pp. 49–56.
88. Kasimtsev A. V., Reutova N. P., Mnasina L. M., Zubkov N. P., Sviridova T. A., Turutin Yu. A. Izvestiya Vuzov. Poroshkovaya Metallurgiya i Funktsional’nye Pokrytiya. 2010. No. 3. pp. 3–10.
89. Jacob K. T., Gupta S. Bulletin of Materials Science. 2009. Vol. 2, Iss. 6. pp. 611–616. DOI: 10.1007/s12034-009-0094-9
90. Meerson G. A., Yakisheva L. M., Shvedova T. A. Proceedings of the USSR Academy of Sciences. Metallurgy and Mining. 1963. No. 1. pp. 69–73.
91. Lobova T. A. Izvestiya Vuzov. Tsvetnaya Metallurgiya. 2001. No. 6. pp. 10–17.
92. Bavbande D. V., Mishra R., Juneja J. M. Journal of Thermal Analysis and Calorimetry. 2004. Vol. 78, Iss. pp. 775–780. DOI: 10.1007/s10973-005-0445-0
93. Kotenev V. I., Kasimtsev A. V., Zhigunov V. V., Koteneva V. Ya. Poroshkovaya Metallurgiya. 1988. No. 3. pp. 12–16.
94. Kasimtsev A. V., Zhigunov V. V., Tabachkova N. Yu. Izvestiya Vuzov. Poroshkovaya Metallurgiya i Funktsional’nye Pokrytiya. 2008. No. 4. pp. 15–19.
95. Kasimtsev A. V., Korneev L. I., Zhigunov V. V. Tyazheloe Mashinostroenie. 2006. No. 11. pp. 6–9.
96. Kiparisov S. S., Levinskii Yu.V. Internal Oxidation and Nitriding of Alloys. Moscow : Metallurgiya, 1979. 199 p.
97. Levinskii Yu. V. Internally Oxidized and Internally Nitrided Nanomaterials. Moscow : EKOMET, 2009. 399 p.
98. Kasimtsev A. V., Levinsky Yu. V., Zhigunov V. V. Izvestiya Vuzov. Poroshkovaya Metallurgiya i Funktsional’nye Pokrytiya. 2008. No. 2. pp. 3–8.

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