Rare Metals

pp 1–7 | Cite as

Sulfur distribution in preparation of high titanium ferroalloy by thermite method with different CaO additions

  • Chu Cheng
  • Zhi-He DouEmail author
  • Ting-An Zhang
  • Jian-Ming Su
  • Hui-Jie Zhang
  • Yan Liu
  • Li-Ping Niu


Ferrotitanium is used as a deoxidizer and alloying agent during steelmaking process, which has a high demand for sulfur control. Sulfur was introduced from raw materials in the process of producing ferrotitanium by thermite method, where CaO was used as fluxing agent. At the same time, CaO has a great desulfurization capability. Effects of CaO addition on the distribution of sulfur in high titanium ferroalloy prepared by thermite method were studied in this work. The equilibrium diagram of Ti–Al–Fe–S system was calculated by FactSage 6.4 software package with FactPS and FTmisc database. The alloy and slag samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma atomic emission spectrometer (ICP-AES), X-ray fluorescence (XRF) and high-frequency infrared ray carbon sulfur analyzer. The result indicates that the sulfur in the alloy firstly exists in the form of liquid FeS, thereafter TiS (s) and eventually Ti2S (s) during cooling. The sulfur is mainly distributed in the alloy, and only a small amount of sulfur remains in the slag. Moreover, it is noted that the sulfur in the alloy does not distribute homogeneously, and it exists in the form of solid solution phase, (Ti, Al, Fe)S. S content in the slag, the sulfur capacity of the slag and the sulfur distribution ratio (LS) all increase with the increment of CaO addition, while S content in alloys decreases.


Desulfurization Sulfur partition ratio Optical basicity High titanium ferroalloy Thermite method 



This study was financially supported by the National Natural Science Foundation of China (Nos. 51422403 and 51504064), the Fundamental Research Funds for the Central Universities (No. N162505002) and the National Basic Research Program of China (No. 2013CB632606).


  1. [1]
    Demos A, Kremin D. Titanium and its alloys for use in iron and steelmaking. J ASTM Int. 1981;10(5):144.Google Scholar
  2. [2]
    Shah SJ, Henein H, Ivey DG. Microstructural characterization of ferrotitanium and ferroniobium. Mater Charact. 2013;78(4):96.CrossRefGoogle Scholar
  3. [3]
    Chen SH, Wang XH, He XF, Wang WJ. Industrial application of desulfurization using low basicity refining slag in tire cord steel. J Iron Steel Res Int. 2013;20(1):26.CrossRefGoogle Scholar
  4. [4]
    Zhang LF, Thomas BG. State of the art in evaluation and control of steel cleanliness. Trans Iron Steel Inst Jpn. 2003;43(3):271.CrossRefGoogle Scholar
  5. [5]
    Xu ZB, Gammal EL. Influence of inclusion content and morphology mechanical properties of steel. J Iron Steel Res. 1994;6(4):18.Google Scholar
  6. [6]
    Zhou Z, Hua Y, Xu C, Li J, Li Y, Gong K, Ru JJ, Xiong L. Preparation of ferrotitanium from ilmenite by electrolysis-assisted calciothermic reduction in CaCl2–NaCl molten salt. JOM. 2016;68(2):532.CrossRefGoogle Scholar
  7. [7]
    Wu Y, Zou ZG, Li XM. Combustion synthesis of fine TiFe series alloy powder by magnesothermic reduction of ilmenite. Rare Met. 2006;25(s1):280.CrossRefGoogle Scholar
  8. [8]
    Zhadkevich ML, Biktagirov FK, Shapovalov VA, Ignatov AP, Gnatushenko AV. Application of electroslag melting for production of ferroalloys from mineral raw material. Sovrem Electrometall. 2005;1:12.Google Scholar
  9. [9]
    Li CH, He J, Zhang Z, Yang B, Leng HY, Lu XG, Li ZL, Wu Z, Wang HB. Preparation of TiFe based alloys melted by CaO crucible and its hydrogen storage properties. J Alloys Compd. 2015;618(5):679.CrossRefGoogle Scholar
  10. [10]
    Cui N, Wang XP, Kong FT, Chen YY, Zhou HT. Microstructure and properties of a beta-solidifying TiAl-based alloy with different refiners. Rare Met. 2016;35(1):42.CrossRefGoogle Scholar
  11. [11]
    Han JC, Xiao SL, Tian J, Chen YY, Xu LJ, Wang XP, Jia Y, Cao SZ. Microstructure characterization and tensile properties of a Ni-containing TiAl-based alloy with heat treatment. Rare Met. 2016;35(1):26.CrossRefGoogle Scholar
  12. [12]
    Cheng XX, Qu SJ, Feng AH, Shen J. Recent advances in size effect of lamellar colony and lamellar spacing in intermetallic titanium aluminides. Chin J Rare Met. 2016;40(4):393.Google Scholar
  13. [13]
    Deng GZ, Wang XF. Methods of preparing high grade titania feedstock from Panzhihua titanium concentrate. Iron Steel Vanadium Titan. 2002;23(4):14.Google Scholar
  14. [14]
    Chumarev VM, Dubrovskii AY, Pazdnikov IP, Shurygin YY, Sel’Menskikh NI. Technological possibilities of manufacturing high-grade ferrotitanium from crude ore. Russ Metall. 2008;2008(6):459.CrossRefGoogle Scholar
  15. [15]
    Dou ZH, Zhang TA, Zhang HB, Zhang ZQ, Niu LP, He JC. Basic research on preparation of high titanium ferroalloy with low oxygen content by thermit reduction. Chin J Process Eng. 2010;10(6):1119.Google Scholar
  16. [16]
    Dou ZH, Zhang TA, Zhang HB, Zhang ZQ, Niu LP, Yao YL, He JC. Preparation of high titanium ferrous with low oxygen content by thermit reduction-SHS. J Cent South Univ Technol, Nat Sci (Chin Ed). 2012;41(5):899.Google Scholar
  17. [17]
    Arthur DP, Gnnar E, Antonio RS. Calculation of sulfide capacities of multi-component slags. Metall Mater Trans B. 1993;24(5):817.CrossRefGoogle Scholar
  18. [18]
    Choi JY, Kim DJ, Lee HG. Reaction kinetics of desulfurization of molten pig iron using CaO–SiO2–Al2O3–Na2O slag systems. ISIJ Int. 2001;41(3):216.CrossRefGoogle Scholar
  19. [19]
    Wei YW, Li N, Chen FY. Effect of Fe2O3 addition in MgO–CaO refractory on desulfurization of liquid iron. J Iron Steel Res Int. 2003;10(4):4.Google Scholar
  20. [20]
    Wang HM, Zhang TW, Zhu H, Li GR, Yuan YQ, Wang JH. Effect of B2O3 on melting temperature, viscosity and desulfurization capacity of CaO-based refining flux. ISIJ Int. 2011;51(5):702.CrossRefGoogle Scholar
  21. [21]
    Lee J, Morita K. Dynamic interfacial phenomena between gas, liquid iron and solid CaO during desulfurization. ISIJ Int. 2004;44(2):235.CrossRefGoogle Scholar
  22. [22]
    Lindström D, Nortier P, Du S. Functions of Mg and Mg–CaO mixtures in hot metal desulfurization. Steel Res Int. 2014;85(1):76.CrossRefGoogle Scholar
  23. [23]
    Niedringhaus JC, Fruehan RJ. Reaction mechanism for the CaO–Al and CaO–CaF2 desulfurization of carbon-saturated iron. Metall Mater Trans B. 1988;19(2):261.CrossRefGoogle Scholar
  24. [24]
    Gao YH, Bian LT. Desulfurization characteristics of CaO–SiO2–BaO–CaF2–Al2O3–MgO refining slag. J Iron Steel Res Int. 2005;12(5):1.Google Scholar
  25. [25]
    Jerebtsov DA, Mikhailov GG. Phase diagram of CaO–Al2O3 system. Ceram Int. 2001;27(1):25.CrossRefGoogle Scholar
  26. [26]
    Duffy JA, Ingram MD, Sommerville ID. Acid-base properties of molten oxides and metallurgical slags. J Chem Soc Faraday Trans. 1978;74(4):1410.CrossRefGoogle Scholar
  27. [27]
    Yang YD, Mclean A, Sommerville ID, Poveromo JJ. The correlation of alkali capacity with optical basicity of blast furnace slags. I&SM. 2000;27(10):103.Google Scholar
  28. [28]
    Zhang GH, Kuo-Chih C, Pal U. Estimation of sulfide capacities of multicomponent slags using optical basicity. ISIJ Int. 2013;53(5):761.CrossRefGoogle Scholar
  29. [29]
    Zhao HM, Wang XH, Xie B. Effect of components on desulfurization of an Al2O3–CaO base premolten slag containing SrO. J Univ Sci Technol Beijing. 2005;12(3):225.Google Scholar
  30. [30]
    Patsiogiannis F, Pal UB, Bogan RS. Laboratory scale refining studies on low carbon aluminum killed steels using synthetic fluxes. ISIJ Int. 1994;34(2):140.CrossRefGoogle Scholar

Copyright information

© The Nonferrous Metals Society of China and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of MetallurgyNortheastern UniversityShenyangChina
  2. 2.Key Laboratory of Ecological Utilization of Multi-Metal Intergrown Ores of Ministry of Education, Northeastern UniversityShenyangChina

Personalised recommendations