洁净钢精炼钙处理技术探析

doi:10.13228/j.boyuan.issn0449-749x.20230054

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Abstract Aiming at a better understanding on calcium treatment technology, the physical and chemical properties of metal calcium were summarized, the modification mechanisms of calcium treatment and the related thermodynamic data based on the study results in literature. According to the studies and industrial practice of the present authors, the problems of calcium treatment were discussed, and the principle and control standard for calcium treatment were recommended. Due to the evolution of inclusions in steel during refining process, the object inclusions for calcium treatment change from Al deoxidation products(Al₂O₃ inclusions) to their evolution products (including MgO·Al₂O₃ inclusions and CaO-Al₂O₃-MgO system inclusions, etc.). Although calcium treatment technology can modify the inclusions in steel and improve the castability of steels, it generally declines the removal efficiency of inclusions, enlarges the frequency of macro-inclusions, and leads to reoxidation of liquid steel and corrosion of refractories. Therefore, calcium treatment pollutes liquid steel in most cases. If there are no special requirement on inclusion modification, and no problem with castability of steels, calcium treatment is not recommended to perform. If in need, Ca should be added as little as possible for calcium treatment, and it should be carried out after refining. Accurate measurement of dissolved [Ca] in steel is still a challenge, and large deviations are existed in the thermodynamic data of Ca. In addition, the yield of Ca is unstable as well, so it is difficult to achieve precise control of calcium treatment. Since the measurement of dissolved [Ca] is avoided, and thermodynamic data are not needed, the standard of w(T[Ca])/w(T[O]) can be practical in industry. In order to improve the castability of low-oxygen and low-sulfur steels, the Ca content can be controlled referring to the recommended value (0.91-1.25) of w(T[Ca])/w(T[O]). Nevertheless, the lowest Ca addition is still suggested for higher steel cleanliness. Also, calcium treatment cannot solve all the castability problems due to the various influential factors.

Key words： calcium treatment clean steel inclusion liquid phase castability

Received: 08 February 2022

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	DENG Zhiyin
	ZHU Miaoyong

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DENG Zhiyin,ZHU Miaoyong. Discussion on calcium treatment technology for clean steel refining[J]. Iron and Steel, 2023, 58(9): 104-115.

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http://www.chinamet.cn/Jweb_gt/EN/10.13228/j.boyuan.issn0449-749x.20230054 OR http://www.chinamet.cn/Jweb_gt/EN/Y2023/V58/I9/104

[1] WATTS O P. Iron and calcium[J]. Journal of the American Chemical Society, 1906, 28(9):1152.
[2] GOLDSCHMIDT H. Neue thermitreaktionen[J]. Zeitschrift für Elektrochemie und Angewandte Physikalische Chemie, 1908, 14(35):558.
[3] GEILENKIRCHEN T. Herstellung dichter Güsse durch desoxydierende Zuschläge[J]. Stahl und Eisen, 1908, 28:592.
[4] ZIELER W. Die nichtmetallischen Einschlüsse im Stahl, ihre Verteilung im Guβblock und ihre Beeinflussung durch Desoxydationsmittel, insbesondere durch Zirkon, Natrium und Kalzium[J]. Archiv für das Eisenhüttenwesen, 1931, 5(6):299.
[5] 音谷登平,形浦安治.钙洁净钢[M].刘新华,韩郁文译.北京:冶金工业出版社,1994.(OTOTANI T, KATAURA Y. Calcium Clean Steel[M]. LIU X H, HAN Y W, Translate. Beijing:Metallurgical Industry Press, 1994.)
[6] YE G Z, JONSSON P, LUND T. Thermodynamics and kinetics of the modification of Al₂O₃ inclusions[J]. ISIJ International, 1996, 36(s):105.
[7] ITO Y, SUDA M, KATO Y, et al. Kinetics of shape control of alumina inclusions with calcium treatment in line pipe steel for sour service[J]. ISIJ International, 1996, 36(s1):148.
[8] 伊藤陽一,奈良正功,加藤嘉英,等.カルシウムの二段添加処理によるアルミナ介在物の形態制御[J].鉄と鋼,2007,93(5):355.(ITO Y,NARA S,KATO Y,et al. Shape control of alumina inclusions by double calcium addition treatment[J]. Tetsu-to-Hagané,2007,93(5):355.)
[9] LIND M, HOLAPPA L. Transformation of alumina inclusions by calcium treatment[J]. Metallurgical and Materials Transactions B, 2010, 41(2):359.
[10] 刘建华,吴华杰,包燕平,等.高级别管线钢钙处理效果评价标准[J].北京科技大学学报,2010,32(3):312.(LIU J H, WU H J, BAO Y P, et al. Evaluation standard of calcium treatment in high grade pipeline steel[J]. Journal of University of Science and Technology Beijing, 2010, 32(3):312.)
[11] YANG S, WANG Q, ZHANG L, et al. Formation and modification of MgO·Al₂O₃-based inclusions in alloy steels[J]. Metallurgical and Materials Transactions B, 2012, 43(4):731.
[12] DENG Z Y, ZHU M Y. A new double calcium treatment method for clean steel refining[J]. Steel Research International, 2013, 84(6):519.
[13] 张彩军,蔡开科,袁伟霞.管线钢硫化物夹杂及钙处理效果研究[J].钢铁,2006,41(8):31.(ZHANG C J, CAI K K, YUAN W X. Study on sulfide inclusions and effect of calcium treatment for pipeline steel[J]. Iron and Steel, 2006, 41(8):21.)
[14] 韩志军,林平,刘浏,等.20CrMnTiH1齿轮钢钙处理热力学[J].钢铁,2007,42(9):32.(HAN Z J, LIN P, LIU L, et al. Thermodynamics of calcium treatment for 20CrMnTiH1[J]. Iron and Steel, 2007, 42(9):32.)
[15] YANG W, ZHANG L, WANG X, et al. Characteristics of inclusions in low carbon Al-killed steel during ladle furnace refining and calcium treatment[J]. ISIJ International, 2013, 53(8):1401.
[16] CHEN G J, HE S P, GUO Y T, et al. Optimization of calcium addition to high-strength low-alloy steels[J]. Journal of Iron and Steel Research International, 2015, 22(7):590.
[17] 罗磊,田志红,赵长亮,等.CSP生产低碳铝镇静钢的钙处理[J].钢铁研究学报,2015,27(4):29.(LUO L, TIAN Z H, ZHAO C L, et al. Calcium treatment of low carbon aluminum killed steel produced by CSP process[J]. Journal of Iron and Steel Research, 2015, 27(4):29.)
[18] 马志飞,孙彦辉,孙赛阳,等.CSP生产低碳高铝钢钙处理与可浇性的控制[J].钢铁研究学报,2014,26(6):17.(MA Z F, SUN Y H, SUN S Y, et al. Calcium treatment and control of castability in low carbon aluminum killed steel produced by CSP process[J]. Journal of Iron and Steel Research, 2014, 26(6):17.)
[19] 孙波,张良明,吴耀光,等.马钢SPHC钢钙处理的热力学分析[J].中国冶金,2017,27(1):50.(SUN B, ZHANG L M, WU Y G, et al. Thermodynamic analysis of calcium treatment for SPHC steel in Masteel[J]. China Metallurgy, 2017, 27(1):50.)
[20] ABRAHAM S, BODNAR R, RAINES J, et al. Inclusion engineering and metallurgy of calcium treatment[J]. Journal of Iron and Steel Research International, 2018, 25(2):133.
[21] 张立峰.钢中非金属夹杂物几个需要深入研究的课题[J].炼钢,2016,32(4):1.(ZHANG L F. Several important scientific research points of non-metallic inclusions in steel[J]. Steelmaking, 2016, 32(4):1.)
[22] SPONSELLER D L, FLINN R A. The solubility of calcium in liquid iron and third-element interaction effects[J]. Transactions of the Metallurgical Society of AIME, 1964, 230:876.
[23] 宮下芳雄,西川勝彦.溶鉄のCa脱酸について[J].鉄と鋼,1971,57(13):1969.(MIYASHITA Y,NISHIKAWA K. The deoxidation of liquid iron with calcium[J]. Tetsu-to-Hagané,1971,57(13):1969.)
[24] 草川隆次,田川寿俊,神尾寛.溶鉄および鉄系合金中へのCaの溶解度[J].鉄と鋼,1972,58(11):S378.(KUSAKAWA T,TAGAWA H,HIROSHI K. Solubility of Ca in molten iron and molten iron-based alloys[J]. Tetsu-to-Hagané,972,58(11):S378.)
[25] SCHÜRMANN E, SCHMID R. Dampfdruckgleichungen und thermodynamische Daten des reinen flüssigen und festen (β)-calciums[J]. Archiv für das Eisenhüttenwesen, 1975, 46(12):772.
[26] 音谷登平,形浦安治,出川通.CaO坩塙による溶鉄と溶融鉄合金のカルシウム脱酸およびアルミニウム脱硫[J].鉄と鋼,1975,61(9):2167.(OTOTANI T,KATAURA Y,DEGAWA T. Calcium deoxidation and aluminium desulphurization of liquid iron and liquid iron alloy with a lime crucible[J]. Tetsu-to-Hagané,1975,61(9):2167.)
[27] FUJIWARA H, TANO M, YAMAMOTO K, et al. Solubility with lime and activity of calcium in molten iron in and thermodynamics of calcium containing equilibrium iron melts[J]. ISIJ International, 1995, 35(9):1063.
[28] KÖHLER M, ENGELL H J, JANKE D. Solubility of calcium in Fe-Ca-X_i melts[J]. Steel Research, 1985, 56(8):419.
[29] BERG M, LEE J, SICHEN D. Study on the equilibrium between liquid iron and calcium vapor[J]. Metallurgical and Materials Transactions B, 2017, 48(3):1715.
[30] DENG Z Y, ZHU M Y, ZHOU Y L, et al. Attachment of alumina on the wall of submerged entry nozzle during continuous casting of Al-killed steel[J]. Metallurgical and Materials Transactions B, 2016, 47(3):2015.
[31] JIANG M, WANG X, CHEN B, et al. Laboratory study on evolution mechanisms of non-metallic inclusions in high strength alloyed steel refined by high basicity slag[J]. ISIJ International, 2010, 50(1):95.
[32] DENG Z Y, ZHU M Y. Evolution mechanism of non-metallic inclusions in Al-killed alloyed steel during secondary refining process[J]. ISIJ International, 2013, 53(3):450.
[33] DENG Z Y, LIU Z H, ZHU M Y, et al. Formation, evolution and removal of MgO·Al₂O₃ spinel inclusions in steel[J]. ISIJ International, 2021, 61(1):1.
[34] 朱苗勇, 邓志银. 钢精炼过程非金属夹杂物演变与控制[J]. 金属学报, 2022, 58(1):28.(ZHU M Y, DENG Z Y. Evolution and control of non-metallic inclusions in steel during secondary refining process[J]. Acta Metallurgica Sinica, 2022, 58(1):28.)
[35] VERMA N, PISTORIUS P C, FRUEHAN R J, et al. Transient inclusion evolution during modification of alumina inclusions by calcium in liquid steel:Part II. Results and discussion[J]. Metallurgical and Materials Transactions B, 2011, 42(2):720.
[36] VERMA N, PISTORIUS P C, FRUEHAN R J, et al. Calcium modification of spinel inclusions in aluminum-killed steel:Reaction steps[J]. Metallurgical and Materials Transactions B, 2012, 43(5):830.
[37] YANG W, GUO C, LI C, et al. Transformation of inclusions in pipeline steels during solidification and cooling[J]. Metallurgical and Materials Transactions B, 2017, 48(5):2267.
[38] The Japan Society for the Promotion of Science. The 19th Committee on Steelmaking. Steelmaking Data Sourcebook[M]. New York:Gordon and Breach Science Publishers,1988.
[39] 伊東裕恭,日野光兀,萬谷志郎.溶鉄のCa脱酸平衡[J].鉄と鋼,1997,83(11):695.(ITOH H,HINO M,BAN-YA S. Deoxidation equilibrium of calcium in liquid iron[J]. Tetsu-to-Hagané,1997,83(11):695.)
[40] HINO M, ITO K. Thermodynamic Data for Steelmaking[M]. Sendai:Tohoku University Press, 2010.
[41] FAULRING G M, FARRELL J W, HILTY D C. Steel flow through nozzles:Influence of calcium[J]. Ironmaking and Steelmaking, 1980, 7(2):14.
[42] 高海潮,刘茂林,张良明,等.CSP连铸浸入式水口结瘤案例研究[J].钢铁,2005,40(11):21.(GAO H C, LIU M L, ZHANG L M, et al. Case study of submerged entry nozzle clogging on CSP line[J]. Iron and Steel, 2005, 40(11):21.)
[43] DENG Z Y, CHEN L, SONG G D, et al. Formation and evolution of non-metallic inclusions in Ti-bearing Al-killed steel during secondary refining process[J]. Metallurgical and Materials Transactions B, 2020, 51(1):173.
[44] HOU Z W, JIANG M, YANG E J, et al. Effect of calcium treatment on control of non-metallic inclusions in high quality low oxygen special steel[C]//7th International Congress on Science and Technology of Steelmaking (ICS 2018). Venice:Associazione Italiana di Metallurgia, 2018:ICS 063.
[45] 秦正丰,薛正良,李金波,等.钙处理钢中大型球状及棒状夹杂的成因[J].钢铁,2020,55(5):31.(QIN Z F, XUE Z L, LI J B, et al. Origin of large spherical or bar-shaped inclusions in calcium treated steel[J]. Iron and Steel, 2020, 55(5):31.)
[46] 王新华,李金柱,姜敏,等.高端重要用途特殊钢非金属夹杂物控制技术研究[J].炼钢,2017,33(2):50.(WANG X H, LI J Z, JIANG M, et al. Investigation on technology of non-metallic inclusion control for high grade special steels of important uses[J]. Steelmaking, 2017, 33(2):50.)
[47] 王新华,李秀刚,李强,等.X80管线钢板中条串状CaO-Al₂O₃系非金属夹杂物的控制[J].金属学报,2013,49(5):553.(WANG X H, LI X G, LI Q, et al. Control of string shaped non-metallic inclusions of CaO-Al₂O₃ system in X80 pipeline steel plates[J]. Acta Metallurgica Sinica, 2013, 49(5):553.)
[48] 邓志银,朱苗勇,钟保军,等.超低氧洁净钢的精炼渣碱度选择[C]//第十七届全国炼钢学术会议论文集.杭州:中国金属学会炼钢分会,2013:400.(DENG Z Y, ZHU M Y, ZHONG B J, et al. Basicity choice of refining slag for ultra-low oxygen clean steels[C]//Proceedings of the 17th CSM Conference on Steelmaking. Hangzhou:Steelmaking Branch, The Chinese Society for Metals, 2013:400.)
[49] 邓志银,周业连,朱苗勇.铝镇静钢中夹杂物形态对其去除的影响[J].钢铁,2018, 53(1):34.(DENG Z Y, ZHOU Y L, ZHU M Y. Effect of state of inclusions on removal in Al-killed liquid steel[J]. Iron and Steel, 2018, 53(1):34.)
[50] REIS B H, BIELEFELDT W V, VILELA A C F. Efficiency of inclusion absorption by slags during secondary refining of steel[J]. ISIJ International, 2014, 54(7):1584.
[51] XU J, HUANG F, WANG X, et al. Investigation on the removal efficiency of inclusions in Al-killed liquid steel in different refining processes[J]. Ironmaking and Steelmaking, 2017, 44(6):455.
[52] 周业连,邓志银,朱苗勇.固/液态夹杂物穿过钢渣界面的分离机理研究[J].过程工程学报,2018,18(1):96.(ZHOU Y L, DENG Z Y, ZHU M Y. Separation mechanism of solid/liquid inclusions transfer at steel-slag interface[J]. The Chinese Journal of Process Engineering,2018, 18(1):96.
[53] 周杨鹏,杨健,鲁欣武,等.钙处理低合金高强钢连铸过程中塞棒侵蚀机理及其改进[J].炼钢,2021,37(3):44.(ZHOU Y P, YANG J, LU X W, et al. Mechanism and improvement of erosion of stopper rod during continuous casting process of high-strength low-alloy steel after calcium treatment[J]. Steelmaking, 2021, 37(3):44.)
[54] 王晗,石干.钙处理钢用滑板的化学侵蚀机理及研究现状[J].河北冶金,2006(3):44.(WANG H, SHI G. Chemical erosion mechanism of slide board in casting of Ca-treated steel and research situation about it[J]. Hebei Metallurgy, 2006(3):44.)
[55] DENG Z Y, ZHU M Y, ZHONG B J, et al. Attachment of liquid calcium aluminate inclusions on inner wall of submerged entry nozzle during continuous casting of calcium-treated steel[J]. ISIJ International, 2014, 54(12):2813.
[56] TODOROKI H, SHIGA N. Classification of clogging behavior of CC immersion nozzle in various stainless steels[C]//4th International Congress on The Science and Technology of Steelmaking (ICS2008). Gifu:ISIJ, 2008:121.
[57] GHOSH A. Thermodynamic evaluation of formation of oxide-sulfide duplex inclusions in steel[J]. ISIJ International, 2008, 48(11):1552.
[58] GELDENHUIS J M A, PISTORIUS P C. Minimisation of calcium additions to low carbon steel grades[J]. Ironmaking and Steelmaking, 2000, 27(6):442.