Development and prospects of molten steel deoxidation in steelmaking process

Abstract

In the long traditional process of steelmaking, excess oxygen is blown into the converter, and alloying elements are used for deoxidation. This inevitably results in excessive deoxidation of products remaining within the steel liquid, affecting the cleanliness of the steel. With the increasing requirements for steel performance, reducing the oxygen content in the steel liquid and ensuring its high cleanliness is necessary. After more than a hundred years of development, the total oxygen content in steel has been reduced from approximately 100 × 10⁻⁶ to approximately 10 × 10⁻⁶, and it can be controlled below 5 × 10⁻⁶ in some steel grades. A relatively stable and mature deoxidation technology has been formed, but further reducing the oxygen content in steel is no longer significant for improving steel quality. Our research team developed a deoxidation technology for bearing steel by optimizing the entire conventional process. The technology combines silicon–manganese predeoxidation, ladle furnace diffusion deoxidation, and vacuum final deoxidation. We successfully conducted industrial experiments and produced interstitial-free steel with natural decarbonization predeoxidation. Non-aluminum deoxidation was found to control the oxygen content in bearing steel to between 4 × 10⁻⁶ and 8 × 10⁻⁶, altering the type of inclusions, eliminating large particle Ds-type inclusions, improving the flowability of the steel liquid, and deriving a higher fatigue life. The natural decarbonization predeoxidation of interstitial-free steel reduced aluminum consumption and production costs and significantly improved the quality of cast billets.

Keywords

steel deoxidation / deoxidizer / metallurgical equipment / bearing steel / IF steel

References

[[1]] Yin RY. Review on the study of metallurgical process engineering. Int. J. Miner. Metall. Mater., 2021, 28(8): 1253,

[[2]] Wang YJ, Zuo HB, Zhao J. Recent progress and development of ironmaking in China as of 2019: An overview. Iron-making Steelmaking, 2020, 47(6): 640,

[[3]] Mousa E. Modern blast furnace ironmaking technology: Potentials to meet the demand of high hot metal production and lower energy consumption. Metall. Mater. Eng., 2019, 25(2): 69,

[[4]] Naito M, Takeda K, Matsui Y. Ironmaking technology for the last 100 years: Deployment to advanced technologies from introduction of technological know-how, and evolution to next-generation process. ISIJ Int., 2015, 55(1): 7,

[[5]] Tang ZD, Xiao HX, Sun YS, Gao P, Zhang YH. Exploration of hydrogen-based suspension magnetization roasting for refractory iron ore towards a carbon-neutral future: A pilot-scale study. Int. J. Hydrogen Energy, 2022, 47(33): 15074,

[[6]] Lv M, Zhu R, Yang LZ. High efficiency dephosphorization by mixed injection during steelmaking process. Steel Res. Int., 2019, 90: 1800454,

[[7]] Liu C, Tang LX, Liu JY, Tang ZH. A dynamic analytics method based on multistage modeling for a BOF steelmaking process. IEEE Trans. Autom. Sci. Eng., 2019, 16(3): 1097,

[[8]] Guo J, Cheng SS, Guo HJ. Thermodynamics and industrial trial on increasing the carbon content at the BOF endpoint to produce ultra-low carbon IF steel by BOF–RH–CSP process. High Temp. Mater. Process., 2019, 38(2019): 822,

[[9]] Choudhary SK, Ghosh A. Mathematical model for prediction of composition of inclusions formed during solidification of liquid steel. ISIJ Int., 2009, 49(12): 1819,

[[10]] Dong PY, Zheng SG, Zhu MY. Numerical study on gas–metal–slag interaction with single-flow postcombustion oxygen lance in the steelmaking process of a top-blown converter. JOM, 2022, 74(4): 1509,

[[11]] Holappa L. Historical overview on the development of converter steelmaking from Bessemer to modern practices and future outlook. Miner. Process. Extr. Metall., 2019, 128(1–2): 3

[[12]] Ji YQ, Liu CY, Yu HX, Deng XX, Huang FX, Wang XH. Oxygen transfer phenomenon between slag and molten steel for production of IF steel. J. Iron Steel Res. Int., 2020, 27(4): 402,

[[13]] Deng ZY, Zhu MY, Du SC. Effect of refractory on non-metallic inclusions in Al-killed steel. Metall. Mater. Trans. B, 2016, 47(5): 3158,

[[14]] Yin HB, Shibata H, Emi T, Suzuki M. “In-situ” observation of collision, agglomeration and cluster formation of alumina inclusion particles on steel melts. ISIJ Int., 1997, 37(10): 936,

[[15]] A. Mehralizadeh, S. Reza Shabanian, and G. Bakeri, Effect of modified surfaces on bubble dynamics and pool boiling heat transfer enhancement: A review, Therm. Sci. Eng. Prog., 15(2020), art. No. 100451.

[[16]] Chen RY, Yeun WYD. Review of the high-temperature oxidation of iron and carbon steels in air or oxygen. Oxid. Met., 2003, 59(5–6): 433,

[[17]] Zhang GH, Chou KC. Deoxidation of molten steel by aluminum. J. Iron Steel Res. Int., 2015, 22(10): 905,

[[18]] W. Xiao, M. Wang, and Y.P. Bao, The research of low-oxygen control and oxygen behavior during RH process in silicon-deoxidization bearing steel, Metal:, 9(2019), No. 8, art. No. 812.

[[19]] Huff GF, Bailey GR, Richards JH. Sampling of liquid steel for dissolved oxygen. JOM, 1952, 4(11): 1162,

[[20]] Kalisz D, Migas P, Karbowniczek M, Moskal M, Hornik A. Influence of selected deoxidizers on chemical composition of molten inclusions in liquid steel. J. Mater. Eng. Perform., 2020, 29(3): 1479,

[[21]] Shi CB, Chen XC, Guo HJ, Zhu ZJ, Ren H. Assessment of oxygen control and its effect on inclusion characteristics during electroslag remelting of die steel. Steel Res. Int., 2012, 83(5): 472,

[[22]] Alley ES, Neu RW. Microstructure-sensitive modeling of rolling contact fatigue. Int. J. Fatigue, 2010, 32(5): 841,

[[23]] Wang W, Liu HJ, Zhu CC, Wei P, Wu W. Micromechanical analysis of gear fatigue-ratcheting damage considering the phase state and inclusion. Tribol. Int., 2019, 136: 182,

[[24]] Z.M. Ma, S.Z. Dong, H. Zhu, et al., Research on the failure mechanism of the high-speed train bearing steel under static load failure, Eng. Fail. Anal., 137(2022), art. No. 106169.

[[25]] Gubenko SI. Plasticity origin of heterophase inclusions at steel forming. Steel Transi, 2020, 50(10): 730,

[[26]] Xiao W, Bao YP, Gu C, et al.. Ultrahigh cycle fatigue fracture mechanism of high-quality bearing steel obtained through different deoxidation methods. Int. J. Miner. Metall. Mater., 2021, 28(5): 804,

[[27]] Gu C, Lyu ZY, Hu Q, Bao YP. Investigation of the structural, electronic and mechanical properties of CaO–SiO₂ compound particles in steel based on density functional theory. Int. J. Miner. Metall. Mater., 2023, 30(4): 744,

[[28]] Wang L, Song B, Yang ZB, Cui XK, Liu Z, Cheng WS, Mao JH. Effects of Mg and La on the evolution of inclusions and microstructure in Ca–Ti treated steel. Int. J. Miner. Metall Mater., 2021, 28(12): 1940,

[[29]] Cao L, Zhu LG, Guo ZH. Research status of inclusions in bearing steel and discussion on non-alloy deoxidation process. J. Iron Steel Res. Int., 2023, 30(1): 1,

[[30]] Lange KW. Thermodynamic and kinetic aspects of secondary steelmaking processes. Int. Mater. Rev., 1988, 33(1): 53,

[[31]] Rimbert N, Claudotte L, Gardin P, Lehmann J. Modeling the dynamics of precipitation and agglomeration of oxide inclusions in liquid steel. Ind. Eng. Chem. Res., 2014, 53(20): 8630,

[[32]] Jansto SG. MicroNiobium alloy approach in medium and high carbon steel bar, plate and sheet products. Metall. Mater. Trans. B, 2014, 45(2): 438,

[[33]] Gokcen NA, Chipman J. Silicon-oxygen equilibrium in liquid iron. JOM, 1952, 4(2): 171,

[[34]] Gokcen NA, Chipman J. Aluminum–oxygen equilibrium in liquid iron. JOM, 1953, 5(2): 173,

[[35]] Semura K, Matsuura H. Past development and future prospects of secondary refining technology. Tetsu-to-Hagane, 2014, 100(4): 456,

[[36]] Nakanishi K, Szekely J, Fujii T, Mihara Y, Iwaoka S. Stirring and its effect on aluminum deoxidation of steel in the ASEA-SKF furnace: Part I. Plant scale measurements and preliminary analysis. Metall. Trans. B, 1975, 6(1): 111,

[[37]] Väinólä RV, Holappa LEK, Karvonen PHJ. Modern steelmaking technology for special steels. J. Mater. Process. Technol., 1995, 53(1–2): 453,

[[38]] Fandrich R, Lüngen H, Wuppermann C. Actual review on secondary metallurgy. Rev. Met. Paris, 2008, 105(7–8): 364,

[[39]] Holappa L. On physic-chemical and technical limits in clean steel production. Steel Res. Int., 2010, 81(10): 869,

[[40]] Wang Y, Karasev A, Park JH, Jónsson PG. Non-metallic inclusions in different ferroalloys and their effect on the steel quality: A review. Metall. Mater. Trans. B, 2021, 52(5): 2892,

[[41]] Roy D, Pistorius P, Fruehan R. Effect of silicon on the desulfurization of Al-killed steels: Part II. Experimental results and plant trials. Metall. Mater. Trans. B, 2013, 44: 1095,

[[42]] C.Y. Chen, Z.H. Jiang, Y. Li, et al., State of the art in the control of inclusions in tire cord steels and saw wire steels–A review, Steel Res. Int., 90(2019), No. 8, art. No. 180054.

[[43]] Suler B, Burja J, Medved J. Modification of non-metallic inclusions with rare-earth metals in 50CrMoV13-1 steel. Mater. Tehnol., 2019, 53(3): 441,

[[44]] Le Coze J. Purification of iron and steels a continuous effort from 2000 BC to AD 2000. Mater. Trans. JIM, 2000, 41(1): 219,

[[45]] Leach J. The application of vacuum to steel making. Vacuum, 1969, 19(4): 155,

[[46]] Tix A. Production-scale vacuum steel degassing. JOM, 1956, 8(4): 420,

[[47]] Tutarova VD, Shapovalov AN, Kalitaev AN. Removal of hydrogen in the vacuum treatment of steel. Steel Transl., 2017, 47(3): 153,

[[48]] Bunshah RF. History and current status of vacuum metallurgy. J. Vac. Sci. Technol. A, 1994, 12(4): 936,

[[49]] Wei JH, Yu NW, Fan YY, Yang SL, Ma JC, Zhu DP. Study on flow and mixing characteristics of molten steel in RH and RH-KTB refining processes. J. Shanghai Univ., 2002, 6(2): 167,

[[50]] Nishioka T, Emoto K. On the ASEA-SKF process. Tetsu-to-Hagane, 1974, 60(12): 1661,

[[51]] Pehlke RD, Fuwa T. Control of sulphur in liquid iron and steel. Int. Met. Rev., 1985, 30(1): 125,

[[52]] Emi T. Steelmaking technology for the last 100 years: Toward highly efficient mass production systems for high quality steels. ISIJ Int., 2015, 55(1): 36,

[[53]] Huang HG, Yan M, Sun JN, Du FS. Heat transfer of calcium cored wires and CFD simulation on flow and mixing efficiency in the argon-stirred ladle. Ironmaking Steelmaking, 2018, 45(7): 626,

[[54]] Hu Y, Chen WQ, Wan CJ, Wang FJ, Han HB. Effect of deoxidation process on inclusion and fatigue performance of spring steel for automobile suspension. Metall. Mater. Trans. B, 2018, 49(2): 569,

[[55]] Gu C, Bao YP, Gan P, Lian JH, Münstermann S. An experimental study on the impact of deoxidation methods on the fatigue properties of bearing steels. Steel Res. Int., 2018, 89: 1800129,

[[56]] Deng ZY, Zhu MY. Deoxidation mechanism of Al-killed steel during industrial refining process. ISIJ Int., 2014, 54(7): 1498,

[[57]] D.L. You, C. Bernhard, A. Viertauer, and B. Linzer, Simulation of the refining process of ultra-low carbon (ULC) steel, Crystals, 11(2021), No. 8, art. No. 893.

[[58]] Way LD. Cleanness, castability, and surface quality of form-able sheet steels. Mater. Sci. Technol., 2001, 17(10): 1175,

[[59]] Choudhary SK, Chandra S, Ghosh A. Prediction of deoxidation and inclusion precipitation in semikilled steel. Metall. Mater. Trans. B, 2005, 36(1): 59,

[[60]] Goto H, Miyazawa KI. Reoxidation behavior of molten steel in non-killed and Al-killed steels. ISIJ Int., 1998, 38(3): 256,

[[61]] Ohta H, Suito H. Activities in CaO-MgO-Al₂O₃ slags and deoxidation equilibria of Al, Mg, and Ca. ISIJ Int., 1996, 36(8): 983,

[[62]] Furukawa T, Saito N, Nakashima K. Evaluation of interfacial energy between molten Fe and Fe–18%Cr–9%Ni alloy and non-metallic inclusion-type oxides. ISIJ Int., 2021, 61(9): 2381,

[[63]] Y.Y. Xiao, G.C. Wang, H. Lei, and S. Sridhar, Formation pathways for MgO·Al₂O₃ inclusions in iron melt, J. Alloys Compd., 813(2020), art. No. 152243.

[[64]] Yang XM, Shi CB, Zhang M, Chai GM, Wang F. A thermodynamic model of sulfur distribution ratio between CaO–SiO₂–MgO–FeO–MnO–Al₂O₃ slags and molten steel during LF refining process based on the ion and molecule coexistence theory. Metall. Mater. Trans. B, 2011, 42(6): 1150,

[[65]] Swinnerton M. . The Influence of Slag Evolution on BOF De-phosphorization, 2005 New South Wales University of Wollongong 107 [Dissertation]

[[66]] Li YH, Bao YP, Wang M, Wang R, Tang DC. Influence of process conditions during Ruhrstahl–Hereaeus refining process and effect of vacuum degassing on carbon removal to ultra-low levels. Ironmaking Steelmaking, 2015, 42(5): 366,

[[67]] Li HB, Lu PC, Feng H, Zhang PF, Zhang SC, Jiang ZH. Influence mechanism of crucible materials on cleanliness and inclusion characteristics of high-nitrogen stainless bearing steel during vacuum carbon deoxidation. Metall. Mater. Trans. B, 2023, 54(3): 1099,

[[68]] Zhu L, Al-Sakeeri A, Lenrick F, et al.. Surface chemistry and diffusion of trace and alloying elements during in vacuum thermal deoxidation of stainless steel. Surf. Interface Anal., 2022, 54(2): 99,

[[69]] Yuan S, Pal UB, Chou KC. Modeling and scaleup of galvanic deoxidation of molten metals using solid electrolyte cells. J. Am. Ceram. Soc., 1996, 79(3): 641,

[[70]] Oberg KE, Friedman LM, Boorstein WM, Rapp RA. Electrochemical deoxidation of induction-stirred copper melts. Metall. Trans., 1973, 4(1): 75,

[[71]] Iwase M, Tanida M, McLean A, Mori T. Electronically driven transport of oxygen from liquid iron to CO + CO₂ gas mixtures through stabilized zirconia. Metall. Trans. B, 1981, 12(3): 517,

[[72]] Yuan S, Pal U, Chou KC. Deoxidation of molten metals by short circuiting yttria-stabilized zirconia electrolyte cell. J. Electrochem. Soc., 1994, 141(2): 467,

[[73]] Kong L, Ouchi T, Zheng CY, Okabe T. Electrochemical deoxidation of titanium scrap in MgCl₂–HoCl₃ system. J. Electrochem. Soc., 2019, 166: E429,

[[74]] Li JJ, Kobayashi Y. A new design of oxygen sensor for electromotive force measurement and electrochemical deoxidation by using oxygen pump. ISIJ Int., 2020, 60(6): 1135,

[[75]] Makarov MA, Aleksandrov AA, Dashevskii VY. Deep decarburization of iron-based melts. Russ. Metall. Met., 2007, 2007(2): 91,

[[76]] Dastur MN, Chipman J. Equilibrium in the reaction of hydrogen with oxygen in liquid iron. JOM, 1949, 1(8): 441,

[[77]] Xing W. . Study on Deoxidation by Hydrogen and Natural Gas in Molten Steel, 2009 Wuhan Wuhan University of Science and Technology 39 [Dissertation]

[[78]] Tung SC, McMillan ML. Automotive tribology overview of current advances and challenges for the future. Tribol. Int., 2004, 37(7): 517,

[[79]] Birat JP. Impact of steelmaking and casting technologies on processing and properties of steel. Ironmaking Steelmaking, 2001, 28(2): 152,

[[80]] Hashimoto K, Fujimatsu T, Tsunekage N, Hiraoka K, Kida K, Santos EC. Study of rolling contact fatigue of bearing steels in relation to various oxide inclusions. Mater. Des., 2011, 32(3): 1605,

[[81]] Melander A, Gustavsson A. An FEM study of driving forces of short cracks at inclusions in hard steels. Int. J. Fatigue, 1996, 18(6): 389,

[[82]] Walker PFF. Improving the reliability of highly loaded rolling bearings: The effect of upstream processing on inclusions. Mater. Sci. Technol., 2014, 30(4): 385,

[[83]] Yoon BH, Heo KH, Kim JS, Sohn HS. Improvement of steel cleanliness by controlling slag composition. Ironmaking Steelmaking, 2002, 29(3): 214,

[[84]] Kato Y, Masuda T, Kawakami K, Hashizume K. Recent improvements in cleanliness in high carbon chromium bearing steel. ISIJ Int., 1996, 36: S89,

[[85]] K. Matsuoka, T. Terabarake and K. Kameyarna, Improvement of quality of steel for bearing at JFE West Japan Works, [in] The 4th International Congress on the Science and Technology of Steelmaking, Gifu, 2008, p. 457.

[[86]] Liu CY, Huang FX, Wang XH. The effect of refining slag and refractory on inclusion transformation in extra low oxygen steels. Metall. Mater. Trans. B, 2016, 47(2): 999,

[[87]] Sorimachi K, Yamada S, Hasunuma J, Nomura H. Kawasaki Steel’s steelmaking technologies for mass production of high quality slabs. Rev. Met. Paris, 1999, 96(4): 465,

[[88]] Xu S, Brown JR, Tyson WR. Influence of residual elements on mechanical properties of two carbon steel grades. Steel Res. Int., 2006, 77(11): 825,

[[89]] Chen SF, Lei H, Wang M, Yang B, Dai LJ, Zhao Y. Two-way coupling calculation for multiphase flow and decar-burization during RH refining. Vacuum, 2019, 167: 255,

[[90]] Zhu S, Zhao QY, Li XL, Liu Y, Li TC, Zhang TA. Flow and penetration behavior of submerged side-blown gas. Int. J. Miner. Metall. Mater., 2023, 30(6): 1067,

[[91]] Takechi H. Metallurgical aspects on interstitial free sheet steel from industrial viewpoints. ISIJ Int., 1994, 34(1): 1,

[[92]] Hoile S. Processing and properties of mild interstitial free steels. Mater. Sci. Technol., 2000, 16(10): 1079,

[[93]] Yang L, Cheng GG. Characteristics of Al₂O₃, MnS, and TiN inclusions in the remelting process of bearing steel. Int. J. Miner. Metall. Mater., 2017, 24(8): 869,

[[94]] Wang ZL, Bao YP, Gu C, Xiao W, Liu Y, Huang YS. Key metallurgical technology for high-quality bearing steel production based on the nonaluminum deoxidation process. Chin. J. Eng., 2022, 44(9): 1607

[[95]] Sun HP, Mori K. Oxidation rate of aluminum in molten iron by CaO–SiO₂–Al₂O₃–FeO-MnO slag. ISIJ Int., 1996, 36: S34,

[[96]] Ling HT, Zhang LF. A mathematical model for prediction of carbon concentration during RH refining process. Metall. Mater. Trans. B, 2018, 49(6): 2963,

[[97]] Guo JL, Zhao LH, Bao YP, Gao S, Wang M. Carbon and oxygen behavior in the RH degasser with carbon powder addition. Int. J. Miner. Metall. Mater., 2019, 26(6): 681,